WO2014045940A1

WO2014045940A1 - Wholly aromatic polyester, polyester resin composition, and a polyester molded article

Info

Publication number: WO2014045940A1
Application number: PCT/JP2013/074382
Authority: WO
Inventors: 俊明横田
Original assignee: ポリプラスチックス株式会社
Priority date: 2012-09-21
Filing date: 2013-09-10
Publication date: 2014-03-27
Also published as: KR20150060712A; CN104662064A; CN104662064B; TWI537303B; JP2014062182A; JP5753143B2; KR101586760B1; TW201422660A

Abstract

A wholly aromatic polyester having excellent heat resistance and toughness, and showing optical anisotropy when molten, and a composition thereof are provided. This wholly aromatic polyester showing optical anisotropy when molten is characterized by containing, as essential constituent components, the constituent units represented by general formulae (I), (II), (III), (IV) and (V), and in that, in relation to the total constituent units, constituent units (I) are 35-75 mol%, constituent units (II) are 2-8 mol%, constituent units (III) are 8.5-31.5 mol%, constituent units (IV) are 2-8 mol%, constituent units (V) are 0.5-29.5 mol%, and constituent units (II)+(IV) are 4-10 mol%. This polyester resin composition is formed by mixing 120 parts by mass or less of an inorganic or organic filler per 100 parts by mass of said wholly aromatic polyester.

Description

Totally aromatic polyester and polyester resin composition, and polyester molded article

The present invention relates to a wholly aromatic polyester and a polyester resin composition which are excellent in heat resistance and toughness and can be produced with a normal polymerization apparatus, and a polyester molded product formed by molding them.

What is currently marketed as a wholly aromatic polyester is mainly composed of 4-hydroxybenzoic acid. However, the homopolymer of 4-hydroxybenzoic acid has a melting point higher than the decomposition point, so it is necessary to lower the melting point by copolymerizing various components.

The wholly aromatic polyester using terephthalic acid, hydroquinone, 4,4'-dihydroxybiphenyl, etc. as a copolymerization component has a high melting point of 350 ° C. or higher and is too high to be melt-processed with a general-purpose apparatus. In addition, various methods have been tried to lower the melting point of such a high melting point to a temperature that can be processed by a general-purpose melt processing machine. There is a problem that heat resistance represented by mechanical strength in the vicinity) cannot be maintained.

In order to solve these problems, Patent Documents 1 to 3 propose copolymer polyesters in which 4-hydroxybenzoic acid is combined with 6-hydroxy-2-naphthoic acid, a diol component, and a dicarboxylic acid component. .

However, the copolyesters proposed in Patent Documents 1 to 3 have low toughness and cause cracks in the molded product during molding, or have high toughness but insufficient heat resistance.

On the other hand, as a wholly aromatic polyester as described above, what shows optical anisotropy at the time of melting is called a liquid crystalline polymer, and is excellent in dimensional accuracy, vibration damping, fluidity, and less burrs are generated at the time of molding. It is useful as a material for various electronic components. In a flat connector having a lattice structure inside an outer frame typified by a CPU socket, the tendency of high heat resistance, high density, and miniaturization is remarkable, and a liquid crystalline polymer composition reinforced with glass fiber Is often adopted. However, even with a glass fiber reinforced liquid crystalline polymer composition having a certain degree of fluidity, the pitch interval between the lattice portions, which is required in recent years, is 2 mm or less, and the width of the resin portion of the lattice portion holding the terminals is 0.5 mm or less. The performance was insufficient for use as a very thin planar connector. That is, in such a planar connector having a very thin grid portion, filling the lattice portion with resin increases the filling pressure due to insufficient fluidity, resulting in the resulting planar connector. There is a problem that the amount of warp deformation increases. In order to solve this problem, it is conceivable to use a liquid crystalline polymer composition having good fluidity with a small amount of glass fiber added. However, such a composition is insufficient in strength and deforms due to reflow during mounting. The problem arises.

Therefore, the present inventors have proposed a planar connector composed of a specific composite resin composition in which the weight average length of the fibrous filler to be blended and the blending amount have a certain relationship (see Patent Document 4). . According to the invention described in Patent Document 4, a thin flat connector having excellent properties such as moldability, flatness, warp deformation, and heat resistance can be obtained.
However, due to factors such as shape changes accompanying an increase in the integration rate in recent planar connectors, particularly an increase in the number of connector pins and a further thinning of the width of the lattice portion, the invention described in Patent Document 4 addresses this. It has been found that there are cases where it cannot be completed.

