TWI675862B - Full aromatic liquid crystal polyester resin - Google Patents

Abstract

The present invention provides a wholly aromatic liquid crystal polyester resin with a high melting point and a low relative dielectric constant, which is composed of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid. It is made up of 100 mole% in total; the origin of the aromatic hydroxycarboxylic acid is composed of chemical formula (1); [化 1] The origin of the aromatic diol is composed of chemical formula (2), chemical formula (3) and / or chemical formula (4); [化 2] [Chemical 3] [Chemical 4] The constituent unit of aromatic dicarboxylic acid is composed of chemical formula (5), or chemical formula (5) and chemical formula (6); [化 5] [Chemical 6] And the Mohr% (total 100 Moll%) of each of the aforementioned constituent units is as follows: The composition of the constituent units of the chemical formula (1) is a predetermined range of the Moire%, and the composition of the chemical formulas (2), (3), (4) The sum of the composition of the units is a predetermined range of mole%, and the sum of the composition of the constituent units of the chemical formulas (5) and (6) is a predetermined range of mole%.

Description

Fully aromatic liquid crystal polyester resin

The present invention relates to a wholly aromatic liquid crystal polyester resin having a low relative dielectric constant.

The resin composition containing a wholly aromatic liquid crystal polyester resin has excellent soldering heat resistance, high rigidity and other mechanical characteristics, thin meat moldability, and low warpage. It is used as an injection molding material for various electronic component structures. . In recent years, the miniaturization, high performance, and high function of information equipment have progressed, and the signal transmission speed of personal computers, peripheral equipment, and digital communication equipment has continued to increase at a high speed.

In addition, for mobile phones and tablet-type terminal devices that have reached an alarmingly high penetration rate, it is predicted that the frequency used will gradually shift to the high-frequency band because of high functionality.

In addition, in recent years, electronics have also been developed for automotive applications, and it is expected that high-speed transmission will occur in car navigation systems, sensors for autonomous driving, and radars for collision prevention. Along with this, for wholly aromatic liquid crystal polyester resin compositions and films used as constituent materials of electronic parts (such as connectors for high-speed transmission or CPU sockets, printed circuit boards, insulating films, etc.), Requires low relative permittivity.

Proposals for solving such problems are roughly divided into two fields, and are carried out by compounding with hollow bodies (Patent Documents 1 to 3) and using fluorine-based monomers (Patent Document 4).

As a completely different approach from these proposals, the present inventors used aromatic aromatic carboxylic acids, aromatic diols, and aromatic dicarboxylic acids from the wholly aromatic liquid crystal polyester constituting monomers in aromatic diols. Used in 4,4'- The dihydroxybiphenyl derivative has finally completed the present invention.

The conventional 4,4'-dihydroxybiphenyl derivative may be a constituent monomer of a wholly aromatic liquid crystal polyester resin, and Patent Document 5 refers to a liquid crystal polyester resin (non-permanently aromatic) containing ethylene glycol in a constituent unit. Group liquid crystal polyester), a specific example of using tetramethylbiphenol as a biphenol alkyl derivative is proposed.

However, these facts or disclosures did not recognize the problem of the low relative permittivity requirements of information and communication machine components in recent years, and did not imply the use of 4,4'-dihydroxybiphenyl in wholly aromatic liquid crystal polyesters. Derivative effects of low relative permittivity.

Advance technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 2004-027021

[Patent Document 2] Japanese Patent Laid-Open No. 2004-143270

[Patent Document 3] Japanese Patent Laid-Open No. 2009-114418

[Patent Document 4] Japanese Patent Laid-Open No. 7-010978

[Patent Document 5] Japanese Patent Laid-Open No. 2000-026743

The object of the present invention is to provide a wholly aromatic liquid crystal polyester resin which can be used in information communication equipment. By specifying an aromatic diol component, the relative dielectric constant of the wholly aromatic liquid crystal polyester resin can be reduced, and the speed can be high. Transmission materials, components such as CPU sockets, printed circuit boards, and anti-collision radars.

