KR20150060712A - Wholly aromatic polyester, polyester resin composition, and a polyester molded article - Google Patents

Abstract

The present invention provides a wholly aromatic polyester excellent in heat resistance and toughness and exhibiting optical anisotropy upon melting and a composition thereof.
The present invention includes, as essential constituents, the constitutional units represented by the following general formulas (I), (II), (III), (IV) and (V) (III) is from 35 to 75 mol%, (II) is from 2 to 8 mol%, (III) is from 8.5 to 31.5 mol%, (IV) is from 2 to 8 mol% , A constituent unit of 0.5 to 29.5 mol%, and a constituent unit of (II) + (IV) of 4 to 10 mol%, and a wholly aromatic polyester exhibiting optical anisotropy upon melting and a wholly aromatic polyester And an inorganic or organic filler in an amount of 120 parts by mass or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a wholly aromatic polyester, a polyester resin composition, and a polyester molded article. BACKGROUND ART < RTI ID = 0.0 >

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

A commercially available wholly aromatic polyester is 4-hydroxybenzoic acid as a main component. However, since the homopolymer of 4-hydroxybenzoic acid has a melting point higher than the decomposition point, it is necessary to lower the melting point by copolymerizing various components.

The wholly aromatic polyester using terephthalic acid, hydroquinone, 4,4'-dihydroxybiphenyl or the like as a copolymerization component has a melting point as high as 350 ° C or higher and is too high for melt processing in a general-purpose apparatus. Various methods for lowering the melting point of such a high melting point to a temperature at which it can be processed in a general purpose melt processing apparatus have been attempted, but a low melting point has been achieved to a certain extent, while mechanical strength at a high temperature There is a problem that the representative heat resistance can not be maintained.

In order to solve such a problem, Patent Literatures 1 to 3 propose copolymerized polyesters in which 6-hydroxy-2-naphthoic acid, a diol component, and a dicarboxylic acid component are combined with 4-hydroxybenzoic acid.

However, the copolyesters proposed in Patent Documents 1 to 3 have a problem that the toughness is low, cracking occurs in the molded article at the time of molding, or the toughness is high, but the heat resistance is not sufficient.

On the other hand, as the above-mentioned wholly aromatic polyester, an optically anisotropic substance exhibiting optical anisotropy at the time of melting is called a liquid crystalline polymer, and is excellent in dimensional accuracy, damping resistance, fluidity, And is useful as a material for electronic parts. In a planar connector having a lattice structure inside an outer frame represented by a CPU socket, a liquid crystal polymer composition reinforced with glass fibers is remarkably used because of its high intrinsic deterioration, high density and miniaturization tendency. However, even in a glass fiber-reinforced liquid crystal polymer composition having a good fluidity to some extent, it is very difficult to obtain a very thin film having a pitch interval of not more than 2 mm and a width of a resin portion of a lattice portion holding a terminal of 0.5 mm or less, The performance was insufficient for use as a planar connector. That is, in the case of the planar connector in which the width of the lattice portion is thin as described above, if filling the lattice portion with resin, fluidity is insufficient, the filling pressure becomes high and the resulting deflection amount of the planar connector becomes large . In order to solve this problem, it is conceivable to use a liquid crystalline polymer composition having a good fluidity with a small addition amount of glass fibers, but such a composition is insufficient in strength and deformed by reflow at the time of mounting .

Therefore, the present inventors have proposed a planar connector composed of a specific composite resin composition in which the weight average length and the blending amount of the fibrous filler to be blended are in a constant relationship (see Patent Document 4). According to the invention described in Patent Document 4, excellent performances such as moldability, flatness, flexural deformation, and heat resistance can be obtained even for thin-walled planar connectors.

However, due to factors such as the shape change due to an increase in the integration ratio of the planar connector in recent years, particularly the increase in the number of connector pins and the further thinning of the lattice width, the invention described in Patent Document 4 can cope with It was found that there is no case.

The present inventors have further proposed a planar connector comprising a specific composite resin composition in which a plate filler and a fibrous filler are blended together with a specific liquid crystalline polymer (see Patent Document 5). According to the invention described in Patent Literature 5, it is possible to obtain thin-plate-shaped connectors having excellent performances such as formability, flatness, flexural deformation and heat resistance, and furthermore, It is possible to cope with a change in shape, in particular, an increase in the number of connector pins and a further reduction in thickness of the lattice portion.

