WO2008041776A1

WO2008041776A1 - Fully aromatic polyester

Info

Publication number: WO2008041776A1
Application number: PCT/JP2007/069637
Authority: WO
Inventors: Toshiaki Yokota; Toshio Shiwaku
Original assignee: Polyplastics Co., Ltd.
Priority date: 2006-10-05
Filing date: 2007-10-02
Publication date: 2008-04-10
Also published as: JP2008088387A; TW200827381A; JP5274761B2

Abstract

Disclosed is a fully aromatic polyester which is particularly suitably used for multilayer films, multilayer sheets, multilayer blow molded articles and the like, since it is excellent in dimensional stability and heat resistance while having low volume expansion rate. Specifically disclosed is a fully aromatic polyester exhibiting optical anisotropy when melted, which contains structural units introduced from 4-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid and hydroquinone at a specific ratio.

Description

Description Fully Aromatic Polyester Technical Field

The present invention relates to wholly aromatic polyesters suitably used for films, blow molded articles and the like. More specifically, since it has a small volume expansion coefficient, excellent high dimensional stability, and excellent heat resistance, it is particularly suitable for multilayer films or multilayer sheets, multilayer multilayer molded products, etc. Related to fully aromatic polyesters

(The background.

Liquid crystalline polymers have a good balance of excellent fluidity, mechanical strength, heat resistance, chemical resistance, and electrical properties, and are therefore widely used as high-performance engineering plastics, but most of them are exclusively used. It was obtained by injection molding.

On the other hand, along with the remarkable industrial development in recent years, the use of powerful liquid crystalline polymers is also becoming more sophisticated and specialized, and it can be efficiently and economically processed by melt drawing and blow molding, It has been expected to obtain a film or sheet, a hollow molded product, a fiber or the like that retains excellent physical properties such as dimensional stability, hygroscopicity and electrical properties of the liquid crystalline polymer. In recent years, in the field of electrical and electronic materials, liquid crystalline polymer films have been used for electronic circuit board applications. However, higher signal speed, higher pattern density, and higher multi-layers have become necessary. Properties, thickness accuracy, heat resistance, dimensional stability during processing, and multilayering are required. For example, when a liquid crystal polymer film and a metal multilayer body are used for an electronic circuit board, the multilayer body will be damaged if the liquid crystal polymer film and the metal have different coefficients of thermal expansion or the film itself is weak. There was a problem.

Existing liquid crystalline polymer films do not have dimensional stability and strength Therefore, it is difficult to make a multilayer of liquid crystalline polymer film and metal. Japanese Patent Application Laid-Open No. 20 0 4-2 4 4 4 5 2 proposes a liquid crystalline polymer film having a small volume expansion coefficient due to heat, but the effect is not sufficient.

In addition, in order to combine dimensional stability and strength, methods such as adding various fillers to liquid crystalline polymers are considered, but the film processability deteriorates, so it is insufficient as a material for electronic circuit board applications. . Disclosure of the invention

The present invention solves the above-mentioned problems of the prior art, has a small volume expansion coefficient, has excellent high dimensional stability, and is excellent in heat resistance. Thus, a multilayer film or a multilayer sheet, a multilayer blow molded article, etc. It is an object of the present invention to provide a wholly aromatic polyester which is particularly preferably used in the present invention.

As a result of intensive research on the provision of wholly aromatic polyesters that achieve the above-mentioned object and maintain good electrical properties while having a small volume expansion coefficient, high dimensional stability, and excellent heat resistance. The inventors have found that it is effective to select three specific raw materials and combine the specific amounts to achieve the above object, and the present invention has been completed.

That is, the present invention includes structural units represented by the following general formulas (I), (II) and (III) as structural components, and the structural unit of (I) is 66 to 5 mole ^_0/0, at the time of melting, wherein the structural unit (II) is 12.5 to 17.0 mole ^_0/0, a structural unit is 12.5 to 17.0 mol% of (III) It is a wholly aromatic polyester that exhibits optical anisotropy.

(Π)

(III) —— o— Ar ₃ -0——

(Where Ai ^ is 1,4 1-phenylene, Ar ₂ is 2,6-naphthalene, and Ar ₃ is 1,4-phenylene.)

The present invention further provides a film or sheet formed from the wholly aromatic polyester and a metal laminate obtained by laminating a metal on the film or sheet.

The present invention also provides a use for producing the above-mentioned fully aromatic polyester film or sheet.

The wholly aromatic polyester and its composition comprising a specific structural unit obtained in the present invention and exhibiting anisotropy at the time of melting are easily melt-drawn and blow-molded, processed efficiently and economically. It is possible to obtain a film or sheet, fiber and blow-molded product having excellent physical properties of liquid crystalline polyester.