As a result of an intensive review by the present inventor, it was found that, for the monomers constituting the wholly aromatic liquid crystal polyester resin, if the 4,4'-dihydroxybiphenyl derivative is used in an aromatic diol in a specific state, A polycondensation reaction is performed to obtain a wholly aromatic liquid crystal polyester resin composition and a film exhibiting low dielectric properties, and the present invention is finally completed.

A first aspect of the present invention relates to a wholly aromatic liquid crystal polyester resin, which includes an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid (including derivatives) represented by the following chemical formulas. Units, made up of 100 mol% in total; the constituent unit of the aromatic hydroxycarboxylic acid is composed of chemical formula (1);

(式中，R1為氫原子或碳數2以下之烷基，且R1中至少有一者為碳數2以下之烷基。又，R2為氫原子或碳數2以下之烷基，且R2中至少有一者為碳數2以下之烷基。) The constituent unit of aromatic diol is composed of chemical formula (2), chemical formula (3) and / or chemical formula (4);

(Wherein R1 is a hydrogen atom or an alkyl group having 2 or less carbon atoms, and at least one of R1 is an alkyl group having 2 or less carbon atoms. Also, R2 is a hydrogen atom or alkyl group having 2 or less carbon atoms, and R2 is At least one is an alkyl group having 2 or less carbon atoms.)

[Chemical 3]

The constituent unit of the aromatic dicarboxylic acid is composed of the chemical formula (5), or the chemical formula (5) and the chemical formula (6);

And the Mohr% relationship of these repeating units (all 100 Moll% in total) is as follows: 15 Molar% ≦ Chemical Formula (1) Composition ≦ 25 Molar%; 15 Molar% ≦ [Chemical Formula (2) Composition + Chemical Formula ( 3) Composition + composition of chemical formula (4)] ≦ 45 mole%; wherein the composition of chemical formula (2) (mol%) ≧ [chemical formula (3) composition + chemical formula (4) composition] (mol%); 15 mole % ≦ [composition of chemical formula (5) + composition of chemical formula (6)] ≦ 45 mole%; wherein the composition of chemical formula (5) (mol%) ≦ composition of chemical formula (6) (mol%).

A second aspect of the present invention is a wholly aromatic liquid crystal polyester tree related to the first aspect of the present invention. The melting point of the aforementioned wholly aromatic liquid crystal polyester resin is 310 ° C. or higher, and the relative dielectric constant at 10 GHz is 3.3 or less.

The third aspect of the present invention relates to the wholly aromatic liquid crystal polyester resin according to the first aspect of the present invention, wherein one of R1 is a methyl group, and R1 of the other three is a constituent unit represented by the chemical formula (2). A hydrogen atom, and one of R2 is a methyl group, and R2 of the other three is a hydrogen atom.

A fourth aspect of the present invention relates to a method for manufacturing a wholly aromatic liquid crystal polyester resin, which comprises polycondensing a total of 100 mol% of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid. The melting point of fully aromatic liquid crystal polyester resin is above 310 ° C, and the relative dielectric constant at 10 GHz is 3.3 or less; the aromatic hydroxycarboxylic acid is composed of chemical formula (7);

(式中，R1為氫原子或碳數2以下之烷基，且R1中至少有一者為碳數2以下之烷基。又，R2為氫原子或碳數2以下之烷基，且R2中至少有一者為碳數2以下之烷基。) The aromatic diol is composed of chemical formula (8), chemical formula (9) and / or chemical formula (10);

(Wherein R1 is a hydrogen atom or an alkyl group having 2 or less carbon atoms, and at least one of R1 is an alkyl group having 2 or less carbon atoms. Also, R2 is a hydrogen atom or alkyl group having 2 or less carbon atoms, and R2 is At least one is an alkyl group having 2 or less carbon atoms.)