However, according to the invention described in Patent Document 5, cracks (cracks) occur in the lattice portions due to variations in manufacturing conditions such as unevenness of production of polymers and molding conditions, and sufficient performance against cracking resistance can not be obtained.

On the other hand, the above-described problems may occur not only in the planar connector but also in various molded products such as various connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, or heating and fixing rolls of OA devices.

Patent Document 1: Japanese Patent Application Laid-Open No. 59-43021 Patent Document 2: JP-A-59-62630 Patent Document 3: JP-A-11-506145 Patent Document 4: JP-A-2005-276758 Patent Document 5: JP-A-2010-3661

An object of the present invention is to provide a wholly aromatic polyester excellent in heat resistance and toughness and exhibiting optical anisotropy at the time of melting by solving the above problems, and a composition thereof.

The present invention also provides a polyester molded article excellent in moldability and excellent in performance such as heat resistance and crack resistance, particularly, in the case of being molded into a shape such as plate or film, And an object of the present invention is to provide a polyester molded article excellent in flatness.

The present inventors have made intensive studies to achieve the above object and as a result, they have found that a polymer composed of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic acid, resorcinol, 4,4'-dihydroxybiphenyl , It has been found that the combination of 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 accomplished.

(I), (II), (III), (IV) and (V) as essential constituent components, (III) is from 8 to 31.5 mol%, (IV) is from 2 to 8 mol%, (V) is from 35 to 75 mol%, the constituent unit is from 2 to 8 mol% Is 0.5 to 29.5 mol%, and the constituent unit of (II) + (IV) is 4 to 10 mol%. The wholly aromatic polyester exhibiting optical anisotropy upon melting.

(2) The wholly aromatic polyester according to (1), wherein the polyester has a melt viscosity of not more than 1 × 10 ⁵ Pa · s at a temperature 10 to 40 ° C. higher than the melting point of the wholly aromatic polyester at a shear rate of 1,000 sec ^-1 .

(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 described in any one of (1) to (3) above.

(5) The polyester resin composition according to the above (4), wherein the inorganic filler is one or more kinds selected from glass fibers, mica and talc, and the amount thereof is 20 to 80 parts by mass based on 100 parts by mass of the wholly aromatic polyester.

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

(7) The polyester molded article according to the above (6), wherein the molded article is a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter case, or a heating fixation roll of an OA appliance.

(8) The polyester molded article according to the above (6), wherein the molded article is a planar connector 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 article according to (6), wherein the molded article is a polyester fiber.

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

According to the present invention, it is possible to provide a wholly aromatic polyester excellent in heat resistance and toughness, exhibiting optical anisotropy upon melting, and a composition thereof.

Further, according to the present invention, in the case of molding in the form of a polyester molded article having excellent moldability, excellent heat resistance and crack resistance, particularly, in the form of plate or film, It is possible to provide a polyester molded article excellent in flatness.

That is, the wholly aromatic polyester exhibiting anisotropy at the time of melting obtained by the specific constitutional unit obtained by the present invention and the composition thereof are excellent in fluidity at the time of melting, heat resistance of the molded article, excellent toughness, Injection molding, extrusion molding and compression molding can be carried out without using a molding machine having a special structure, so that it can be processed into various molded articles, fibers, films and the like. 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 heating and fixing roll of an OA device. Further, the above-mentioned performance makes it possible to obtain a planar-type connector excellent in moldability, less deflection, and excellent in performance such as flatness, heat resistance and crack resistance.

Fig. 1 is a plan view of a connector molded in the embodiment. Fig. 1 (a) is a plan view and Fig. 1 (b) is a detailed view of part A. In the figure, the unit of the figure is mm.
Fig. 2 is a view showing a molded article used for evaluating crack resistance of a molded article in the embodiment, wherein Fig. 2 (a) is a plan view thereof, and Fig. 2 (b) is a view showing its dimensions. In the figure, the unit of the figure is mm.