Therefore, the present inventors have further proposed a planar connector composed of a specific composite resin composition in which a specific filler is combined with a specific liquid crystalline polymer (Patent Document 5). reference.). According to the invention described in Patent Document 5, a thin planar connector having excellent properties such as moldability, flatness, warpage deformation, heat resistance, and the like, and further, the integration rate in recent planar connectors is obtained. It is possible to cope with a change in shape accompanying an increase in the thickness, particularly an increase in the number of connector pins and a further reduction in the width of the lattice portion.
However, in the invention described in Patent Document 5, cracks after the molding may occur in the lattice part due to fine changes in the manufacturing conditions such as polymer manufacturing variations and molding conditions, and sufficient performance in crack resistance. Could not get.
On the other hand, the above problems occur not only in flat connectors, but also in various molded products such as various connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, and heat fixing rolls for office automation equipment. Sometimes.

JP 59-43021 A JP 59-62630 A Japanese Patent Laid-Open No. 11-506145 JP 2005-276758 A JP 2010-3661

The object of the present invention is to provide a wholly aromatic polyester that solves the above-mentioned problems and has excellent heat resistance and toughness and exhibits optical anisotropy when melted, and a composition thereof.
In addition, the present invention has a good moldability and is excellent in performances such as heat resistance and crack resistance. In particular, when molded into a shape such as a plate shape or a film shape, in addition to the above excellent performance. An object of the present invention is to provide a polyester molded article with less warpage deformation and excellent flatness.

As a result of intensive studies to achieve the above object, the present inventors have found that in a polymer composed of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic acid, resorcinol, and 4,4′-dihydroxybiphenyl, It has been found that combining 6-hydroxy-2-naphthoic acid and resorcinol in a specific limited amount is effective for achieving the above object, and the present invention has been completed.

(1) Including constituent units represented by the following general formulas (I), (II), (III), (IV) and (V) as essential constituent components, and the constituent of (I) with respect to all constituent units 35 to 75 mol% of units, 2 to 8 mol% of structural units of (II), 8.5 to 31.5 mol% of structural units of (III), 2 to 8 mol% of structural units of (IV) And (V) the structural unit is 0.5 to 29.5 mol%, and the structural unit (II) + (IV) is 4 to 10 mol%. Totally aromatic polyester.

(2) The wholly aromatic polyester according to (1), wherein the melt viscosity is 1 × 10 ⁵ Pa · s or less at a shear rate of 1000 sec ⁻¹ at a temperature 10 to 40 ° C. higher than the melting point of the wholly aromatic polyester.

(3) The wholly aromatic polyester according to (1) or (2), which has a melting point of 280 to 390 ° C.

(4) A polyester resin composition comprising 120 parts by mass or less of an inorganic or organic filler based on 100 parts by mass of the wholly aromatic polyester according to any one of (1) to (3).

(5) The inorganic filler is one or more selected from glass fiber, mica and talc, and the blending amount is 20 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester (4) The polyester resin composition as described in 2.

(6) A polyester molded article obtained by molding the wholly aromatic polyester according to any one of (1) to (3) or the polyester resin composition according to (4) or (5).

(7) The polyester molded product according to (6), wherein the molded product is a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, or a heat fixing roll of an OA device.

(8) The polyester molded product according to (6), wherein the molded product is a planar connector characterized by a structure having a lattice structure inside the outer frame and a pitch interval of the lattice portion of 1.5 mm or less.

(9) The polyester molded product according to (6), wherein the molded product is a polyester fiber.

(10) The polyester molded product according to (6), wherein the molded product is a polyester film.

ADVANTAGE OF THE INVENTION According to this invention, the wholly aromatic polyester which is excellent in heat resistance and toughness, and shows optical anisotropy at the time of fusion | melting, and its composition can be provided.
Further, according to the present invention, the above-mentioned excellent performance is obtained when the molded product has good moldability and is excellent in performance such as heat resistance and crack resistance, particularly in the shape of plate or film. In addition, it is possible to provide a polyester molded article with less warpage deformation and excellent flatness.
That is, the wholly aromatic polyester that exhibits anisotropy at the time of melting comprising the specific structural unit obtained in the present invention and the composition thereof have good fluidity at the time of melting and heat resistance of the molded article, and are excellent in toughness. In addition, because the molding temperature is not so high, injection molding, extrusion molding, and compression molding are possible without using a molding machine with a special structure, and it can be processed into various three-dimensional molded products, fibers, films, etc. can do. Particularly, it is suitable for a molded product such as a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, or a heat fixing roll of OA equipment. Furthermore, the above-mentioned various performances can provide a planar connector that has good moldability, little warping deformation, and excellent performance such as flatness, heat resistance, and crack resistance.