[Chemical 10]

The aromatic dicarboxylic acid is composed of chemical formula (11), or chemical formula (11) and chemical formula (12);

And the Mohr% relationship of the constituent units derived from each of the foregoing monomers (total 100 Moire% in total) is as follows: 15 Moire% ≦ the composition of the constituent units derived from chemical formula (7) ≦ 25 Moore%; 15 Moire% ≦ [Composition of constituent units derived from chemical formula (8) + composition of constituent units derived from chemical formula (9) + composition of constituent units derived from chemical formula (10)] ≦ 45 mole%; of which the constituent units derived from chemical formula (8) Composition (Mole%) ≧ [Composition of constituent units derived from Chemical Formula (9) + Composition of constituent units derived from Chemical Formula (10)] (Mole%); 15 Mol% ≦ [Composition unit derived from Chemical Formula (11) Composition + composition of constituent units derived from chemical formula (12)] ≦ 45 mole%; of which composition of constituent units derived from chemical formula (11) (mol%) ≧ composition of constituent units derived from chemical formula (12) (mol %); And includes a step of melt polycondensation for all hydroxyl groups in (7), (8), (9), (10) by allowing 1.05 to 1.15 mol equivalent of acetic anhydride to be present under reflux of acetic acid.

A fifth aspect of the present invention relates to a method for manufacturing a fully aromatic liquid crystal polyester resin according to the fourth aspect of the present invention, wherein one of the aromatic diols represented by the chemical formula (8) is R1, and the other three Among them, R1 is a hydrogen atom, and one of R2 is a methyl group, and R2 of the other three is a hydrogen atom.

A sixth aspect of the present invention relates to a molded body composed of the wholly aromatic liquid crystal polyester resin described in any one of the first to third aspects of the present invention.

A seventh aspect of the present invention relates to a film composed of the wholly aromatic liquid crystal polyester resin described in any one of the first to third aspects of the present invention.

An eighth aspect of the present invention relates to an electronic component, which is composed of the wholly aromatic liquid crystal polyester resin described in any one of the first to third aspects of the present invention.

The wholly aromatic liquid crystal polyester resin of the present invention is a wholly aromatic polyester with solder heat resistance (melting point exceeding 310 ° C) and low relative permittivity. It is compounded with molding materials such as electronic parts, especially with various filling materials. After conversion, it is extremely useful as an injection molding material.

The fully aromatic liquid crystal polyester of the present invention can be measured for its melting point by thermal analysis of a differential scanning calorimeter (DSC). According to the inventor's discretion, if the melting point measured by the same method exceeds 310 ° C, it has sufficient solder resistance. Heat resistance.

Forms used to implement the invention

The wholly aromatic polyester resin of the present invention is obtained by polycondensing a total of 100 mol% of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid (including derivatives thereof. The same applies hereinafter).

The wholly aromatic polyester resin of the present invention is composed of a constituent unit derived from an aromatic hydroxycarboxylic acid. The formula (1) can be obtained by using, for example, p-hydroxybenzoic acid (chemical formula (7)).

In the wholly aromatic polyester of the present invention, the constituent unit (chemical formula (1)) is set to 15 mol% to 65 mol% (including a threshold value, the same applies hereinafter). It is preferably 20 mol% to 65 mol%, and further preferably 25 mol% to 60 mol%. If it is out of this range, heat resistance may be insufficient, and if it exceeds the range, a high molding temperature is required, and thermal decomposition may occur in the injection molding machine, so injection molding stability is not good.

In the wholly aromatic polyester resin of the present invention, there are three types of constituent units derived from aromatic diols, which are represented by chemical formula (2), chemical formula (3), and chemical formula (4). These can be obtained by using, for example, 4,4'-dihydroxybiphenyl derivative (chemical formula (8)), 4,4'-dihydroxybiphenyl derivative (chemical formula (9)), hydroquinone (chemical formula (10)).

(式中，R1為氫原子或碳數2以下之烷基，且R1中至少有一者為碳數2以下之烷基。又，R2為氫原子或碳數2以下之烷基，且R2中至少有一者為碳數2以下之烷基。)

(Wherein R1 is a hydrogen atom or an alkyl group having 2 or less carbon atoms, and at least one of R1 is an alkyl group having 2 or less carbon atoms. Also, R2 is a hydrogen atom or alkyl group having 2 or less carbon atoms, and R2 is At least one is an alkyl group having 2 or less carbon atoms.)