<Whole aromatic polyester>

The wholly aromatic polyester of the present invention is a wholly aromatic polyester exhibiting optical anisotropy at the time of melting, and is preferably an aromatic polyester having the following general formulas (I), (II), (III), (IV) (I) is contained in an amount of 35 to 75 mol%, (II) is contained in an amount of 2 to 8 mol%, and the constituent unit (III) is contained in an amount of 8.5 to 31.5 mol , The constituent unit of (IV) is 2 to 8 mol%, the constituent unit of (V) is 0.5 to 29.5 mol%, and the constituent unit of (II) + (IV) is 4 to 10 mol%.

In order to realize the constitutional units of the general formulas (I) to (V), various compounds having an ordinary ester forming ability (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 in order.

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

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

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

The constituent unit (IV) is introduced from resorcinol.

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

In the present invention, the content of the constituent units (I) to (V) is 35 to 75 mol% (preferably 40 to 65 mol%), (Preferably 3 to 7 mol%), the constituent unit of (III) is 8.5 to 31.5 mol% (preferably 14 to 29 mol%), the constituent unit of (IV) is 2 (IV) is 4 to 8 mol% (preferably 3 to 7 mol%), the constituent unit of (V) is 0.5 to 29.5 mol% (preferably 10 to 22 mol% To 10 mol% (preferably 6 to 10 mol%).

When the content of the structural unit (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, It is not preferable.

(II) is less than 2 mol%, the toughness is low. If it is more than 8 mol%, the heat resistance of the polymer is lowered, which is not preferable.

(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 not be produced It is not preferable.

When the content of the constituent unit (IV) is less than 2 mol%, the toughness is low, which is not preferable. If it is more than 8 mol%, the heat resistance of the polymer is lowered, which is not preferable.

If 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 solidifies in the reactor during production, Which is undesirable.

When the content of the constituent unit of (II) + (IV) is less than 4 mol%, the crystallization heat of the polymer obtained by the differential thermal calorimetric measurement showing the crystallization state of the polymer is 2.0 J / g or more, not. The preferred value of the crystallization heat amount is 1.8 J / g or less, and more preferably 1.6 J / g or less. On the other hand, if it is more than 10 mol%, the heat resistance of the polymer is lowered.

The term "crystallization calorie" refers to the temperature difference between the endothermic peak temperature (Tm1) measured at room temperature and the endothermic peak temperature (Tm1) observed at 20 ° C / Min 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.

To the wholly aromatic polyester of the present invention, a small amount of known constituent units other than the above-mentioned (I) to (V) may be introduced as long as the effect of the present invention is not impaired.

As described above, in Japanese Laid-Open Patent Application 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) -Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, a diol component and a dicarboxylic acid component has been proposed. For example, Japanese Patent Application Laid-Open No. 59-62630 (Patent Document 2) In Example 22, there is proposed a liquid crystal polymer comprising 57 mol% of the constituent unit (I), 3 mol% of (II), 20 mol% of (III) and 20 mol% of (V) , There was a problem that the toughness was low. In Example 14 of Japanese Patent Application Laid-Open No. 11-506145 (Patent Document 3), 20 mol% of the constituent unit (I), 30 mol% of (II), 25 mol% of (III) IV) of 5 mol% and (V) of 20 mol%. However, this liquid crystal polymer has a problem that the toughness is high, but the heat resistance is insufficient.

By contrast, in the present invention, by regulating the amounts of the constitutional units (I) to (V) and the amounts of the constitutional units (II) + (IV) in the above-mentioned range, excellent heat resistance, easy workability, A wholly aromatic polyester can be obtained.

The wholly aromatic polyester of the present invention is polymerized by a direct polymerization method or an ester exchange method, and in the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method and the like are used.

In the present invention, an acylating agent for a polymerization monomer or a monomer having a terminal activated at an acid chloride derivative may be used in the polymerization. Examples of the acylating agent include acid anhydrides such as acetic anhydride and the like.

In these polymerization it can be used various catalysts, typical is a dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates acids, carboxylic acid alkali and alkaline earth metal salts, such as BF ₃ of Lewis acid salts and the like. The amount of the catalyst to be used is generally about 0.001 to 1% by mass, particularly about 0.003 to 0.2% by mass, based on the total weight of the monomer.

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

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

The reaction can be started by introducing the entire raw material monomer, the acylating agent and the catalyst into the same reaction vessel to initiate the reaction (once-manner), and the hydroxyl groups of the raw materials monomers (I), (II), (IV) Acylation with an acylating agent, followed by reaction with a carboxy group of (III) (two-step method).