It is a figure which shows the planar connector shape | molded in the Example, (a) is a top view, (b) is a detail drawing of the A section. The unit of numerical values in the figure is mm. It is a figure which shows the molded article used for the crack-proof evaluation of a molded article in an Example, (a) is the top view, (b) is a figure which shows the dimension. The unit of numerical values in the figure is mm.

<Totally aromatic polyester>
The wholly aromatic polyester of the present invention is a wholly aromatic polyester that exhibits optical anisotropy when melted, and has the following general formulas (I), (II), (III), (IV) and (IV) as essential constituent components. V), the structural unit of (I) is 35 to 75 mol%, the structural unit of (II) is 2 to 8 mol%, and the structural unit of (III) is 8.5 to 31.5 mol%, (IV) constituent unit is 2 to 8 mol%, (V) constituent unit is 0.5 to 29.5 mol%, (II) + (IV) constituent unit Is 4 to 10 mol%.

In order to embody the structural units of the above general formulas (I) to (V), various compounds having ordinary ester forming ability are used. Hereinafter, the raw material compounds necessary for forming the wholly aromatic polyester constituting the present invention will be described in detail step by step.

Structural unit (I) is introduced from 4-hydroxybenzoic acid.

The structural unit (II) is introduced from 6-hydroxy-2-naphthoic acid.

The structural unit (III) is introduced from terephthalic acid.

The structural unit (IV) is introduced from resorcinol.

The structural unit (V) is introduced from 4,4'-dihydroxybiphenyl.

The present invention includes the structural units (I) to (V), wherein the structural unit of (I) is 35 to 75 mol% (preferably 40 to 65 mol%) and (II) based on the total structural units. The unit is 2 to 8 mol% (preferably 3 to 7 mol%), the structural unit (III) is 8.5 to 31.5 mol% (preferably 14 to 29 mol%), and the structural unit (IV) is 2 to 8 mol% (preferably 3 to 7 mol%), (V) is 0.5 to 29.5 mol% (preferably 10 to 22 mol%), (II) + (IV) The unit needs to be in the range of 4 to 10 mol% (preferably 6 to 10 mol%).

When the constituent unit of (I) is less than 35 mol% and more than 75 mol%, the melting point becomes remarkably high, and in some cases, the polymer solidifies in the reactor during production, making it impossible to produce a polymer having a desired molecular weight. Therefore, it is not preferable.
If the structural unit (II) is less than 2 mol%, the toughness is low and this is not preferred. Moreover, since it will become low in the heat resistance of a polymer when it exceeds 8 mol%, it is unpreferable.
When the structural unit of (III) is less than 8.5 mol% and more than 31.5 mol%, the melting point becomes remarkably high, and in some cases, the polymer solidifies in the reactor during production, and a polymer having a desired molecular weight can be produced. Since it becomes impossible, it is not preferable.
When the constituent unit of (IV) is less than 2 mol%, the toughness is low and not preferable. Moreover, since it will become low in the heat resistance of a polymer when it exceeds 8 mol%, it is unpreferable.
In addition, when the constituent unit of (V) is less than 0.5 mol% and more than 29.5 mol%, the melting point becomes remarkably high, and in some cases, the polymer is solidified in the reactor during production to produce a polymer having a desired molecular weight. This is not preferable because it cannot be performed.
In addition, when the structural unit of (II) + (IV) is less than 4 mol%, the heat of crystallization of the polymer determined by differential calorimetry showing the crystallization state of the polymer is 2.0 J / g or more, and the toughness is preferably reduced. Absent. A preferable value of the heat of crystallization is 1.8 J / g or less, and more preferably 1.6 J / g or less. On the other hand, if it exceeds 10 mol%, the heat resistance of the polymer is lowered, which is not preferable.
Note that the heat of crystallization is a differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured from room temperature to 20 ° C / min, the temperature is maintained at Tm1 + 40 ° C for 2 minutes. Then, the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when the temperature is measured at 20 ° C./min.

Incidentally, in the wholly aromatic polyester of the present invention, a small amount of other structural units other than the above-mentioned (I) to (V) can be introduced within a range not inhibiting the effects of the present invention.