In the wholly aromatic polyester of the present invention, the constituent units shown by the chemical formulas (2), (3), and (4) are set to a total of 15 mol% to 45 mol%, and more preferably 20 mol% to 40 mol%. When it is out of this range, the dielectric constant is not sufficiently reduced, and when it exceeds the above range, solder heat resistance may be insufficient.

In any case, in the wholly aromatic polyester resin of the present invention, the molar number of the structural unit represented by the chemical formula (2) is the structural unit represented by the chemical formula (3) and the chemical formula (4). The sum of the respective mole numbers is more than. When the threshold is not met, the standard value of the low relative permittivity, that is, the phase at 10GHz The dielectric constant cannot sometimes be lower than 3.3.

In the wholly aromatic polyester of the present invention, the constituent units derived from an aromatic carboxylic acid are chemical formula (5) and chemical formula (6). This can be achieved by using, for example, terephthalic acid (chemical formula (11)), isophthalic acid (Chemical Formula (12)).

In the wholly aromatic polyester resin of the present invention, the constituent unit represented by the chemical formula (5) is set to 15 mol% to 45 mol%. When it is less than 15 mol%, moldability at the time of injection molding is poor, and when it exceeds 45 mol%, solder heat resistance may be reduced. In addition, the composition of the constituent unit of the chemical formula (5) ≧ the composition of the constituent unit of the chemical formula (6)] (mole%). When the threshold value is exceeded, solder heat resistance may decrease.

The wholly aromatic polyester resin of the present invention has a melting point of 310 ° C or higher. The relative dielectric constant at 10 GHz is 3.3 or less.

The melting point value is measured using, for example, a differential scanning calorimeter (DSC) manufactured by SEICO Electronics Co., Ltd. and using α-alumina as a reference. At this time, the temperature was raised from 20 ° C / min to room temperature to 390 ° C to completely melt the polymer, and then the temperature was lowered to 10 ° C / min and 50 ° C, and the temperature was further increased at a temperature of 20 ° C / min. The highest point of the endothermic peak obtained at 420 ° C can be determined as the melting point.

In addition, the relative dielectric constant value can be, for example, the liquid crystal polyester resin of the present invention thin-filmed (50 mm × 50 mm × 1 mm) by a compression stamping method (molding temperature + 20 ° C.) and analyzed by a network manufactured by Agilent Technologies. (8510C), using a fixture made of QWED, and measured by SPDR method (23 ° C, 10GHz).

As mentioned above, regarding each constituent unit, when overlooking the molecular structure, the wholly aromatic polyester resin of the present invention is a unit derived from both a p-aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid, and has at least one aromatic ring embedded therein. The family has a structure with strong main chain rigidity. Only in the constituent units derived from aromatic diols, it is arranged a carbon-carbon bond that can rotate freely, and an aromatic ring with a substituent having a carbon number of 2 or less.

The present inventors and others believe that by these differences, the following two effects can be efficiently and balancedly achieved: crystals or mesogens are formed due to aromatic hydroxycarboxylic acids and aromatic dicarboxylic acid moieties. , Which brings the heat resistance of the molded body and the high fluidity of the melt; and the dielectric constant of the bulkiness (also called the increase in free volume or the relaxation of tightness) due to the aromatic diol substituents decline. The density of the wholly aromatic polyester resin of the present invention will not exceed 1.36.

Regarding the aromatic diol (chemical formula (8)) which dominates the above-mentioned effect, in addition to the molar unit of the constituent unit, the substituent has a preferable range. From the viewpoint of bulkiness (increase in free volume), the larger the number of carbon atoms of the substituent is, the better, but it is preferable that the polycondensation reaction of the wholly aromatic liquid crystal polyester does not constitute a steric hindrance. From this point of view, the carbon number of the substituent is 2 or less, and the methyl group with 1 carbon number is more suitable. The number of generation bases should also be 2 or less. That is, it is most preferably a dimethyl derivative of a 4,4'-dihydroxybiphenyl derivative. Examples thereof include 3,3'-dimethyl-4,4'-dihydroxybiphenyl.

The manufacturing method of the wholly aromatic liquid crystal polyester resin according to the present invention may be a conventional method for manufacturing a liquid crystal polyester resin, and a manufacturing method using only melt polymerization or a two-stage polymerization using melt polymerization and solid phase polymerization may be used. Production method.

