KR20110004283A - Method for producing liquid-crystalline polyester - Google Patents

Abstract

PURPOSE: A method for producing liquid crystal polyester is provided to enable the efficient production of liquid crystal polyester with a high polymerization degree. CONSTITUTION: A method for producing liquid crystal polyester comprises: a melt polycondensation step for preparing liquid crystal polyester with a low polymerization degree through melt polycondensation; a grinding step for grinding the manufactured liquid crystal polyester; and a solid phase polymerization step for preparing liquid crystal polyester with a high polymerization degree through solid phase polymerization of the ground liquid crystal polyester.

Description

Manufacturing method of liquid crystalline polyester {METHOD FOR PRODUCING LIQUID-CRYSTALLINE POLYESTER}

TECHNICAL FIELD This invention relates to the manufacturing method of liquid crystalline polyester suitable for using as an insulating resin base material for electronic devices, such as a printed wiring board (printed board and a printed circuit board) and a package board | substrate.

In this type of electronic device, an insulating resin substrate used by attaching a conductive layer to a surface is used, and the insulating resin substrate is required to have properties such as heat resistance, electrical characteristics, low hygroscopicity, and dimensional stability. Conventionally, as such an insulating resin base material, the base material which impregnated the epoxy resin in the glass cross has been used widely.

By the way, as the digital signal propagation speed of electronic devices has recently increased (hundreds of MHz or more), the high frequency of the digital signal frequency has been advanced, and an insulating resin base material having higher electrical characteristics (low dielectric loss tangent) is desired. . Therefore, it is a situation that the base material which impregnated the epoxy resin in the conventional glass cross cannot necessarily correspond enough.

Therefore, in order to meet such a request, for example, Patent Document 1 proposes a resin-impregnated base material impregnated with a solvent-soluble liquid crystalline polyester, and discloses that in addition to high electrical properties, solder heat resistance can be maintained. . This solvent-soluble liquid crystalline polyester has an amide bond in a part of bond. As a method of making high molecular weight of such liquid crystalline polyester, after obtaining a low molecular weight liquid crystalline polyester by melt polycondensation, the method of high molecular weighting this liquid crystalline polyester by solid state polymerization was known. (See, for example, Japanese Laid-Open Patent Publication No. 2007-146139)

However, when industrially manufacturing by applying the well-known technique 1 to the liquid-crystal polyester of a specific structure, especially the liquid-crystal polyester containing many amide bonds, there existed a subject that productivity could not be improved by the following manufacturing problems.

First, in the melt polycondensation step, when liquid crystal polyester having a flow initiation temperature of 250 ° C. or more is prepared in order to maintain high solder heat resistance, the liquid crystal polyester becomes semi-solidified and loses fluidity. It cannot be taken out from the reaction vessel.

Secondly, in the solid phase polymerization step, even when the powdery liquid crystal polyester is subjected to the solid phase polymerization, the liquid crystal polyester changes from a powder state into a molten state at a reaction temperature of about 170 ° C, so that a large amount of liquid crystal polyester adheres to the tray. As a result, the yield of liquid crystalline polyester falls significantly. When the liquid crystal polyester is polymerized in the solid phase at a reaction temperature of less than 160 ° C, the liquid crystal polyester remains in a powder state, but the flow start temperature of the liquid crystal polyester, that is, the degree of polymerization is hardly improved.

Then, in view of such a situation, an object of this invention is to provide the manufacturing method of the liquid crystal polyester which can manufacture high polymerization liquid crystal polyester industrially with high efficiency.

As a result of earnestly examining by this inventor in order to achieve such an objective, in the melt polycondensation process, in order to be able to extract liquid crystalline polyester from a reaction container in a molten state, while reducing the molecular weight of liquid crystalline polyester, In the subsequent solid-phase polymerization process, in order to raise the polymerization degree of this liquid crystalline polyester, it focused on carrying out two-step solid-state polymerization with respect to liquid crystalline polyester, and came to complete this invention.