As described above, in Japanese Patent Application Laid-Open No. 59-43021 (Patent Document 1), Japanese Patent Application Laid-Open No. 59-62630 (Patent Document 2), and Japanese Patent Application Laid-Open No. 11-506145 (Patent Document 3), 4-hydroxybenzoic acid is used. A liquid crystal polymer in which 6-hydroxy-2-naphthoic acid, a diol component, and a dicarboxylic acid component are combined with an acid has been proposed. For example, in Example 22 of JP-A-59-62630 (Patent Document 2), A liquid crystal polymer composed of 57 mol% of structural unit (I), 3 mol% of (II), 20 mol% of (III) and 20 mol% of (V) has been proposed. There was a problem of low toughness. In Example 14 of JP-A-11-506145 (Patent Document 3), the structural unit (I) is 20 mol%, (II) is 30 mol%, (III) is 25 mol%, and (IV). Has been proposed, but this liquid crystal polymer has high toughness but insufficient heat resistance.

On the other hand, in the present invention, by controlling the amount of the structural units (I) to (V) and the amount of the structural units (II) + (IV) to the above ranges, heat resistance, easy processability, manufacturability Thus, a wholly aromatic polyester excellent in both toughness could be obtained.

The wholly aromatic polyester of the present invention is polymerized using a direct polymerization method or a transesterification method, and a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like is used for the polymerization.
In the present invention, at the time of polymerization, an acylating agent for the polymerization monomer or a monomer having terminal activated as an acid chloride derivative can be used. Examples of the acylating agent include acid anhydrides such as acetic anhydride.
Various catalysts can be used for these polymerizations, and typical ones include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali and alkaline earth of carboxylic acids. Metal salts, Lewis acid salts such as BF _{3 and} the like. The amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.003 to 0.2% by mass, based on the total weight of the monomers.

Also, when performing solution polymerization or slurry polymerization, liquid paraffin, high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.

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

In the reaction, all the raw material monomers, the acylating agent and the catalyst can be charged in the same reaction vessel to start the reaction (one-stage system), or the raw material monomers (I), (II), (IV) and (V) The hydroxyl group can be acylated with an acylating agent and then reacted with the carboxyl group of (III) (two-stage system).

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

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

The liquid crystalline polymer exhibiting optical anisotropy when melted is an indispensable element in the present invention in order to have both thermal stability and easy processability. The wholly aromatic polyesters comprising the structural units (I) to (V) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer, but the polymer according to the present invention is melted. Limited to wholly aromatic polyesters that sometimes exhibit optical anisotropy.

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

In the wholly aromatic polyester of the present invention, liquid crystallinity and melting point (liquid crystallinity expression temperature) can be considered as an index of processability. Whether or not it exhibits liquid crystallinity is deeply related to the fluidity during melting, and it is essential that the wholly aromatic polyester of the present invention exhibits liquid crystallinity in a molten state.

Since nematic liquid crystalline polymers cause a significant decrease in viscosity at the melting point or higher, generally exhibiting liquid crystallinity at the melting point or higher is an index of workability. The melting point (liquid crystallinity expression temperature) is preferably as high as possible from the viewpoint of heat resistance, but it is 280 to 390 ° C in consideration of thermal degradation during polymer melt processing and heating capability of the molding machine. Is a preferred guideline. In addition, More preferably, it is 380 degrees C or less.

Furthermore, the melt viscosity at a shear rate of 1000 sec ⁻¹ at a temperature 10 to 40 ° C. higher than the melting point is preferably 1 × 10 ⁵ Pa · s or less. More preferably, it is 5 Pa · s or more and 1 × 10 ² Pa · s or less. These melt viscosities are generally realized by having liquid crystallinity.

<Polyester resin composition>
The polyester resin composition of the present invention is characterized by blending 120 parts by mass or less of an inorganic or organic filler with respect to 100 parts by mass of the wholly aromatic polyester of the present invention described above.
Examples of inorganic and organic fillers include fibrous, granular, and plate-like ones.

Fiber fillers include glass fibers, asbestos fibers, silica fibers, silica / alumina fibers, alumina fibers, zirconia fibers, silicon nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, silicates such as wollastonite. Inorganic fibrous materials such as fibers, magnesium sulfate fibers, aluminum borate fibers, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A particularly typical fibrous filler is glass fiber. High melting point organic fibrous materials such as polyamide, fluorine resin, polyester resin, and acrylic resin can also be used.

On the other hand, as particulate filler, silicates such as carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite , Iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other ferrites, carbonization Examples thereof include silicon, silicon nitride, silicon nitride, and various metal powders.

In addition, examples of the plate-like filler include mica, glass flakes, talc, and various metal foils.

Examples of organic fillers include heat-resistant high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamides, and polyimide fibers.

These inorganic and organic fillers can be used alone or in combination of two or more. The combined use of the fibrous filler and the granular or plate-like filler is a preferable combination particularly in combination of mechanical strength, dimensional accuracy, electrical properties and the like. The blending amount of the inorganic filler is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester.