Among these methods, from the viewpoint that the wholly aromatic polyester compound of the present invention can be efficiently obtained, it is preferable to make a predetermined blend so that the constituent units of the chemical formula (7) to the chemical formula (12) total 100 mol%. For all the hydroxyl groups of the chemical formula (7) to the chemical formula (10) in these compounds, there is 1.05 to 1.15 mol equivalent of acetic anhydride and the melt polycondensation is performed under reflux of acetic acid.

In addition, if the molar equivalent of the acetic anhydride to be added greatly exceeds the above range, the reaction may not easily proceed or the heat resistance may be reduced.

For the polymer obtained by melt polymerization, when further solid-phase polymerization is performed, the prepolymer obtained by melt polymerization is pulverized after cooling and solidification to form a powder or a sheet. The solid-phase polymerization method is, for example, a method in which a prepolymer resin is heat-treated in an inert atmosphere such as nitrogen at a temperature range of 200 to 350 ° C for 1 to 30 hours. The solid-phase polymerization may be carried out while stirring or without stirring, and may be carried out in a static state.

For polymerization, catalysts can be used with or without catalyst. As the catalyst used, conventionally known polycondensation catalysts for polyesters can be used, and examples include magnesium acetate, first tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and dioxide. Metal salt catalysts such as antimony, nitrogen-containing heterocyclic compounds such as N-methylimidazole, etc., organic compound catalysts, etc.

The polymerization reaction apparatus for the melt polymerization is not particularly limited, and a reaction apparatus used for general high-viscosity fluid reaction is preferably used. Examples of such a reaction device include a stirring type polymerization reaction device, Or kneader, roller mill, Banbury closed mixer, etc. are generally used for resin kneading mixing equipment, etc., and the aforementioned stirring type polymerization reaction device has anchor type, multi-stage type, spiral belt type, spiral shaft type, etc. Or a stirring device of various shapes of the stirring blades which are deformed.

When the wholly aromatic polyester resin of the present invention is used as a material for injection molding, 10 to 40 parts by weight of ground glass fiber, talc, mica, glass flakes, clay, sericite, calcium carbonate, and silicic acid are melt-kneaded in accordance with ordinary examples. Fillers such as calcium, silicon dioxide, aluminum oxide, aluminum hydroxide, calcium hydroxide, graphite, amorphous carbon, potassium titanate, carbon fiber, and various whiskers can also be used as a resin composition. In addition to the foregoing, other fillers, colorants, dispersants, plasticizers, antioxidants, flame retardants, and the like may be added.

In addition, the wholly aromatic polyester resin of the present invention may be formed into a film by a conventional method. The film formation method may be any method such as blow molding, melt extrusion molding, and solution casting molding. The resin may be directly used, or the above additives may be added. Then, the formed film may be a single-layer film or a multilayer film composed of different materials.

Furthermore, for the purpose of improving dimensional stability and mechanical properties, the uniaxially or biaxially-stretched film may be processed by melt extrusion molding and solution casting molding. Moreover, you may heat-process for the purpose of removing the anisotropy of these films.

In addition, in the present invention, a so-called aromatic polyfunctional monomer can be used in a range that does not impair the effects of the present invention, and is used for the synthesis of a liquid crystal polyester. In particular, substituting a part of p-hydroxybenzoic acid with 6-hydroxy-2-naphthoic acid has the effect of reducing the molding processing temperature.

In addition, in the present invention, it may be mixed with other resins within a range that does not impair the effects of the present invention. Other resins include polyethylene terephthalate, polyethylene terephthalate, polycarbonate, polyarylate, polyamide, polyimide, polyether, polyetheretherketone, and polybenzene. Sulfide, polytetrafluoroethylene, etc.

The liquid crystal polyester of the present invention can be used as a low-dielectric material and an insulating material in the fields of electric and electronic industries, communication equipment industries, and the like. Examples include high-speed transmission connectors or CPU sockets, circuit boards, flexible circuit boards, laminated circuit boards, anti-collision radars, RFID tags, capacitors, inverter parts, insulating films, and lithium-ion batteries. Insulating materials for secondary batteries, speaker diaphragms, etc.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the following examples.