That is, the invention according to claim 1 includes a melt polycondensation step of preparing a low-polymerization liquid crystal polyester by melt polycondensation, a pulverization step of pulverizing the liquid crystal polyester prepared in the melt polycondensation step, and the pulverization step A method for producing a liquid crystal polyester comprising a solid phase polymerization step of preparing a high polymerization degree liquid crystal polyester by solid phase polymerization from a liquid crystal polyester pulverized in the above, wherein in the melt polycondensation step, a liquid crystal having a flow start temperature of 220 ° C. or lower A polyester is prepared and the solid polymer is prepared by heating the liquid crystal polyester prepared in the said melt polycondensation process at the reaction temperature of 180 degreeC or more, and solidifying in the said solid-phase polymerization process, and grind | pulverizing this solid polymer. And then solidified by heating to liquid crystal polyester It characterized in that one of the production method.

Moreover, the invention of Claim 2 has the structural unit represented by following formula (1), (2) and (3) in addition to the structure of Claim 1, and total content of all the structural units. About content of the structural unit represented by Formula (1) is 20-70 mol%, content of the structural unit represented by Formula (2) is 40-15 mol%, and content of the structural unit represented by Formula (3) is 40- It is 15 mol% of liquid crystalline polyester, It is characterized by the above-mentioned.

(1) -O-Ar ¹ -CO-

(2) -CO-Ar ² -CO-

(3) -X-Ar ³ -Y-

(In the formula, Ar ¹ represents a phenylene group or a naphthylene group, Ar ² represents a phenylene group, a naphthylene group or a group represented by the following formula (4), and Ar ³ represents a group represented by a phenylene group or the following formula (4). And X and Y each independently represent O or NH. The hydrogen atoms in the groups represented by Ar ¹ , Ar ² or Ar ³ may be each independently substituted with a halogen atom, an alkyl group or an aryl group.)

(4) -Ar ¹¹ -Z-Ar ^12-

(In the formula, Ar ¹¹ And Ar ¹² each independently represent a phenylene group or a naphthylene group, and Z represents O, CO or SO ₂ )

Moreover, in addition to the structure of Claim 2, invention of Claim 3 is at least one of X and Y of the structural unit represented by said Formula (3), It is characterized by the above-mentioned.

Moreover, in addition to the structure of any one of Claims 1-3, the invention of Claim 4 made the reaction temperature of the solid-phase polymerization of the said liquid crystalline polyester to 280 degreeC or less in the said solid-state polymerization process, It is characterized by the above-mentioned. .

And in addition to the structure of any one of Claims 1-4, invention of Claim 5 made the reaction temperature of the solid-state polymerization of the said solid polymer into 180 degreeC or more in the said solid-state polymerization process, It is characterized by the above-mentioned. do.

According to the present invention, the liquid crystal polyester prepared in the melt polycondensation step is a low molecular weight having a flow start temperature of 220 ° C. or lower, so that the liquid crystal polyester can be maintained and the liquid crystal polyester can be easily extracted from the reaction vessel. can do. Moreover, in a solid-phase polymerization process, by setting the lower limit of the reaction temperature of solid-state polymerization of liquid crystalline polyester to 180 degreeC, the amount of solidification shrinkage at the time of cooling of liquid crystalline polyester can be increased, and peelability can be improved.

As a result of these, it is possible to manufacture high-polymerization liquid crystalline polyester industrially with high efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS It is process drawing which shows the manufacturing method of the liquid crystal polyester which concerns on Embodiment 1 of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

[Embodiment 1 of the invention]

1 shows Embodiment 1 of the present invention. In this Embodiment 1, the structure and the manufacturing method are demonstrated in order about the liquid crystal polyester of a specific structure.

<Configuration of Liquid Crystal Polyester>

The liquid crystalline polyester which concerns on this invention is polyester with the characteristic which shows optical anisotropy at the time of melting, and forms an anisotropic melt at the temperature of 450 degrees C or less. As this liquid crystalline polyester, the structural unit represented by following formula (1) (henceforth a "formula (1) structural unit"), and the structural unit represented by following formula (2) (hereinafter, "formula (2) structure Unit ”) and a structural unit represented by the following formula (3) (hereinafter referred to as“ formula (3) structural unit ”), and the total content of all structural units (of each structural unit constituting the liquid crystal polyester). By dividing the mass by the formula amount of each structural unit, the content of the structural unit is 20 to 70 mol% based on the value obtained by calculating the content of each structural unit by the amount equivalent to the amount of the substance (mol) and totaling them). It is preferable that content of a formula (2) structural unit is 40-15 mol%, and content of a formula (3) structural unit is 40-15 mol%.