Particularly preferably, the fibrous filler is glass fiber, and the platy filler is mica and talc. The blending amount is 30 to 80 parts by mass with respect to 100 parts by mass of the total aromatic polyester. In addition, it is preferable that the fiber length of glass fiber is 200 micrometers or more. A composition containing such a glass fiber in the above blending amount is particularly remarkable in improving the heat distortion temperature and mechanical properties.

When using these fillers, a sizing agent or a surface treatment agent can be used if necessary.

Furthermore, another thermoplastic resin may be supplementarily added to the wholly aromatic polyester of the present invention as long as the purpose intended by the present invention is not impaired.

Examples of the thermoplastic resin used in this case include polyolefins such as polyethylene and polypropylene, aromatic polyesters composed of aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, and diols, polyacetals (homo or copolymers), Examples thereof include polystyrene, polyvinyl chloride, polyamide, polycarbonate, ABS, polyphenylene oxide, polyphenylene sulfide, and fluororesin. These thermoplastic resins can be used in combination of two or more.

<Polyester molded product>
The polyester molded product of the present invention is formed by molding the wholly aromatic polyester of the present invention described above or the polyester resin composition of the present invention.
Specific examples of the polyester molded product of the present invention include a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, and a heat fixing roll of OA equipment. Other examples include polyester fibers and polyester films. These can be molded by a known resin molding method using the wholly aromatic polyester of the present invention or the polyester resin composition of the present invention.
Moreover, as a specific aspect of the polyester molded article, a planar connector characterized by a structure having a lattice structure inside the outer frame and a pitch interval of the lattice portion of 1.5 mm or less. Hereinafter, the planar connector will be described in detail.

By molding the wholly aromatic polyester of the present invention or the polyester resin composition of the present invention, various planar connectors can be obtained, but conventionally, industrially practical ones have not been provided, Especially effective for very thin planar connectors where the pitch of the grid is 1.5 mm or less, the width of the resin part of the grid holding the terminal is 0.5 mm or less, and the overall height of the product is 5.0 mm or less. is there.
If explaining such a planar connector in more detail, it is a connector as shown in FIG. 1 formed in the embodiment, and an outer frame portion having a thickness of 4.0 mm or less and a lattice portion having a thickness of 4.0 mm or less. The lattice portion has a number of pin holes of several hundreds in a product of about 40 mm × 40 mm × 1 mm. As shown in FIG. 1, injection molding is very difficult, with the pitch interval of the lattice portions being 1.5 mm or less and the width of the resin portion holding the terminals being 0.5 mm or less. The planar connector referred to in the present invention includes one having an opening of an appropriate size in the lattice portion.

By using the wholly aromatic polyester or polyester resin composition of the present invention, as shown in FIG. 1, the pitch interval of the lattice portion is 1.5 mm or less (1.2 mm), and the width of the resin portion of the lattice portion that holds the terminal It is possible to form a flat connector having a very thin resin portion width of the lattice portion of 0.5 mm or less (0.18 mm) with good moldability and excellent flatness.
If this flatness is specified numerically, the flatness before the IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C is 0.05 mm or less, and the difference in flatness before and after reflow is Those having a thickness of 0.10 mm or less can be said to have excellent flatness in practical use.

The molding method for obtaining a connector having such excellent flatness is not particularly limited, but an economical injection molding method is preferably used. In order to obtain a connector having such excellent flatness by injection molding, it is important to use the wholly aromatic polyester of the present invention described above or the polyester resin composition of the present invention. It is preferable to select molding conditions that do not have any. In order to lower the filling pressure and reduce the residual internal stress of the resulting connector, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point T ° C of the wholly aromatic polyester, and if the cylinder temperature is too high, the resin is decomposed. Since problems such as nasal sagging from the cylinder nozzle occur due to the above, the cylinder temperature is T ° C. to (T + 30) ° C., preferably T ° C. to (T + 15) ° C. The mold temperature is preferably 70 to 100 ° C. When the mold temperature is low, the filled resin composition is unfavorably caused by flow failure, and when the mold temperature is too high, problems such as generation of burrs are not preferable. The injection speed is preferably 150 mm / sec or more. If the injection speed is low, only unfilled molded products can be obtained, or even if a completely filled molded product is obtained, the molded product has a high filling pressure and a large residual internal stress, and only a connector with poor flatness can be obtained. May not be possible

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the physical-property measurement and the test method in an Example are as follows.