In addition, because of its small volume expansion coefficient and excellent dimensional stability, it can be used as a multilayer film or sheet formed from other polymers and metals, and as a multilayer pro-molded product formed from other polymers. Used especially well. Other polymers used here are not particularly limited, but polyolefins, particularly high-density polyethylene are preferred.

Detailed Description of the Invention

In order to realize the structural units (I) to (III) above, it has ordinary ester forming ability. Various compounds are used. Hereinafter, the raw material compounds necessary for forming the wholly aromatic polyester constituting the present invention will be described in detail step by step.

The constitutive position (I) is introduced from 4-hydroxybenzoic acid and its derivatives. The structural unit (II) is derived from 2,6-naphthalenedicarboxylic acid and its derivatives.

The structural unit (III) is introduced from hydroquinone and its derivatives.

In the structural unit (III), Ar ₃ needs to be 1,4-phenylene, and, for example, 4, 4, biphenyl, etc. are not preferable because the melting point is remarkably high.

In the present invention, the copolymerization ratio of each structural unit is important for the purpose of the present invention, in order to maintain good heat resistance and to exhibit a small volume expansion coefficient and excellent dimensional stability. . Therefore, in the present invention comprise the structural units (I) ~ a (ΙΠ), constituent units ^66-75 mol% of the total constitutional units 100 mole% (I) (preferably 68 to 72 mole ^_0/0 ), the structural unit (II) 12. 5 to 17. 0 mole ^_0/0 (preferably 14-16 mole ^_0/0), the structural unit (III) 12. 5 to 17. 0 mole ^_0/0 (Preferably 14 to 16 mol%).

If the structural unit of (I) is less than 6 mol%, it is not preferable because it adversely affects the target dimensional stability (volume expansion coefficient). On the other hand, if it exceeds 75 mol%, the melting point becomes remarkably high, and in some cases, the polymer is solidified in the reactor at the time of production, which makes it impossible to produce a polymer having a desired molecular weight.

In addition, when the constituent unit of (II) is less than 12.5 mol%, the melting point is remarkably high, and in some cases, the polymer solidifies in the reactor at the time of production, making it impossible to produce a polymer with a desired molecular weight. It is not preferable. Further, there is no properly preferred because an adverse effect on I ^7. 0 mole ^_0/0 becomes Ri many good when dimensional stability of interest (volume expansion ratio).

If the structural unit of (III) is less than 12.5 mol%, the melting point becomes remarkably high, and in some cases, the polymer solidifies in the reactor during production, making it impossible to produce a polymer having a desired molecular weight. Therefore, it is not preferable. In addition, if it exceeds 17.0 mol%, the target dimensional stability (volume expansion coefficient) is adversely affected. It ’s not.

Incidentally, in the wholly aromatic polyester of the present invention, a small amount of other known structural units can be introduced as long as the object of the present invention is not impaired, but these structural units may not be actually included. preferable.

The wholly aromatic polyester of the present invention is polymerized using a direct polymerization method or a transesterification method, and a melt polymerization method, a solution polymerization method, a slurry polymerization method or the like is used for the polymerization.

In the present invention, an acylating agent for the polymerization monomer or a monomer having an active end as an acid chloride derivative can be used in the polymerization. Examples of the acylating agent include acid anhydrides such as anhydrous acetic acid, and the amount used is preferably 1.01 to 1.10 times the total equivalent weight of hydroxyl groups, more preferably 1. 02 to 1 · 05 times. Various catalysts can be used for these polymerizations. Typical examples are dialkyltin oxide, dialyl tin oxide, titanium dioxide, alkoxytitanium silicates, titanium alcoholates, and carboxylic acids. And alkaline earth metal salts, Lewis acid salts such as BF _{3 and} the like. The amount of catalyst used is generally from about 0.001 to 1% by weight, especially from about 0.003 to 0.2% by weight, based on the total weight of the monomer.

In the case of performing solution polymerization or slurry polymerization, liquid paraffin, high heat resistant synthetic oil, inert mineral oil, etc. are used as a solvent.

The reaction conditions are a reaction temperature of 200 to 380 ^D C and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to: L01, 080 Pa). Especially for melt reactions, the reaction temperature is 260 to 380 ° C, preferably 300 to 360 ° C, and the final pressure is! ~ LOOTorr (ie, 133-13, 300 Pa), preferably l-50 Torr (ie, 133-6, 670 Pa).