(1) -O-Ar ¹ -CO-

(2) -CO-Ar ² -CO-

(3) -X-Ar ³ -Y-

(In the formula, Ar ¹ represents a phenylene group or a naphthylene group, Ar ² represents a phenylene group, a naphthylene group or a group represented by the following formula (4), and Ar ³ represents a group represented by a phenylene group or the following formula (4). And X and Y each independently represent O or NH, and the hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ may be each independently substituted with a halogen atom, an alkyl group or an aryl group)

(4) -Ar ¹¹ -Z-Ar ^12-

(In the formulas, Ar ¹¹ and Ar ¹² each independently represent a phenylene group or a naphthylene group, and Z represents O, CO, or SO ₂ ).

Here, the structural unit of formula (1) is a structural unit derived from aromatic hydroxycarboxylic acid, and as this aromatic hydroxycarboxylic acid, p-hydroxy benzoic acid, m-hydroxy benzoic acid, 2-hydroxy Hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, etc. are mentioned.

In addition, the structural unit of formula (2) is a structural unit derived from aromatic dicarboxylic acid, and as this aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, diphenyl ketone-4,4'-dicarboxylic acid, etc. Can be mentioned.

The structural unit of formula (3) is a structural unit derived from an aromatic amine or an aromatic diamine having an aromatic diol and a phenolic hydroxyl group (phenolic hydroxyl group). As this aromatic diol, for example, hydroquinone, resorcin, 1,2-benzenediol, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl ) Ether, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, etc. are mentioned.

Moreover, as aromatic amine which has this phenolic hydroxyl group, p-aminophenol, 3-aminophenol, etc. are mentioned, As aromatic diamine, 1, 4- phenylenediamine, 1, 3- phenylenediamine Etc. can be mentioned.

In the liquid crystal polyester according to the present invention, when the structural unit of formula (2) is resorcin, 1,2-benzenediol as its aromatic diol, and / or isophthalic acid as its aromatic dicarboxylic acid, When the structural unit is a resorcin, 1,2-benzenediol as the aromatic diol, and / or a structural unit derived from an aromatic amine or aromatic diamine having a phenolic hydroxyl group, the solvent is soluble. It becomes liquid crystalline polyester of.

Such solvent solubility means melt | dissolving in a solvent (solvent) at the temperature of 50 degreeC in 1 mass% or more. The solvent in this case is any one of solvents suitable for dissolving the liquid crystal polyester according to the present invention to prepare a liquid composition (solution composition), and details thereof will be described later.

As liquid crystalline polyester which has such solvent solubility, it is preferable to contain the structural unit derived from the aromatic amine and / or aromatic diamine which have a phenolic hydroxyl group as said structural unit of said Formula (3). That is, it is preferable that at least one of X and Y contains a structural unit which is NH as a structural unit represented by Formula (3), and substantially all structural formula (3) structural units are represented by the following formula (3 '). It is more preferable that it is (hereinafter referred to as "formula (3 ') structural unit").

(3 ')-X-Ar ³ -NH-

(Wherein Ar ³ and X have the same meaning as above)

The structural unit of the formula (3 ') is more preferably contained in the range of 40 to 15 mol% with respect to the total content of all the structural units, and more preferably in the range of 35 to 20 mol%. By doing so, solvent solubility is further improved. Thus, the liquid crystalline polyester which has a formula (3 ') structural unit as a formula (3) structural unit is further excellent in the solubility to a solvent, and manufacture of the insulated resin base material using the liquid composition mentioned later becomes easier. There is also an advantage.

The structural unit of formula (1) is 20 to 70 mol% with respect to the total content of all the structural units, and it is more preferable if it is 25 to 55 mol%. The liquid crystalline polyester containing a structural unit of Formula (1) by such a mole fraction tends to be more excellent in solubility to a solvent, while maintaining liquid crystallinity sufficiently. And as aromatic hydroxycarboxylic acid which guide | induces a structural unit of formula (1), p-hydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid are preferable at the point which can be obtained easily. 2-hydroxy-6-naphthoic acid is preferable from the viewpoint of improving the solvent solubility of the liquid crystalline polyester and decreasing the dielectric loss tangent.