[Melting point]
After measuring the endothermic peak temperature (Tm1) observed when measuring fully aromatic polyester from room temperature to 20 ° C / min with a Perkin Elmer DSC, 2 minutes at a temperature of (Tm1 + 40) ° C After being held, it was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then the temperature of the endothermic peak observed when measured under a temperature rise condition of 20 ° C./min was measured again.

[Crystallizing temperature]
After observing the endothermic peak temperature (Tm1) observed when the fully aromatic polyester and polyester resin composition were measured at room temperature to 20 ° C / min on a Perkin Elmer DSC, (Tm1 + 40) ° C After maintaining at a temperature of 2 minutes, an exothermic peak temperature observed when measured under a temperature drop condition of 20 ° C./minute was measured.

[Amount of crystallization]
After observing the endothermic peak temperature (Tm1) observed when the fully aromatic polyester and polyester resin composition were measured at room temperature to 20 ° C / min on a Perkin Elmer DSC, (Tm1 + 40) ° C After maintaining at a temperature of 2 minutes, the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when the temperature was measured under a temperature drop condition of 20 ° C./min was measured.

[Melt viscosity]
The total aromatic polyester and polyester resin composition was measured with a Toyo Seiki Capillograph using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 20 ° C. higher than the melting point, and the melt viscosity at a shear rate of 1000 sec ⁻¹ was measured. Calculated (ISO 11443 compliant).

[Softening temperature]
A disk with a thickness of 1mm is formed from wholly aromatic polyester using a hot press, and the temperature is raised at 20 ° C / min on a hot plate while applying a constant load of 12.7MPa to the molded product. The temperature at which the needle reached 5% of the thickness of the molded product was defined as the softening temperature.

[Measurement of connector flatness]
From a polyester resin composition containing an inorganic filler, a flat connector having a total size of 39.82 mm × 41.82 mm × 1 mmt and a lattice pitch of 1.2 mm as shown in FIG. Pin) was injection molded.
The gate was a film gate from a long side (side of 41.82 mm), and the gate thickness was 0.3 mm.
The obtained connector was allowed to stand on a horizontal desk, and the height of the connector was measured with Mitutoyo Quick Vision 404PROCNC image measuring machine. At that time, 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 was defined as flatness.
[Measurement of connector deformation]
Furthermore, IR reflow was performed under the following conditions, the flatness was measured by the above-described method, and the difference in flatness before and after the reflow was determined as the amount of connector deformation.

-Molding conditions-
Molding machine; Sumitomo Heavy Industries SE30DUZ
Cylinder temperature;
(Nozzle) 370 ° C-375 ° C-360 ° C-350 ° C (Examples 4-6)
340 ° C-340 ° C-330 ° C-320 ° C (Comparative Example 8)
370 ℃ -375 ℃ -360 ℃ -350 ℃ (Comparative Example 9)
350 ° C-350 ° C-340 ° C-330 ° C (Comparative Example 10)
Mold temperature: 80 ℃
Injection speed: 300mm / sec
Holding pressure: 50MPa
Holding pressure time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2MPa

-IR reflow conditions-
Measuring machine: RF-300 (using far-infrared heater)
Sample feed rate: 140mm / sec
Reflow furnace transit time: 5 min
Temperature conditions Preheat zone: 150 ° C, reflow zone: 225 ° C, peak temperature: 287 ° C

[Connector minimum filling pressure]
The minimum injection filling pressure at which a good molded product can be obtained when the planar connector of FIG.

[Load deflection temperature]
Under the following molding conditions, each polyester resin composition containing an inorganic filler was injection molded and measured in accordance with ISO75-1,2.
-Molding conditions-
Molding machine: Sumitomo Heavy Industries SE100DU
Cylinder temperature;
(Nozzle) 370 ° C-375 ° C-360 ° C-350 ° C (Examples 4-6)
340 ° C-340 ° C-330 ° C-320 ° C (Comparative Example 8)
370 ℃ -375 ℃ -360 ℃ -350 ℃ (Comparative Example 9)
350 ° C-350 ° C-340 ° C-330 ° C (Comparative Example 10)
Mold temperature: 80 ℃
Injection speed: 2m / min
Holding pressure: 50MPa
Holding pressure time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2MPa