The melt polymerization is carried out at a predetermined reduced pressure after decompression is started after the reaction system reaches a predetermined temperature. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced to discharge the polymer from the reaction system under a reduced pressure, a normal pressure, and a predetermined pressure.

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

The liquid crystalline polymer exhibiting optical anisotropy at the time of melting is an indispensable element to combine thermal stability and easy processability in the present invention. The wholly aromatic polyester composed of the constituent units (I) to (V) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but the polymer according to the present invention has optical anisotropy Lt; RTI ID = 0.0 &gt; wholly aromatic &lt; / RTI &gt;

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

In the wholly aromatic polyester of the present invention, liquid crystallinity and melting point (liquid crystallization temperature) can be considered as an index of workability. Whether or not liquid crystalline properties are exhibited is closely related to the fluidity at the time of melting, and it is indispensable for the wholly aromatic polyester of the present invention to exhibit liquid crystallinity in a molten state.

Since the nematic liquid crystalline polymer causes a remarkable decrease in viscosity at a melting point or higher, it is an index of workability that exhibits liquid crystallinity at a melting point or higher. The melting point (liquid crystallization temperature) is preferably as high as possible from the viewpoint of heat resistance, but it is preferable that the temperature is 280 to 390 占 폚 in consideration of thermal degradation during melt processing of the polymer and heating ability of the molding machine. More preferably, it is 380 占 폚 or less.

Further, it is preferable that the melt viscosity at a temperature higher than the melting point by 10 to 40 캜 and a shear rate of 1000 sec ^-1 is 1 x 10 ⁵ Pa · s or less. More preferably ⁵ Pa · s or more and 1 × 10 ² Pa · s or less. This melt viscosity is generally realized by having liquid crystallinity.

&Lt; Polyester resin composition >

The polyester resin composition of the present invention is characterized by comprising an inorganic or organic filler in an amount of 120 parts by mass or less based on 100 parts by mass of the wholly aromatic polyester of the present invention.

Examples of inorganic and organic fillers include fibrous, granular, and plate-like ones.

Examples of the fibrous filler include fibers of silicate such as glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber and wollastonite, magnesium sulfate fiber, Aluminum fibers, and metallic fibrous materials such as stainless steel, aluminum, titanium, copper and brass. Typical fibrous fillers are glass fibers. High melting point organic fibrous materials such as polyamide, fluororesin, polyester resin and acrylic resin can also be used.

On the other hand, examples of the filler in the granular phase include silicates such as carbon black, graphite, silica, quartz powder, glass beads, glass milled glass, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, diatomaceous earth, , Oxides of metals such as zinc oxide, antimony trioxide and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, other ferrites, silicon carbide, silicon nitride, boron nitride, various metal powders And the like.

Examples of the plate filler include mica, glass flake, talc, various metal foils and the like.

Examples of the organic filler 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 may be used alone or in combination of two or more. The use of a fibrous filler in combination with a granular or plate filler is a particularly desirable combination to combine 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, relative to 100 parts by mass of the wholly aromatic polyester.

Particularly preferable are glass fibers as fibrous fillers, mica and talc as plate fillers, and the blending amount thereof is 30 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester. The fiber length of the glass fiber is preferably 200 mu m or more. The composition containing such a glass fiber in the above amount is particularly remarkable in terms of improvement in heat distortion temperature, mechanical properties and the like.

In the use of these fillers, a converging agent or a surface treatment agent may be used if necessary.

Further, the wholly aromatic polyester of the present invention may be supplementarily added with another thermoplastic resin within a range not hindering the object of the present invention.

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

<Polyester molded article>

The polyester molded article of the present invention is formed by molding the above-mentioned wholly aromatic polyester of the present invention or the polyester resin composition of the present invention.

Specifically, the polyester molded article of the present invention can be a connector, a CPU socket, a relay switch part, a bobbin, an actuator, a noise reduction filter case, or a heating fixation roll of an OA device. Other examples include polyester fibers and polyester films. These can be molded according to a known molding method of a resin by using the wholly aromatic polyester of the present invention or the polyester resin composition of the present invention.