Formula (2) is a range of 40-15 mol% with respect to the total content of all the structural units, and it is more preferable if it is 37.5-22.5 mol%. The liquid crystalline polyester containing a structural unit of Formula (2) by such a mole fraction tends to be more excellent in solubility to a solvent, while maintaining liquid crystallinity sufficiently. As aromatic dicarboxylic acid which guide | induces a structural unit of formula (2), at least 1 sort (s) chosen from the group which consists of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid is easily obtained at the point which can be obtained easily. . Isophthalic acid is preferable from the viewpoint of solvent solubility improvement of liquid crystalline polyester, and 2, 6- naphthalenedicarboxylic acid is preferable from a viewpoint of lowering of dielectric loss tangent.

In addition, the mole fraction of a structural unit of formula (2) and a structural unit of formula (3) is [formula (2) structural unit] / [formula (3) from the point which liquid crystalline polyester obtained shows higher liquid crystalline. Structural unit], the range of 0.9 / 1-1 / 0.9 is preferable.

<Method for producing liquid crystal polyester>

Next, the manufacturing method of the liquid crystal polyester which concerns on this invention is demonstrated based on FIG.

First, in the addition process (step S1 of FIG. 1), after inject | pouring powdery raw material monomer, it transfers to an acylation process (step S2 of FIG. 1), acylating this raw material monomer, and ester formation property and amide formation property. Convert to derivatives. Thus, the method of acylating a raw material monomer before melt polycondensation mentioned later is preferable because operation is easy.

Here, the ester-forming and amide-forming derivatives will be described by way of example.

As ester-forming and amide-forming derivatives of monomers having a carboxyl group, such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid, acid chlorides and acid anhydrides so as to promote the reaction in which the carboxyl group forms a polyester or a polyamide. The thing which becomes group with high reaction activity, etc., What forms ester with alcohol, ethylene glycol, etc. so that the said carboxyl group may produce polyester and a polyamide by transesterification-amide exchange reaction, etc. are mentioned.

As ester-forming and amide-forming derivatives of monomers having phenolic hydroxyl groups, such as aromatic hydroxycarboxylic acids and aromatic diols, phenolic hydroxides are produced so as to produce polyesters or polyamides by transesterification reactions. The actual group forms ester with carboxylic acid, etc. are mentioned.

Moreover, as an amide forming derivative of the monomer which has an amino group like aromatic diamine, the amino group forms carboxylic acid and an amide, etc. so that polyamide may be produced | generated by an amide exchange reaction, etc. are mentioned, for example. .

Among these, in manufacturing liquid crystal polyester more easily, the monomer which has aromatic hydroxycarboxylic acid, phenolic hydroxyl group and / or amino group, such as aromatic diol, aromatic amine which has phenolic hydroxyl group, and aromatic diamine, After acylating with a fatty acid anhydride to form an ester-forming and amide-forming derivative (acylate), the acyl group of the acyl group and the carboxyl group of the monomer having a carboxyl group are polymerized to cause transesterification and amide exchange, thereby polymerizing the liquid crystal. Particular preference is given to a process for producing the ester.

The manufacturing method of such liquid crystalline polyester is described, for example in Unexamined-Japanese-Patent No. 2002-220444 or Unexamined-Japanese-Patent No. 2002-146003.

In acylation, it is preferable that the usage-amount of fatty acid anhydride is 1-1.2 times equivalent with respect to the sum total of a phenolic hydroxyl group and an amino group, and it is more preferable if it is 1.05-1.1 times equivalent. When the amount of the fatty acid anhydride used is less than 1 equivalent, the acyl compound and the raw material monomer tend to sublimate during polymerization, and the reaction system tends to be blocked. When the amount exceeds 1.2 times, the coloration of the obtained liquid crystal polyester is remarkable. There is a tendency to lose.

It is preferable to make acylation react at 130-180 degreeC for 5 minutes-10 hours, and it is more preferable to make it react at 140-160 degreeC for 10 minutes-3 hours.

The fatty acid anhydride used for the acylation is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride or a mixture of two or more selected from these, and particularly preferably acetic anhydride from the viewpoint of price and handleability.

Next, it transfers to a melt polycondensation process (step S3 of FIG. 1), and prepares low-polymerization liquid crystal polyester (specifically, liquid crystal polyester whose flow start temperature is 220 degrees C or less) by melt polycondensation.