[Crack resistance]
From the polyester resin composition containing the inorganic filler, an evaluation molded product as shown in FIG. 2 was injection molded under the following molding conditions.
The evaluation injection-molded product shown in FIG. 2 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 cracks in the molded product, and observe the occurrence of cracks around the hole at a magnification of 5 times. If the molded product is cracked, “X”; if not, “○”. It was judged.
-Molding conditions-
Molding machine; Sumitomo Heavy Industries SE30DUZ
Cylinder temperature;
(Nozzle) 370 ° C-375 ° C-360 ° C-350 ° C (Examples 4-6)
340 ° C-340 ° C-330 ° C-320 ° C (Comparative Example 8)
370 ℃ -375 ℃ -360 ℃ -350 ℃ (Comparative Example 9)
350 ° C-350 ° C-340 ° C-330 ° C (Comparative Example 10)
Mold temperature: 140 ℃
Injection speed: 50mm / sec
Holding pressure: 100MPa
Holding pressure time: 2 sec
Cooling time: 10 sec
Screw rotation speed: 120rpm
Screw back pressure: 1.2MPa

[Example 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 monomer, metal catalyst, and acylating agent, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 145 g (48 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 12 g (3 mol%) (HNA)
(III) Terephthalic acid: 89 g (24.7 mol%) (TA)
(IV) Resorcinol: 8 g (3.5 mol%) (RES)
(V) 4,4′-dihydroxybiphenyl 85 g (20.8 mol%) (BP)
Potassium acetate catalyst: 15mg
Acetic anhydride: 229 g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 3 hours. Thereafter, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (ie, 1330 Pa) over 20 minutes, and melt polymerization is performed while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. went. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from a reduced pressure state to an ordinary pressure, and the polymer was discharged from the lower part of the polymerization vessel.
The obtained polymer had a melting point of 357 ° C., a crystallization temperature of 298 ° C., a heat of crystallization of 1.2 J / g, a softening temperature of 246 ° C., and a melt viscosity of 16 Pa · s.
Table 1 shows the raw material monomer composition of Example 1 and the results of measurement of physical properties of the obtained polymer. In Table 1, each raw material monomer is indicated by using abbreviations shown in parentheses such as HBA and HNA.

[Examples 2 to 3]
Polymerization was carried out in the same manner as in Example 1 except that the types of raw material monomers and the charging ratio were as shown in Table 1, and the polymer was discharged from the lower part of the polymerization vessel. The results of measuring the physical properties of the obtained polymer are shown in Table 1.

[Comparative Examples 1 to 7]
Polymerization was carried out in the same manner as in Example 1 except that the types of raw material monomers and the charging ratio were as shown in Table 1, and the polymer was discharged from the lower part of the polymerization vessel. The results of measuring the physical properties of the obtained polymer are shown in Table 1. In Comparative Examples 6 and 7, the polymer solidified in the reactor at the time of production, and a polymer having a desired molecular weight could not be produced. In Table 1, APAP is 4-acetamidophenol.

Table 1 shows that the wholly aromatic polyesters of Examples 1 to 3 have a high softening temperature and a heat of crystallization of 1.8 J / g or less, and are excellent in heat resistance and toughness.
On the other hand, Comparative Examples 1 and 5 in which RES was not used and Comparative Example 2 in which HNA + RES (general formula (II) + (IV)) was less than 4 mol% were inferior in toughness. Further, Comparative Examples 3 and 4 in which HNA + RES (general formula (II) + (IV)) exceeds 10 mol% were inferior in heat resistance. Furthermore, Comparative Examples 6 and 7 in which the feed ratio of raw material monomers (particularly HBA) was outside the scope of the present invention could not even produce a polymer.

[Example 4]
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 monomer, metal catalyst, and acylating agent, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 1061 g (48 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 90 g (3 mol%) (HNA)
(III) Terephthalic acid: 657 g (24.7 mol%) (TA)
(IV) Resorcinol: 62 g (3.5 mol%) (RES)
(V) 4,4′-dihydroxybiphenyl 620 g (20.8 mol%) (BP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1676 g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 3 hours. Thereafter, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (ie, 667 Pa) over 20 minutes, and melt polymerization is carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. went. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure state to a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize.
The obtained polymer had a melting point of 355 ° C., a crystallization temperature of 298 ° C., a heat of crystallization of 1.2 J / g, and a melt viscosity of 10 Pa · s.

Mixing and kneading 33.3 parts by mass of mica (Yamaguchi Mica Kogyo Co., Ltd., AB-25S, average particle size 25 μm) with a twin-screw extruder to 100 parts by mass of the above pellets, a pellet-shaped wholly aromatic polyester resin composition Got. Various tests such as physical property measurement and “measurement of connector flatness” were performed on the obtained resin composition. The results are shown in Table 2.