Melt polymerization is carried out after the reaction system reaches a predetermined temperature, and then the pressure reduction is started to a predetermined pressure reduction degree. After the agitator torque reaches a predetermined value, an inert gas is introduced, and the polymer is discharged from the reaction system through a normal pressure from a reduced pressure state to a predetermined pressure state. The liquid crystalline polymer exhibiting optical anisotropy when melted is an indispensable element in the present invention in order to have both thermal stability and easy processability. From the above unit There are some wholly aromatic polyesters that do not form an anisotropic melt phase depending on the sequence distribution in the constituent components and the polymer. However, the polymer according to the present invention has an optical anisotropy when melted. Are limited to wholly aromatic polyesters.

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

The wholly aromatic polyester of the present invention preferably has a melt viscosity of 1 × 10 ⁶ Pa · s or less at a shear rate of lOOOOsec- ¹ at a temperature 10 ° C. or more higher than the melting point. More preferably, it is 1 × 10 ³ Pa · s or less. These melt viscosities are generally realized by having liquid crystallinity.

The wholly aromatic polyester of the present invention can be formed into a film by melt extrusion molding, inflation molding or the like.

Melt extrusion molding is a molding method in which a wholly aromatic polyester is melt-kneaded with an extruder and a melt-extruded melt is stretched from a slit portion of a T die, and a stretched and oriented film can be obtained.

The setting of the extruder during film formation can be appropriately set according to the skeleton composition ratio of the wholly aromatic polyester. The cylinder temperature of the extruder is preferably from 300 to 380 ° C, more preferably from 320 to 370 ° C. At temperatures outside this range, the wholly aromatic polyester tends to be thermally decomposed and film formation tends to be difficult. The slit interval used is preferably 0.1 to 1.0mra. When the slit interval is larger than 1.0 mm, uneven orientation or the like occurs and the shape of the film tends to deteriorate.

—The drift ratio of the axially oriented film (the value obtained by dividing the cross-sectional area of the T-die slit by the cross-sectional area of the MD direction) is preferably in the range of 2.0-30. When the drift ratio is less than 2.0, the film strength tends to be insufficient, and when the drift ratio exceeds 30, the smoothness of the film tends to be insufficient. Biaxially stretched film is a method in which a melt sheet extruded from a T die is stretched simultaneously in the longitudinal direction (MD) and in both the longitudinal direction and the vertical direction (transverse direction (TD)), or a melt extruded from a T die. The sheet can be obtained by stretching in the V1D direction and then in the TD direction. The draw ratio in the MD direction and TD direction is preferably 1.0 or more, and more preferably 1.5 to 20. If the draw ratio is out of the above range, it tends to be difficult to obtain a film having a mechanical balance and a uniform thickness.

Inflation molding is a molding method in which a wholly aromatic polyester is melt-kneaded with an extruder and an inert gas is blown from the inside of a cylindrical sheet melt-extruded from a circular ring die, and a stretched and oriented film can be obtained. it can.

The setting of the extruder during film formation can be appropriately set according to the skeleton composition ratio of the wholly aromatic polyester. The cylinder temperature of the extruder is preferably 300 to 380 ° C, more preferably 320 to 370 ° C. At temperatures outside this range, the wholly aromatic polyester tends to be thermally decomposed and film formation tends to be difficult. The ring slit interval used is preferably 0.1 to 3.0 mm, more preferably 0.2 to 1.5 mm. In inflation molding, the draw ratio and blow ratio are used as equivalent to the draw ratio in the MD direction and TD direction in the T-die method. The draw ratio corresponds to the draw ratio in the MD direction, preferably 1.5 to 40, and the blow ratio corresponds to the draw ratio in the TD direction, preferably 2.0 to 10. If the setting conditions at the time of film formation are outside the above range, it tends to be difficult to obtain a film having a mechanical balance and a uniform thickness.

The thickness of the wholly aromatic polyester film obtained by the present invention is preferably 1 to 500 μm and more preferably 5 to 300 μm from the viewpoints of film forming property, mechanical properties and processability.

The wholly aromatic polyester film obtained by the present invention can be formed into a metal laminate by laminating a metal layer on its surface, or a multilayer laminate of two or more layers of a wholly aromatic polyester film and a metal layer. You can also. Further, in order to improve strength and adhesion, the metal laminate may be heat-treated as necessary. Examples of the metal used include gold, silver, copper, nickel, and aluminum. Copper is preferable for printed wiring board applications, and aluminum is preferable for capacitor applications.

Next, the wholly aromatic polyester of the present invention can be blended with various fibrous, powdery, and plate-like inorganic and organic fillers within a range that does not affect the film processability.

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

On the other hand, as the granular filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, potassium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollastonite Silicates such as iron oxide, iron oxide, titanium oxide, zinc oxide, antimony trioxide, oxides of metals such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfuric acids of metals such as calcium sulfate and barium sulfate Examples include salts, other ferrites, silicon carbide, silicon nitride, boron nitride, and various metal powders.