A specific example of the polyester molded article is a planar connector having a lattice structure inside the outer frame and characterized by a structure in which the pitch interval of the lattice portions is 1.5 mm or less. Hereinafter, the planar connector will be described in detail.

Various types of planar connectors can be obtained by molding the wholly aromatic polyester of the present invention or the polyester resin composition of the present invention. However, conventionally industrially practicable ones have not been provided. The pitch interval of the lattice portions is 1.5 mm or less, In which the width of the resin portion of the lattice portion is 0.5 mm or less and the height of the entire product is 5.0 mm or less.

The planar connector will be described in more detail. A connector as shown in Fig. 1 formed in the embodiment is composed of 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 is 40 mm x 40 mm There are hundreds of pinholes in the product of about 1mm. As shown in Fig. 1, the pitch interval of the lattice portions is 1.5 mm or less, and the width of the resin portion for holding the terminals is 0.5 mm or less. The planar connector referred to in the present invention also includes an opening having an appropriate size in the lattice portion.

By using the wholly aromatic polyester or polyester resin composition of the present invention, the pitch interval of the lattice portions is 1.5 mm or less (1.2 mm), the width of the resin portion of the lattice portion holding the terminals is 0.5 mm or less (0.18 mm), the planar connector having a very thin width of the resin portion of the lattice portion can be molded with good formability, and the flatness is also excellent.

Numerically, such a flatness is numerically expressed as follows. When 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 0.10 mm or less, It can be said to have a flatness.

A molding method for obtaining such a connector having an 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 above-mentioned wholly aromatic polyester of the present invention or the polyester resin composition of the present invention, and it is preferable to select molding conditions without residual internal stress . In order to lower the filling pressure and lower the residual internal stress of the resulting connector, the temperature of the cylinder of the molding machine is preferably not lower than the melting point T ° C of the wholly aromatic polyester. If the cylinder temperature is too high, The cylinder temperature is in the range of T ° C to (T + 30) ° C, preferably T ° C to (T + 15) ° C. The mold temperature is preferably 70 to 100 占 폚. If the mold temperature is low, the filled resin composition causes flow defects, which is undesirable. If the mold temperature is too high, problems such as generation of burrs may occur. The injection speed is preferably 150 mm / sec or more. If the injection speed is low, only a non-filled molded article can be obtained, or even if a completely filled molded article is obtained, a molded article having a high residual stress due to a high filling pressure causes only a connector with poor flatness to be obtained .

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The measurement and test methods for physical properties in the examples are as follows.

[Melting point]

After observing the endothermic peak temperature (Tm1) observed when the wholly aromatic polyester was measured at room temperature from a room temperature by a temperature elevation condition of 20 ° C / min, the temperature was maintained at (Tm1 + 40) ° C for 2 minutes , And the temperature of the endothermic peak observed when the sample was once cooled to room temperature under the condition of lowering the temperature at 20 ° C / min and then measured again at a temperature increase rate of 20 ° C / min.

[Crystallization temperature]

After observing the endothermic peak temperature (Tm1) observed when the wholly aromatic polyester and polyester resin compositions were measured from room temperature at a temperature elevation rate of 20 deg. C / min, the temperature was measured at a temperature of (Tm1 + 40) Kept for 2 minutes, and then the exothermic peak temperature observed when the temperature was lowered to 20 DEG C / min was measured.

[Crystallization heat quantity]

After observing the endothermic peak temperature (Tm1) observed when the wholly aromatic polyester and polyester resin compositions were measured from room temperature at a temperature elevation rate of 20 deg. C / min, the temperature was measured at a temperature of (Tm1 + 40) After maintaining for 2 minutes, the calorific value of the exothermic peak, which was obtained from the peak of the exothermic peak temperature observed when the temperature was measured under a condition of lowering the temperature to 20 DEG C / min, was measured.

[Melting point]

The wholly aromatic polyester and polyester resin compositions were measured by a capillograph manufactured by Toyosai KK using an orifice having an inner diameter of 1 mm and a length of 20 mm at a temperature higher than the melting point by 10 to 20 ° C to obtain a melt viscosity at a shear rate of 1000 sec ^-1 (Based on ISO11443).