At this time, it is preferable to perform melt polycondensation following acylation, heating up at a ratio of 0.1-50 degreeC / min at 130-400 degreeC, heating up at a rate of 0.3-5 degreeC / min at 150-350 degreeC It is more preferable to carry out.

Moreover, in melt polycondensation, it is preferable that the acyl group of an acylide is 0.8-1.2 times equivalent of a carboxyl group.

During acylation and / or melt polycondensation, the equilibrium is shifted according to the Le Chatelier-Brown law (the principle of equilibrium transfer). desirable.

Moreover, you may carry out in the presence of a catalyst in acylation and melt polycondensation. As such a catalyst, what has conventionally been known as a catalyst for the polymerization of polyester can be used. For example, magnesium acetate, tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, etc. And organic compound catalysts such as metal salt catalysts, N, N-dimethylaminopyridine and N-methylimidazole.

However, since the catalyst containing a metal affects the electrical characteristics at the time of manufacturing a semiconductive resin belt, nitrogen atoms, such as N, N- dimethylamino pyridine and N-methylimidazole, among these catalysts, too. Heterocyclic compounds containing two or more of them are preferably used (see, for example, Japanese Unexamined Patent Publication No. 2002-146003).

This catalyst is usually added together at the time of input of the raw material monomer, and does not necessarily have to be removed even after acylation. When the catalyst is not removed, the catalyst can be transferred to the melt polycondensation as it is in the same state.

The low-polymerization liquid crystalline polyester obtained in this melt polycondensation step needs to have a flow start temperature of 220 ° C. or lower in consideration of dischargeability (easiness of extraction) from the reaction vessel. Preferably it is 160-215 degreeC, More preferably, it is 170-210 degreeC. When the flow start temperature is higher than 220 ° C., solidification of the liquid crystal polyester is promoted in the reaction vessel, and the discharge of the liquid crystal polyester becomes difficult.

In the evaluation of the melt viscosity by a flow tester, the flow start temperature referred here refers to a temperature at which the melt viscosity of the liquid crystal polyester becomes 4800 Pa · s or less under a pressure of 9.8 MPa (100 kg / cm 2). Moreover, this flow start temperature is a fact well-known to those skilled in the art as a reference of the molecular weight of liquid crystalline polyester. See June 5).

Thereafter, the process proceeds to a cooling and solidifying step (step S4 in FIG. 1), and the liquid crystal polyester is cooled and solidified.

Next, it transfers to a grinding | pulverization process (step S5 of FIG. 1), and liquid crystal polyester is grind | pulverized. This results in a powder or flake prepolymer.

Thereafter, in order to further improve the solder heat resistance, the prepolymer thus obtained is subjected to high molecular weight by two stages of solid state polymerization. Here, in order to maintain high solder heat resistance, it is necessary to make the flow start temperature of liquid crystalline polyester 260 degreeC or more. Therefore, the solid-phase polymerization is applied by heating at a reaction temperature of 180 ° C. or higher to melt the liquid crystal polyester, and after cooling to give a solid polymer (one-step solid-state polymerization), the solid polymer is then pulverized, and the reaction temperature is 180 ° C. or higher again. Heat is applied (two stage solid phase polymerization).

That is, it transfers first to a solid-state polymerization process (step S6 of FIG. 1), and solid-polymerizes this prepolymer, and prepares a solid polymer.

Regarding this one-stage solid phase polymerization, the liquid crystal polyester after grinding | pulverization is heat-processed in solid state for 5 minutes-30 hours at reaction temperature of 180-280 degreeC in atmosphere of inert gas, such as nitrogen, for example. It can be carried out. Preferable reaction temperature is 180-240 degreeC, More preferably, it is 200-240 degreeC. By one-step solid phase polymerization, the powdery or flake-shaped prepolymer is changed into a solid polymer by fusion.

Here, when reaction temperature is less than 180 degreeC, the fusion of the solid polymer obtained after 1st solid-state polymerization and a solid-state polymerization reaction container is strong, and since it does not peel easily, a yield will fall remarkably. Moreover, when reaction temperature exceeds 280 degreeC, since the liquid crystal polyester obtained after the two-step solid-state superposition | polymerization mentioned later tends to be colored, it is unpreferable.

Then, the solid polymer obtained by the one-step solid phase polymerization is taken out from the reaction vessel.