<Manufacture of wholly aromatic liquid crystal polyester resin>

(Example 1: Fully aromatic liquid crystal polyester resin (A))

In a 200 ml three-necked flask with a stirring wing, p-hydroxybenzoic acid (chemical formula (7)) 0.24 mol (40 mol%), 3,3'-dimethyl-4,4'-dihydroxybiphenyl (Chemical formula (8)) 0.12 mol (20 mol%), hydroquinone (chemical formula (10)) 0.06 mol (10 mol%), terephthalic acid (chemical formula (11)) 0.18 mol ( 30 mol%), 0.15 g of potassium acetate and 0.015 g of magnesium acetate as catalysts, and after depressurizing and nitrogen injecting the flask three times to perform nitrogen substitution, 66.15 g of acetic anhydride was further added (1.08 mol relative to the hydroxyl group). Equivalent), the rotation speed of the stirring blade was set to 200 rpm, the temperature was raised to 160 ° C., and the acetylation reaction was performed under reflux for 2 hours.

After the completion of the acetylation, the flask in the acetic acid distillation state was heated at 0.5 ° C / min. When the melt temperature in the tank became 307 ° C, the polymer was drawn out and cooled and solidified. The obtained polymer was pulverized to a size passing through a sieve having a pore size of 1.0 mm to obtain a prepolymer.

Next, the prepolymer obtained above was filled in a glass tube oven made by Shibata Scientific, and while rotating at a temperature of 20 ° C / hour from room temperature, the temperature was maintained at 290 ° C for 1 hour to perform solid-phase polycondensation. After that, while rotating the groove, the heat was naturally radiated at room temperature to obtain a wholly aromatic liquid crystal polyester. Resin A. The molten state of the same resin was observed under a polarizing microscope, and liquid crystallinity was confirmed from optical anisotropy.

(Example 2: Fully aromatic liquid crystal polyester resin (B))

The monomer of Example 1 was prepared and changed to 0.36 mol (60 mol%) of paraben and 3,3'-dimethyl-4,4'-dihydroxybiphenyl (20 mol). Ear%) and terephthalic acid 0.12 mol (20 mol%). A liquid crystal polyester resin was obtained in the same manner as described below, and liquid crystallinity was confirmed in the same manner as described above.

(Example 3: Fully aromatic liquid crystal polyester resin (C))

The monomer of Example 1 was prepared and changed to 0.15 mol (25 mol%) of paraben and 3,3'-dimethyl-4,4'-dihydroxybiphenyl (20 mol). Ear%), hydroquinone 0.105 mole (17.5 mole%), terephthalic acid 0.225 mole (37.5 mole%), the following operations were performed to obtain a liquid crystal polyester resin, and the liquid crystal was confirmed in the same manner as described above. Sex.

(Example 4: Fully aromatic liquid crystal polyester resin (D))

The monomer of Example 1 was prepared and changed to 0.12 mol (20 mol%) of paraben and 3,3'-dimethyl-4,4'-dihydroxybiphenyl (20 mol). Ear%), 4,4'-dihydroxybiphenyl (chemical formula (9)) 0.12 mole (20 mole%), terephthalic acid 0.24 mole (40 mole%). The liquid crystal polyester resin was checked for liquid crystallinity in the same manner as described above.

(Example 5: Fully aromatic liquid crystal polyester resin (E))

The monomer of Example 1 was prepared and changed to 0.12 mole (20 mole%) of paraben, 4,2'-dihydroxybiphenyl (20 mole%), and 3,3'- Dimethyl-4,4'-dihydroxybiphenyl 0.12 mole (20 mole%), terephthalic acid 0.15 mole (25 mole%), isophthalic acid (chemical formula (11)) 0.09 mole (15 mol%), a liquid crystal polyester resin was obtained in the same manner as described below, and liquid crystallinity was confirmed in the same manner as described above.