[Softening temperature]

A disk having a thickness of 1 mm was molded with a wholly aromatic polyester using a hot press, and the molded article was heated at a rate of 20 ° C / minute on a hot plate under a constant load of 12.7 MPa to obtain a needle having a diameter of 1 mm The temperature when the thickness reached 5% was defined as the softening temperature.

[Measurement of connector flatness]

(A pinhole number of 750 picoseconds) having an overall size of 39.82 mm x 41.82 mm x 1 mm and a lattice pitch pitch of 1.2 mm as shown in Fig. 1 under the following molding conditions with a polyester resin composition containing an inorganic filler, ).

The film gate of the long side (41.82 mm side) was used as the gate, and the gate thickness was 0.3 mm.

The obtained connector was placed on a horizontal desk and the height of the connector was measured using a Quickvision 404 PROCNC image measuring instrument manufactured by Mitsutoyo Corporation. At this 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 determined as flatness.

[Measurement of connector deformation amount]

Further, IR reflow was performed under the following conditions, flatness was measured by the above-described method, and the difference in flatness before and after reflow was determined as the amount of deformation of the connector.

~ Molding conditions ~

Molding machine; Sumitomo Heavy Industries Machinery SE30DUZ

Cylinder temperature;

     (Nozzles) 370 캜 -375 캜 -360 캜 -350 캜 (Examples 4 to 6)

             340 占 폚 -340 占 폚 -330 占 폚 -320 占 폚 (Comparative Example 8)

             370 占 폚 -375 占 폚 -360 占 폚 -350 占 폚 (Comparative Example 9)

             350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 10)

Mold temperature; 80 ℃

Injection speed; 300mm / sec

Beam pressure; 50 MPa

Hold time; 2 sec

Cooling time; 10sec

Screw rotation speed; 120rpm

Screw back pressure; 1.2 MPa

~ IR reflow condition ~

Measuring instrument; Japan Pulse Technology Laboratory Products Large table top reflow soldering machine RF-300

        (Using far infrared heater)

Sample transfer rate; 140mm / sec

Reflow furnace passing time; 5min

Temperature condition preheating zone; 150 캜, reflow zone; 225 占 폚, peak temperature; 287 ° C

[Connector Minimum Charging Pressure]

The minimum injection filling pressure at which a good molded article can be obtained when the planar connector of Fig. 1 is injection molded is defined as the connector minimum filling pressure.

[Load deformation temperature]

Each of the polyester resin compositions containing the inorganic filler was subjected to injection molding under the following molding conditions and measured according to ISO 75-1,2.

~ Molding conditions ~

Molding machine; Sumitomo Heavy Industries Machinery SE100DU

Cylinder temperature;

     (Nozzles) 370 캜 -375 캜 -360 캜 -350 캜 (Examples 4 to 6)

             340 占 폚 -340 占 폚 -330 占 폚 -320 占 폚 (Comparative Example 8)

      370 占 폚 -375 占 폚 -360 占 폚 -350 占 폚 (Comparative Example 9)

      350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 10)

Mold temperature; 80 ℃

Injection speed; 2m / min

Beam pressure; 50 MPa

Hold time; 2 sec

Cooling time; 10sec

Screw rotation speed; 120rpm

Screw back pressure; 1.2 MPa

[Crack resistance]

The molded article for evaluation as shown in Fig. 2 was injection-molded from the polyester resin composition containing the inorganic filler under the following molding conditions.

The injection molded article for evaluation shown in Fig. 2 has a diameter of 23.6 mm in outer diameter and 31 holes of 3.2 mm in diameter, and the minimum thickness of the inter-hole distance is 0.16 mm. The gate employs the three-point gate of the arrow in Fig. The occurrence of cracking around the hole was observed at a magnification of 5 times using a stereomicroscope to observe the fracture of the molded article. When the molded article was cracked, it was judged "x"

~ Molding conditions ~

Molding machine; Sumitomo Heavy Industries Machinery SE30DUZ

Cylinder temperature;

    (Nozzles) 370 캜 -375 캜 -360 캜 -350 캜 (Examples 4 to 6)

           340 占 폚 -340 占 폚 -330 占 폚 -320 占 폚 (Comparative Example 8)

           370 占 폚 -375 占 폚 -360 占 폚 -350 占 폚 (Comparative Example 9)