Subsequently, the process proceeds to the pulverization process (step S7 in FIG. 1), and the solid polymer is pulverized into powder or flake form.

Finally, the process proceeds to the ash solid polymerization process (step S8 in FIG. 1), and the powdery or flake solid polymer is solidified. As a result, liquid-crystal polyester whose flow start temperature is 260 degreeC or more is obtained.

Regarding this two-stage solid state polymerization, the liquid crystal polyester after pulverizing a solid polymer is heat-processed in the solid state state for 5 minutes-30 hours at 180-350 degreeC of reaction temperature in the atmosphere of inert gas, such as nitrogen, for example. Can be carried out by an operation.

Here, from the viewpoint of stably obtaining the liquid crystalline polyester of the preferable flow start temperature mentioned later, in detail, preferable conditions of solid state polymerization are preferable, as reaction temperature, it is more than 200 degreeC, More preferably, it is 210 degreeC-350 It is the range of ° C. It is preferable that reaction time is chosen from 1 to 10 hours.

Moreover, it is preferable from the viewpoint of heat resistance that the flow start temperature of the liquid crystalline polyester which concerns on this invention is 260 degreeC or more and 380 degrees C or less. When the flow start temperature is 330 ° C. or lower, in addition to the better solubility of the liquid crystalline polyester in the solvent, when the liquid crystalline polyester of the present invention is dissolved in a solvent to obtain a liquid composition, the viscosity is not significantly increased. Since it does not, there exists a tendency for the handleability of this liquid composition to become favorable. From such a viewpoint, the liquid crystal polyester whose flow start temperature is 260 degreeC or more and 320 degrees C or less is more preferable. Moreover, what is necessary is just to optimize the polymerization conditions of the said solid state polymerization suitably in order to control the flow start temperature of liquid crystalline polyester to such a preferable range.

Here, the manufacturing process of liquid crystalline polyester is complete | finished.

As described above, in the first embodiment, since the liquid crystal polyester prepared in the melt polycondensation step is made to have a low molecular weight of 220 ° C. or less at the fluidization start temperature, the fluidity of the liquid crystal polyester is maintained and the liquid crystal polyester is reacted. It can be made easy to extract from a container.

Moreover, in the solid-state polymerization process, since the lower limit of the reaction temperature of solid-state polymerization of liquid crystalline polyester was 180 degreeC, the amount of solidification shrinkage at the time of cooling of liquid crystalline polyester can be increased, and peelability can be improved.

As a result, it becomes possible to manufacture highly polymerizable liquid crystalline polyester (liquid crystalline polyester whose flow start temperature is 260 degreeC or more) industrially with high efficiency.

Moreover, when manufacturing liquid crystalline polyester in this way, what is necessary is just to set reaction conditions, such as the temperature rising conditions in a melt polycondensation process, reaction temperature, reaction time, etc. in a solid state polymerization process and a stock polymerization process, Existing liquid crystal polyester production equipment can be used as it is. Therefore, manufacturing cost of liquid crystalline polyester can be suppressed and it is excellent in economic efficiency.

[Other Embodiments of the Invention]

Moreover, in Embodiment 1 mentioned above, the case where the acylation process was provided before the melt polycondensation process was demonstrated, It is also possible to omit this acylation process depending on the kind of raw material monomer to be used.

Example

Hereinafter, although the Example of this invention is described, this invention is not limited to an Example.

Synthesis Example 1

A relatively low molecular weight prepolymer was prepared as follows.

That is, 19.8 kg (105 mol) of 2-hydroxy-6-naphthoic acid and 14.7 kg (97.5 mol) of 4-hydroxyacetoanilides in a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer, and a reflux condenser. ), 16.2 kg (97.5 mol) of isophthalic acid and 23.8 kg (233 mol) of acetic anhydride were added. After sufficiently replacing the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 30 minutes under a nitrogen gas stream, and the temperature was maintained at 150 ° C. for reflux for 3 hours.

Then, while distilling off the by-product acetic acid and unreacted acetic anhydride distilled off, it heated up to 300 degreeC over 240 minutes, and after reaching 300 degreeC, it took out continuously continuously in thin plate shape on the belt conveyor with water cooling apparatus. It was. The plate-like content taken out in this way was pulverized by the grinder, and the comparatively low molecular weight powdery prepolymer was obtained.