[Example 5]
A polymer was obtained in the same manner as in Example 4 except that the raw material monomer type and charging ratio were as shown in Table 2. Next, pelletization was performed in the same manner as in Example 4. The obtained polymer had a melting point of 355 ° C., a crystallization temperature of 298 ° C., a heat of crystallization of 1.2 J / g, and a melt viscosity of 10 Pa · s.
Moreover, 23.1 parts by mass of talc (manufactured by Matsumura Sangyo Co., Ltd., crown talc PP, average particle size 12.8 μm) and glass fiber (ECS03T-786H, fiber by mass with 100 parts by mass of the above pellets) 30.8 parts by mass of a chopped strand having a diameter of 10 μm and a length of 3 mm was compounded and kneaded by a twin screw extruder to obtain a pellet-shaped wholly aromatic polyester resin composition. Various tests such as physical property measurement and “measurement of connector flatness” were performed on the obtained resin composition. The results are shown in Table 2.

[Example 6]
A polymer was obtained in the same manner as in Example 4 except that the raw material monomer type and charging ratio were as shown in Table 2. Next, pelletization was performed in the same manner as in Example 4. The obtained polymer had a melting point of 355 ° C., a crystallization temperature of 298 ° C., a heat of crystallization of 1.2 J / g, and a melt viscosity of 10 Pa · s.
Further, 66.7 parts by mass of glass fiber was blended and kneaded with 100 parts by mass of the pellets using a twin-screw extruder to obtain a pellet-shaped wholly aromatic polyester resin composition. Various tests such as physical property measurement and “measurement of connector flatness” were performed on the obtained resin composition. The results are shown in Table 2.

[Comparative Examples 8 to 10]
In Comparative Examples 8 to 10, polymers were obtained in the same manner as in Example 4 except that the types of raw material monomers and the charging ratios were as shown in Table 2. Next, pelletization was performed in the same manner as in Example 4. The polymer obtained in Comparative Example 8 had a melting point of 323 ° C., a crystallization temperature of 276 ° C., a heat of crystallization of 2.0 J / g, and a melt viscosity of 12 Pa · s. The polymer obtained in Comparative Example 9 had a melting point of 357 ° C., a crystallization temperature of 305 ° C., a crystallization heat amount of 2.1 J / g, and a melt viscosity of 10 Pa · s. Further, the polymer obtained in Comparative Example 10 had a melting point of 335 ° C., a crystallization temperature of 291 ° C., a crystallization heat amount of 3.1 J / g, and a melt viscosity of 20 Pa · s.
Further, with respect to 100 parts by mass of the pellets, the compounding amounts as shown in Table 2 were respectively compounded and kneaded by a twin screw extruder to obtain a pellet-shaped wholly aromatic polyester resin composition. Various tests such as physical property measurement and “measurement of connector flatness” were performed on the obtained resin composition. The results are shown in Table 2.

Table 2 shows that all of the planar connectors of Examples 4 to 6 have good moldability, little warpage deformation, and excellent flatness, heat resistance, and crack resistance. On the other hand, in Comparative Examples 8 to 10, all the evaluations could not be made good at the same time.

Claims

Including the structural units represented by the following general formulas (I), (II), (III), (IV) and (V) as essential structural components, the structural unit of (I) is 35 with respect to all the structural units. ~ 75 mol%, (II) constituent unit is 2 to 8 mol%, (III) constituent unit is 8.5 to 31.5 mol%, (IV) constituent unit is 2 to 8 mol%, (V ), 0.5 to 29.5 mol%, and (II) + (IV) is 4 to 10 mol%. polyester.
2. The wholly aromatic polyester according to claim 1, which has a melt viscosity of 1 × 10 5 Pa · s or less at a shear rate of 1000 sec −1 at a temperature 10 to 40 ° C. higher than the melting point of the wholly aromatic polyester.
The wholly aromatic polyester according to claim 1, having a melting point of 280 to 390 ° C.
A polyester resin composition obtained by blending 120 parts by mass or less of an inorganic or organic filler with 100 parts by mass of the wholly aromatic polyester according to any one of claims 1 to 3.
The polyester according to claim 4, wherein the inorganic filler is one or more selected from glass fiber, mica and talc, and the blending amount is 20 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester. Resin composition.
A polyester molded product obtained by molding the wholly aromatic polyester according to any one of claims 1 to 3 or the polyester resin composition according to claim 4 or 5.
The polyester molded product according to claim 6, wherein the molded product is a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, or a heat fixing roll of an OA device.
7. The polyester molded product according to claim 6, wherein the molded product is a planar connector characterized by a structure having a lattice structure inside the outer frame and a pitch interval of the lattice portion of 1.5 mm or less.
The polyester molded product according to claim 6, wherein the molded product is a polyester fiber.
7. The polyester molded product according to claim 6, wherein the molded product is a polyester film.