Examples of the plate-like filler include My strength, glass flakes, Tanorek, and various metal foils.

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

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

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

In addition, other thermoplastic resins may be further added to the wholly aromatic polyester of the present invention as long as the purpose of the present invention is not impaired.

Examples of the thermoplastic resin used in this case are: Polyoleins such as polyethylene and polypropylene; Aromatic polyesters composed of aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate and diol; Polyacetal ( Homo or copolymer), polystyrene, polychlorinated butyl, polyamide, polycarbonate, ABS, polyphenylene oxide, polyphenylene sulfide, fluororesin, and the like. Two or more of these thermoplastic resins can be used in combination. Example

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

[Melting point]

It was measured with a differential running calorimeter (DSC 7 manufactured by Perkin Elma Co., Ltd.) under a temperature rising condition of 20 ° CZ.

[Melting viscosity 3

Measurement temperature was 360 ° (: shear rate lOOOsecf ¹ ), measured with Toyo Seiki Capirodharaf using an orifice with an inner diameter of 1 ram and a length of 20 mm.

[Volume expansion]

The linear expansion coefficient at 50-100 ° C in the MD and TD directions of the film plane and in the ZD direction of the film thickness with a temperature rise condition of 10 ° C / min. The average value was calculated, and the sum of the linear expansion coefficients in the three directions was taken as the volume expansion coefficient. Example 1 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a vacuum Z effluent line was charged with the following raw material monomers, metal catalyst, and acylating agent, and nitrogen substitution was started.

(I) 4 over arsenate Dorokishi acid 227. 3 g (70 mol ^_0/0)

(II) 2,6_Naphthalenedicarboxylic acid 76.2 g (15 mol%)

(III) human Dorokinon 38. 8 g (15 mole ^_0/0)

Acetate-powered rhodium catalyst 25.5 mg (30 ppm by weight as metal-based lithium (total weight of polymer))

Acetic anhydride 244.8 g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C and reacted at 140 ° C for 1 hour. After that, the temperature was further increased to 360 ° C over 5 hours, and then over 15 minutes, lOTorr

The pressure was reduced to (that is, 1330 Pa), and melt polymerization was carried out while distilling acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state, and the polymer was discharged from the lower part of the polymerization vessel.

Next, a film was prepared by adjusting the temperature and pressure so that the thickness of the film became 0.05 mm with a hot press, and the volume expansion coefficient was measured.

Comparison example: ~ 3

Polymerization was carried out in the same manner as in Example 1 except that the types and amounts of raw material monomers were as shown in Table 1. These results are shown in Table 1. In Comparative Example 3, the polymer solidified in the reactor at the time of production, and a polymer having a desired molecular weight could not be produced.

Comparative Example 4

A polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen inlet, and vacuum / outflow line was charged with the following raw material monomers, metal catalyst, and acylating agent, and nitrogen substitution was started.

6 arsenide Dorokishi _ 2 Nafute acid 193. 2 g (60 mole ^_0/0)

2, 6 _ naphthalenedicarboxylic acid 74. 0 g (20 mole ^_0/0) 4, 4, Jihi Dorokishibifue two Norre 63. 7 g (20 mole ^_0/0)

Acetic anhydride 178.1 g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C and reacted at 140 ° C for 1 hour. After that, the temperature was further raised to 350 ° C over 5 hours, and then over 15 minutes, lOTorr

Next, the film was prepared by adjusting the temperature and pressure so that the thickness of the film became 0.05 mm by hot pressing, and the volume expansion coefficient was measured.

The results are shown in Table 1.

table 1

(註 in the table)

HB A; 4-Hydroxybenzoic acid

NDA: 2, 6 Naphthalene dicarboxylic acid

HQ ： Hydroquinone

HNA; 6-hydroxy-2-naphthoic acid BP; 4, 4, monodihydroxybiphene

Claims

The scope of the claims

1. Containing constituent units represented by the following general formulas (I), (II), and (III) as constituent components, and the constituent unit of (I) is 66-75 mol% with respect to 100 mol% of all constituent units,

A wholly aromatic polyester exhibiting optical anisotropy upon melting, characterized in that the structural unit of (II) is 12.5 to 17.0 mol% and the structural unit of (III) is 12.5 to 17.0 mol%.

0

,,

( _τ I) — O— Ar— C II—

(III) — O— Ar ₃ -0——

(Where is 1,4 monophenylene, Ar ₂ is 2,6-naphthalene, and Ar ₃ is 1,4 monophenylene.)

2. A film or sheet formed from the wholly aromatic polyester according to claim 1.

3. A metal laminate obtained by laminating a metal on the film or sheet according to claim 2.