Example 1

A tray made of SUS (manufactured by Nagaoka Metal Industry Co., Ltd., 30 cm × 40 cm × 66 cm) was prepared as a solid phase polymerization reaction vessel, and 3.0 kg of the prepolymer obtained in Synthesis Example 1 was filled into this SUS tray, and then 1 hour. It heated up from 30 degreeC to 220 degreeC over 35 minutes, and then thermally polymerized by keeping warm at the same temperature (220 degreeC) for 5 hours (one-phase solid-state polymerization). Then, as a result of cooling this, solid liquid crystal polyester (henceforth "liquid crystal polyester A") was obtained. This liquid crystal polyester A was grind | pulverized with the grinder, and powdery liquid crystal polyester A was obtained.

Subsequently, 2.5 kg of the powdery liquid crystalline polyester A obtained in this way were charged to the said SUS tray, and it heated up from 30 degreeC to 180 degreeC over 1 hour, and then 215 at the same temperature (180 degreeC) over 5 hours 50 minutes. It heated up to ° C, and then maintained at the same temperature (215 ° C) for 5 hours to perform solid phase polymerization (two-stage solid phase polymerization). Then, as a result of cooling this, powdery liquid crystalline polyester was obtained.

[Example 2]

A powdery liquid crystalline polyester was obtained by the same method as in Example 1 described above except that the reaction temperature in the one-step solid phase polymerization was 180 ° C.

Example 3

A powdery liquid crystalline polyester was obtained by the same method as in Example 1 described above except that the reaction temperature in the one-step solid phase polymerization was 200 ° C.

Example 4

A powdery liquid crystal polyester was obtained by the same method as in Example 1 described above except that the reaction temperature in the one-step solid phase polymerization was 210 ° C.

Example 5

Powdery liquid crystalline polyester was obtained by the method similar to Example 1 mentioned above except the reaction temperature in 1st stage solid-state polymerization was 240 degreeC.

Comparative Example 1

3.0 kg of the prepolymer obtained in Synthesis Example 1 was charged into a tray made of SUS similar to that of Example 1, and the temperature was raised from 30 ° C to 170 ° C over 1 hour and 10 minutes, followed by thermal insulation at the same temperature (170 ° C) for 5 hours. Polymerized. Then, as a result of cooling this, solid liquid crystal polyester was obtained.

[Measurement of Flow Start Temperature]

About the synthesis example 1, Example 1, Example 2, Example 3, Example 4, Example 5, and the comparative example 1 which were obtained in this way, the flow start temperature of liquid crystalline polyester was measured by the following measuring method. That is, about 2 g of a liquid crystal polyester sample was filled into a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm using a flow tester (CFT-500 type manufactured by Shimadzu Corporation). It was. Subsequently, under a load of 9.8 MPa, the liquid crystal polyester was extruded from the nozzle under the condition of a temperature increase rate of 4 ° C./min, and the temperature at which the melt viscosity was 4800 Pa · s (48000 poise) was determined by the flow start temperature (unit). : ° C).

As a result, regarding the synthesis example 1, the flow start temperature was 193 degreeC.

Moreover, about Example 1, the flow start temperature was 249 degreeC and the flow start temperature was 270 degreeC at the time of complete | finish 2 stage solid-state superposition | polymerization when the 1st stage solid-phase polymerization was complete | finished.

In addition, about Example 2, the flow start temperature was 248 degreeC and the flow start temperature was 268 degreeC at the time of complete | finish two stage solid-phase polymerization at the time of completion | finish of 1st stage solid-state polymerization.

Moreover, about Example 3, the flow start temperature was 248 degreeC and the flow start temperature was 270 degreeC at the time of complete | finishing two stage solid phase polymerization at the time of complete | finish of 1st stage solid state polymerization.

In addition, about Example 4, the flow start temperature was 249 degreeC and the flow start temperature was 270 degreeC at the time of complete | finish 2 stage solid phase polymerization at the time of complete | finish of 1st stage solid-state polymerization.

Moreover, about Example 5, the flow start temperature was 258 degreeC and the flow start temperature was 288 degreeC at the time of complete | finish 2 stage solid phase polymerization at the time of complete | finish of 1st stage solid-state polymerization.

On the other hand, regarding the comparative example 1, the flow start temperature was 270 degreeC.