(Example 6: Fully aromatic liquid crystal polyester resin (F))

The monomer of Example 1 was prepared and changed to 0.12 mole (20 mole%) of paraben and 3,3'-dimethyl-4,4'-dihydroxybiphenyl (22.5 mole). Ear%), hydroquinone 0.105 mole (17.5 mole%), terephthalic acid 0.24 mole (40 mole%), the following operations were performed to obtain a liquid crystal polyester resin, and the liquid crystal was confirmed in the same manner as above. Sex.

(Example 7: Fully aromatic liquid crystal polyester resin (G))

The monomer of Example 1 was prepared and changed to 0.15 mol (25 mol%) of paraben and 3,3'-dimethyl-4,4'-dihydroxybiphenyl (0.12 mol). Ear%), hydroquinone 0.09 mol (15 mol%), terephthalic acid 0.225 mol (37.5 mol%), the same operation as described below was performed to obtain a liquid crystal polyester resin, and the liquid crystal was confirmed in the same manner as described above. Sex.

(Comparative Example 1: Fully aromatic liquid crystal polyester resin (H))

The monomer of Example 1 was prepared and changed to 0.36 mole (60 mole%) of paraben, 0.12 mole (20 mole%) of 4,4'-dihydroxybiphenyl, and 0.09 terephthalic acid. Molar (15 mol%) and isophthalic acid 0.03 mol (5 mol%) were obtained in the same manner as described below to obtain a liquid crystal polyester resin, and liquid crystallinity was confirmed in the same manner as described above.

(Characteristic measurement)

(Liquid crystal confirmation)

A polarizing microscope BH-2 manufactured by OLYMPUS Co., Ltd. equipped with a cooling and heating stage 10002 for microscopes manufactured by JAPAN HIGH TECH was used, and the polyester sample was heated and melted on the microscope heating stage. The magnification observation confirmed the liquid crystallinity from the presence or absence of optical anisotropy.

(Melting point measurement)

The melting point of the liquid crystal polyester resin was measured using a differential scanning calorimeter (DSC) manufactured by SEICO Electronics Industry Co., Ltd., using α-alumina as a reference. At this time, the temperature was raised from 20 ° C / min. After the temperature is raised to 390 ° C, the polymer is completely melted, and then the temperature is reduced to 10 ° C / min, and the temperature is reduced to 50 ° C, and the temperature is further increased to 20 ° C / min. Measured as the melting point.

(Determination of relative permittivity and dielectric tangent)

The compression-stamping method (molding temperature + 20 ° C) was used to thin the liquid crystal polyester resins A to H (50mm × 50mm × 1mm). The network analyzer (8510C) manufactured by Agilent Technologies was used for the analysis. The jig was measured by SPDR method (23 ° C, 10GHz).

(Density measurement)

The molded film prepared as described above was measured using an AUW220 specific gravity measuring device manufactured by Shimadzu Corporation.

The results are shown in Table 1. It can be seen that the wholly aromatic liquid crystal polyester resin of the present invention maintains solder heat resistance and has an excellent relative dielectric constant of 3.3 or less.

Industrial availability

The wholly aromatic liquid crystal polyester resin of the present invention is excellent in solder heat resistance and low relative permittivity, and can be used as a base resin for a wholly aromatic liquid crystal polyester resin composition. It is used in various parts of high-function information equipment. For example, connectors for high-speed transmission or CPU sockets, films for circuit boards, anti-collision radars, RFID tags, capacitors, inverter parts, insulating films, insulating materials for secondary batteries such as lithium-ion batteries, and speaker diaphragms material.

Claims (8)