           350 ° C -350 ° C -340 ° C -330 ° C (Comparative Example 10)

Mold temperature; 140 ° C

Injection speed; 50mm / sec

Beam pressure; 100 MPa

Hold time; 2 sec

Cooling time; 10sec

Screw rotation speed; 120rpm

Screw back pressure; 1.2 MPa

[Example 1]

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

(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 85g (20.8 mol%) (BP)

Potassium acetate catalyst: 15 mg

Acetic anhydride: 229 g

After the raw materials were added, the temperature of the reaction system was raised to 140 캜, and the reaction was carried out at 140 캜 for 3 hours. The temperature was raised to 360 deg. C for 5.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) over 20 minutes from here, and molten polymerization was carried out while distilling out acetic acid, excess acetic anhydride and other low boiling point components. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the pressure from the reduced pressure state to the normal pressure, and the polymer was discharged from the lower part of the polymerization vessel.

The obtained polymer had a melting point of 357 占 폚, a crystallization temperature of 298 占 폚, a crystallization heat of 1.2 J / g, a softening temperature of 246 占 폚 and a melt viscosity of 16 Pa 占 퐏.

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 represented by using the abbreviations indicated in parentheses, such as HBA, HNA and the like.

[Examples 2 to 3]

Polymerization was carried out in the same manner as in Example 1 except that the kind of raw material monomer and the charging ratio were changed as shown in Table 1, and the polymer was discharged from the lower part of the polymerization vessel. The measurement results of 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 kind of raw material monomer and the charging ratio were changed as shown in Table 1, and the polymer was discharged from the lower part of the polymerization vessel. The measurement results of the physical properties of the obtained polymer are shown in Table 1. With respect to 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. Also in Table 1, APAP is 4-acetamidophenol.

In Table 1, it is found that the wholly aromatic polyester of Examples 1 to 3 has a high softening temperature and a crystallization heat amount of 1.8 J / g or less, and is excellent in heat resistance and toughness.

On the other hand, Comparative Example 2 in which RES was not used and Comparative Example 2 in which HNA + RES (general formula (II) + (IV)) was less than 4 mol% were decreased in toughness. Further, in Comparative Examples 3 and 4 in which HNA + RES (formula (II) + (IV)) exceeded 10 mol%, the heat resistance was poor. In Comparative Examples 6 and 7 in which the ratio of the raw material monomers (in particular, HBA) was outside the range of the present invention, the polymer could not be produced.

[Example 4]

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

(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: 62g (3.5 mol%) (RES)

(V) 4, 4'-dihydroxybiphenyl 620 g (20.8 mol%) (BP)

Potassium acetate catalyst: 110 mg

Acetic anhydride: 1676 g

After the raw materials were added, the temperature of the reaction system was raised to 140 캜, and the reaction was carried out at 140 캜 for 3 hours. Next, the temperature was raised to 360 deg. C over 5.5 hours, and the pressure was reduced to 5 Torr (i.e., 667 Pa) over 20 minutes from this point, and molten polymerization was carried out while distilling out acetic acid, excess acetic anhydride and other low- Respectively. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from the reduced pressure state to the atmospheric pressure state, and the polymer was discharged from the lower part of the polymerization vessel to pelletize the strands to form pellets.

The obtained polymer had a melting point of 355 캜, a crystallization temperature of 298 캜, a crystallization heat of 1.2 J / g and a melt viscosity of 10 Pa s.

To 100 parts by mass of the above pellets, 33.3 parts by mass of Mica (product of Yamaguchi Mica Co., Ltd., AB-25S, average particle diameter 25 m) were blended and kneaded in a twin-screw extruder to obtain a pelletized wholly aromatic polyester resin composition. The resulting resin composition was subjected to various tests such as physical property measurement and &quot; measurement of connector flatness &quot;. The results are shown in Table 2.

[Example 5]

A polymer was obtained in the same manner as in Example 4 except that the kind of raw material monomer and the charging ratio were changed as shown in Table 2. Subsequently, pelletization was carried out in the same manner as in Example 4. The obtained polymer had a melting point of 355 캜, a crystallization temperature of 298 캜, a crystallization heat of 1.2 J / g and a melt viscosity of 10 Pa s.