[Evaluation of Resin Peelability]

In addition, about Example 1, Example 2, Example 3, Example 4, Example 5, and the comparative example 1, this tray was made 40 cm in height in the state which the liquid crystalline polyester after solid state polymerization adhered to the tray made from SUS. It dropped to the concrete bottom surface at the position of, and peeled liquid crystal polyester from the tray made from SUS. At that time, the weight of the liquid crystalline polyester attached to the tray made of SUS was measured, and this was made into resin adhesion amount (unit: g).

As a result, regarding Example 1, when the one-step solid-state polymerization was complete | finished, it was proved that resin adhesion amount was very small as 0.9 g and it was excellent in resin peelability.

In addition, regarding Example 2, when the one-step solid-state polymerization was complete | finished, it was proved that resin adhesion amount was very small as 1.2 g, and it was excellent in resin peelability.

Moreover, regarding Example 3, when the one-step solid-state polymerization was complete | finished, it was turned out that resin adhesion amount was very small at 1.2 g and it was excellent in resin peelability.

In addition, regarding Example 4, when the one-step solid-state polymerization was complete | finished, it was proved that resin adhesion amount was very small as 1.2 g, and it was excellent in resin peelability.

And about Example 5, when the one-step solid-state polymerization was complete | finished, it was proved that resin adhesion amount was very small at 1.3 g and it was excellent in resin peelability.

On the other hand, regarding Comparative Example 1, it was found that the resin adhesion amount was very large at 520 g, and the resin peelability was not excellent.

INDUSTRIAL APPLICABILITY The present invention can be widely applied to the production of liquid crystal polyester used as an insulating resin base material for electronic devices such as printed wiring boards and package substrates.

Claims (5)

A melt polycondensation step of preparing a low-polymerization liquid crystal polyester by melt polycondensation,
A grinding step of grinding the liquid crystal polyester prepared in the melt polycondensation step;
As a manufacturing method of the liquid crystal polyester containing the solid-state polymerization process which prepares the high-polymerization liquid crystal polyester by solid-phase polymerization from the liquid-crystal polyester grind | pulverized at the said grinding | polishing process,
In the said melt polycondensation process, liquid-crystal polyester whose flow start temperature is 220 degrees C or less is prepared,
In the solid phase polymerization step, the liquid crystal polyester prepared in the melt polycondensation step is heated at a reaction temperature of 180 ° C. or higher to solidify the polymer, thereby preparing a solid polymer, pulverizing the solid polymer, and then heating to solid phase polymerization. The manufacturing method of liquid crystalline polyester characterized by the above-mentioned. The method of claim 1,
The said liquid crystalline polyester has the structural unit represented by the following formula (1), (2), and (3), and content of the structural unit represented by Formula (1) is 20-70 mol with respect to the total content of all the structural units. %, Content of the structural unit represented by Formula (2) is 40-15 mol%, content of the structural unit represented by Formula (3) is 40-15 mol% of liquid crystalline polyester, The manufacturing method of liquid crystalline polyester characterized by the above-mentioned. .
(1) -O-Ar ¹ -CO-
(2) -CO-Ar ² -CO-
(3) -X-Ar ³ -Y-
(In the formula, Ar ¹ represents a phenylene group or a naphthylene group, Ar ² represents a phenylene group, a naphthylene group or a group represented by the following formula (4), and Ar ³ represents a group represented by a phenylene group or the following formula (4). And X and Y each independently represent O or NH. The hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ may be each independently substituted with a halogen atom, an alkyl group or an aryl group.)
(4) -Ar ¹¹ -Z-Ar ^12-
(In the formulas, Ar ¹¹ and Ar ¹² each independently represent a phenylene group or a naphthylene group, and Z represents O, CO, or SO ₂ ). The method of claim 2,
At least one of X and Y of the structural unit represented by the said Formula (3) is NH, The manufacturing method of the liquid crystal polyester characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The said solid-state polymerization process WHEREIN: The reaction temperature of the solid-state polymerization of the said liquid crystal polyester was 280 degreeC or less, The manufacturing method of the liquid crystal polyester characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The said solid-state polymerization process WHEREIN: The reaction temperature of the solid-state polymerization of the said solid polymer was 180 degreeC or more, The manufacturing method of the liquid crystal polyester characterized by the above-mentioned.

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