A wholly aromatic liquid crystal polyester resin comprising 100 mol% of each constituent unit derived from an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid (including a derivative) represented by the following chemical formula. The origin of the aromatic hydroxycarboxylic acid is composed of chemical formula (1); The constituent unit of aromatic diol is composed of chemical formula (2), chemical formula (3) and / or chemical formula (4); (Wherein R1 is a hydrogen atom or an alkyl group having 2 or less carbon atoms, and at least one of R1 is an alkyl group having 2 or less carbon atoms. Also, R2 is a hydrogen atom or alkyl group having 2 or less carbon atoms, and R2 is At least one is an alkyl group having 2 or less carbon atoms.) The constituent unit of the aromatic dicarboxylic acid is composed of the chemical formula (5), or the chemical formula (5) and the chemical formula (6); And the Mohr% relationship of the foregoing constituent units (all 100 Moll% in total) is as follows: 15 Molar% ≦ Chemical Formula (1) Composition ≦ 25 Molar%; 15 Molar% ≦ [Chemical Formula (2) Composition + Chemical Formula ( 3) Composition + composition of chemical formula (4)] ≦ 45 mole%; wherein the composition of chemical formula (2) (mol%) ≧ [chemical formula (3) composition + chemical formula (4) composition] (mol%); 15 mole % ≦ [composition of chemical formula (5) + composition of chemical formula (6)] ≦ 45 mole%; wherein the composition of chemical formula (5) (mol%) ≧ the composition of chemical formula (6) (mol%). For example, the wholly aromatic liquid crystal polyester resin of the first patent application range, wherein the melting point of the foregoing wholly aromatic liquid crystal polyester resin is 310 ° C. or higher, and the relative dielectric constant at 10 GHz is 3.3 or less. For example, the wholly aromatic liquid crystal polyester resin of the first patent application scope, in which the constituent unit shown in chemical formula (2), one of R1 is a methyl group, R1 of the other three is a hydrogen atom, and one of R2 Is a methyl group, and R2 of the other three is a hydrogen atom. A method for manufacturing a wholly aromatic liquid crystal polyester resin, which comprises polycondensing a total of 100 mol% of aromatic hydroxycarboxylic acid, aromatic diol and aromatic dicarboxylic acid, and the melting point of the foregoing wholly aromatic liquid crystal polyester resin It is above 310 ° C, and the relative dielectric constant at 10 GHz is 3.3 or less; the aromatic hydroxycarboxylic acid is composed of chemical formula (7); The aromatic diol is composed of chemical formula (8), chemical formula (9) and / or chemical formula (10); (Wherein R1 is a hydrogen atom or an alkyl group having 2 or less carbon atoms, and at least one of R1 is an alkyl group having 2 or less carbon atoms. Also, R2 is a hydrogen atom or alkyl group having 2 or less carbon atoms, and R2 is At least one is an alkyl group having 2 or less carbon atoms.) The aromatic dicarboxylic acid is composed of chemical formula (11), or chemical formula (11) and chemical formula (12); And the Mohr% relationship of the constituent units derived from each of the foregoing monomers (total 100 Moire% in total) is as follows: 15 Moire% ≦ the composition of the constituent units derived from chemical formula (7) ≦ 25 Moore%; 15 Moire% ≦ [Composition of constituent units derived from chemical formula (8) + composition of constituent units derived from chemical formula (9) + composition of constituent units derived from chemical formula (10)] ≦ 45 mole%; of which the constituent units derived from chemical formula (8) Composition (Mole%) ≧ [Composition of constituent units derived from Chemical Formula (9) + Composition of constituent units derived from Chemical Formula (10)] (Mole%); 15 Mol% ≦ [Composition unit derived from Chemical Formula (11) Composition + composition of constituent units derived from chemical formula (12)] ≦ 45 mole%; of which composition of constituent units derived from chemical formula (11) (mol%) ≧ composition of constituent units derived from chemical formula (12) (mol %); And a step of melt-condensing all hydroxy groups in (7), (8), (9), and (10) by allowing 1.05 to 1.15 molar equivalents of acetic anhydride to be present under reflux of acetic acid. For example, in the method for manufacturing a wholly aromatic liquid crystal polyester resin according to item 4 of the patent application, in the aromatic diol represented by chemical formula (8), one of R1 is a methyl group, and R1 of the other three is a hydrogen atom, and One of R2 is a methyl group, and R2 of the other three is a hydrogen atom. A molded body is composed of a wholly aromatic liquid crystal polyester resin according to any one of claims 1 to 3. A film is composed of a wholly aromatic liquid crystal polyester resin according to any one of claims 1 to 3. An electronic part is composed of a wholly aromatic liquid crystal polyester resin according to any one of the scope of claims 1 to 3.