23.1 parts by mass of talc (Matsumura Industrial Co., Ltd., Crown Talc PP, average particle size of 12.8 占 퐉) and 100 parts by mass of glass fiber (ECS03T-786H, manufactured by Nippon Electric Glass Co., 10 탆, length 3 mm) 30.8 parts by mass were compounded and kneaded in a twin-screw extruder to obtain a pellet-shaped wholly aromatic polyester resin composition. The obtained resin composition was subjected to various tests such as physical property measurement and &quot; measurement of connector flatness &quot;. The results are shown in Table 2.

[Example 6]

A polymer was obtained in the same manner as in Example 4 except that the kind of raw material monomer and the charging ratio were changed as shown in Table 2. Subsequently, pelletization was carried out in the same manner as in Example 4. The obtained polymer had a melting point of 355 캜, a crystallization temperature of 298 캜, a crystallization heat of 1.2 J / g and a melt viscosity of 10 Pa s.

Further, 66.7 parts by mass of glass fiber was mixed and kneaded with 100 parts by mass of such pellets in a twin-screw extruder to obtain a pellet-shaped wholly aromatic polyester resin composition. The obtained resin composition was subjected to various tests such as physical property measurement and &quot; measurement of connector flatness &quot;. The results are shown in Table 2.

[Comparative Examples 8 to 10]

Polymers were obtained in the same manner as in Example 4 except that the kind of raw material monomer and the charging ratio were changed as shown in Table 2 in Comparative Examples 8 to 10. Subsequently, pelletization was carried out in the same manner as in Example 4. The polymer obtained in Comparative Example 8 had a melting point of 323 占 폚, a crystallization temperature of 276 占 폚, a crystallization heat amount of 2.0 J / g and a melt viscosity of 12 Pa 占 퐏. The polymer obtained in Comparative Example 9 had a melting point of 357 占 폚, a crystallization temperature of 305 占 폚, a crystallization heat of 2.1 J / g and a melt viscosity of 10 Pa 占 퐏. 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, 100 parts by mass of the pellets were compounded and kneaded in a biaxial extruder as shown in Table 2 to obtain a pellet-like wholly aromatic polyester resin composition. The resulting resin composition was subjected to various tests such as physical property measurement and &quot; measurement of connector flatness &quot;. The results are shown in Table 2.

In Table 2, all of the planar connectors of Examples 4 to 6 are found to be excellent in moldability, less deflection, flatness, heat resistance, and crack resistance. On the other hand, in Comparative Examples 8 to 10, all evaluations were not simultaneously regarded as good results.

Claims (10)

(I), (II), (III), (IV) and (V) as essential constituents and the constitutional unit (I) (IV) is contained in an amount of 2 to 8 mol%, the constituent unit of (V) is contained in an amount of 2 to 8 mol%, the constituent unit of (II) is contained in an amount of 2 to 8 mol% 0.5 to 29.5 mol%, and (II) + (IV) is 4 to 10 mol%.
[Chemical Formula 1]

The method according to claim 1,
A wholly aromatic polyester having a melt viscosity of 1 x 10 &lt; ⁵ &gt; Pa s or less at a temperature higher than the melting point of the wholly aromatic polyester by 10 to 40 DEG C at a shear rate of 1000 sec &lt; ^{-1 &} gt ;. 3. The method according to claim 1 or 2,
A wholly aromatic polyester having a melting point of 280 to 390 ° C. A polyester resin composition comprising 100 parts by mass of a wholly aromatic polyester according to any one of claims 1 to 3 and 120 parts by mass or less of an inorganic or organic filler. 5. The method of claim 4,
Wherein the inorganic filler is one or more kinds selected from glass fibers, mica and talc, and the amount of the inorganic filler is 20 to 80 parts by mass based on 100 parts by mass of the wholly aromatic polyester. A polyester molded article molded from 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 method according to claim 6,
A polyester molded article wherein the molded article is a heat-setting roll of a connector, a CPU socket, a relay switch part, a bobbin, an actuator, a noise reduction filter case, or an OA device. The method according to claim 6,
Wherein the molded article is a planar connector having a lattice structure inside the outer frame and a pitch interval of the lattice portion of 1.5 mm or less. The method according to claim 6,
Wherein the molded article is a polyester fiber. The method according to claim 6,
Wherein the molded article is a polyester film.

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