JPH06239982A - Copolyester and polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a copolyester giving optical anisotropy when melted, excellent in heat resistance and processability, useful for precision parts, electric wire covering materials, etc., made up of each specific hydroxycarboxylic acid component, arylate component and polyester component at specified proportion. CONSTITUTION:This copolyester is made up of, as the essential constituents, (A) 1-90mol% of constituent of formula I (Ar1 is 2,6-naphthalene), (B) 1-95mol% of constituent of formula II (Ar2 is 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene or 2,6-naphthalene; Ar3 is 1,3-phenylene, 1,4-phenylene, 2,6-naphthalene, etc.) and (C) 1-80mol% of constituent of formula III (Ar4 is 1,3-phenylene, 4,4'- biphenylene, etc.; (l) is 2-200; (n) is 2-6). This copolyester resin composition is further incorporated with <=95wt.%, based on the final composition, of an inorganic filler.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can perform melt processing with a conventionally used apparatus, and can impart excellent heat resistance and high mechanical properties to the obtained molded product. The present invention relates to a novel copolyester showing optical anisotropy when melted and a composition thereof.

[0002]

2. Description of the Related Art Polyester exhibiting anisotropy when melted using a polyalkylene terephthalate such as polyethylene terephthalate, which is commercially available at present, is disclosed in Japanese Patent Publication No. 56-18016. As described above, a polymer obtained by polymerizing p-acetoxybenzoic acid and polyethylene terephthalate while undergoing acidolysis. The polymer has a liquid crystal transition temperature of 230 ° C.
Before and after, it has excellent mechanical properties. However, this polymer has, for example, a heat distortion temperature of 65 to 70 ° C.
However, it cannot be used in applications requiring heat resistance, because it has a drawback of being poor in so-called thermal characteristics. Further, the above-mentioned polymer also has a drawback that an insoluble insoluble matter derived from p-acetoxybenzoic acid is formed during the polymerization.

[0003]

Means for Solving the Problems The present inventors have the above-mentioned problems
As a result of earnest research efforts to solve the problem, p-acetoxy
High heat resistance and excellent machine without using benzoic acid
Optical anisotropy during melting that can obtain a molded product with physical properties
To complete the present invention by finding the copolymerized polyester shown
I arrived. That is, the present invention has the following essential components.
Including the structural units represented by general formulas (1), (2), and (3),
1 to 90 mol% of the component of (1), (2)
1 to 95 mol% of the component of (3) and 1 to 80 mol% of the component of (3).
Shows optical anisotropy when melted, characterized by
It is a copolyester. (1) -OC-Ar₁-O- (2) -OC-Ar₂-COO-Ar₃-O- (3)-{OC-Ar_Four-COO- (CH₂)_nO}_l-(Where Ar₁Is 2,6-naphthalene, Ar₂Is 1,3 −
Phenylene, 1,4-phenylene, 4,4'-biphenylene,
One or more selected from 2,6-naphthalene,
Ar₃Is 1,3-phenylene, 1,4-phenylene, 2,6-
Naphthalene, phenylene number of 2 or more connected in para position
-O-, -CH between the compound residue and the phenylene at the para position₂-
 , -CO-, -S-, -SO-, -SO₂-, -C (CH₃)₂-, -C (CF₃)₂-
 And -O- (CH ₂)_m-O- {m = 2-6}
One or more selected from compound residues, Ar
_FourIs 1,3-phenylene, 1,4-phenylene, 4,4'-biphenyl.
One kind younger than phenylene and 2,6-naphthalene
Is two or more kinds, l is 2 to 200, n is an integer of 2 to 6
is there. ) To embody the constituent units of (1) to (3) above,
Various compounds having ordinary ester forming ability are used.
It Below, the copolyester forming the present invention is formed.
The raw material compounds required for
Explain.

The hydroxycarboxylic acid component (1) is 6-hydroxy-2-naphthoic acid, the amount of which is 1 to 90 mol%, preferably 1 to 85 mol% based on all the constituent units.
Is. Outside of these ranges, the melting point of the produced polymer remarkably rises and the molecular weight decreases, which is not preferable. Further, since this hydroxycarboxylic acid unit is introduced into the polymer, hydroxycarboxylic acid or other ester-forming derivative can be used.

Next, the arylate component (2) is composed of a dicarboxylic acid and a diol, and the dicarboxylic acid component Ar ₂ is 1,3-
Phenylene, 1,4-phenylene, 4,4'-biphenylene,
One or more selected from 2,6-naphthalene. The diol component Ar ₃ is 1,3-phenylene, 1,4-
Phenylene, 2,6-naphthalene, and a residue of a compound having a phenylene number of 2 or more connected at the para position (for example, 4,4'-biphenylene) and -O- between the phenylene at the para position (for example, 4,4 ').
-Dihydroxydiphenyl ether and the like),
-CH ₂ - (e.g. 4,4'-dihydroxydiphenyl methane), - CO- (such as 4,4'-dihydroxydiphenyl ketone), - S- (such as 4,4'-dihydroxydiphenyl sulfide), - SO ₂ - ( such as 4,4'-dihydroxydiphenyl _{sulfone), - C (CH 3)} 2 - ( e.g. _{4,4'-isopropylidenediphenol), - C (CF 3)} 2 - ( e.g. 4,4'-hexafluoroisopropylidene Redene diphenol) and -O- (CH ₂ ) _m
It may be one kind or two or more kinds selected from the residues of the compounds bonded by -O- {m = 2 to 6} (for example, 4,4 '-(ethylenedioxy) diphenol). The amounts of the dicarboxylic acid and the diol are substantially the same, and the total amount is 1 to 95 mol% based on all the constituent units.
And preferably 1 to 90 mol%. Outside of these ranges, the melting point of the produced polymer remarkably rises and the molecular weight decreases, which is not preferable. In order to introduce the above dicarboxylic acid and diol units into the polymer, a diester-forming derivative other than the dicarboxylic acid or diol can be used.

On the other hand, in the polyester component (3), Ar ₄ is 1,
One or more selected from 3-phenylene, 1,4-phenylene, 4,4'-biphenylene, 2,6-naphthalene, n is an integer of 2 to 6, and specifically polyethylene terephthalate, Examples thereof include polyethylene naphthalate, and the amount thereof is 1 to 80 mol%, preferably 1 to 60 mol% based on all the constituent units. Outside of these ranges, the melting point of the produced polymer remarkably rises, the molecular weight decreases, and the heat resistance decreases, which is not preferable.
The number l of the average repeating units is selected from 2 to 200, and the form may be pellets or recycled pulverized products. These raw material polyesters can be manufactured by a general method well known in the art.

The copolyester of the present invention is polymerized by a direct polymerization method or a transesterification method, and in the polymerization, a solvent polymerization method, a melt polymerization method, a slurry polymerization method or the like is usually used. In these polymerizations, various catalysts can be used, and typical ones are dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, carboxylic acid alkali and alkali. Examples thereof include earth metal salts and Lewis acids such as BF ₃ . Generally, the amount of catalyst used is preferably about 0.001 to 1% by weight, based on the total weight of the monomers. The polymers produced by these polymerization methods can be further increased in molecular weight by solid phase polymerization in which the polymer is further heated under reduced pressure or in an inert gas.

A copolyester which exhibits optical anisotropy when melted is an essential element in the present invention in order to have both thermal stability and easy processability. The property of melt anisotropy can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the melt anisotropy was confirmed by using a polarizing microscope manufactured by Olympus, melting the sample placed on the hot stage manufactured by Rincom, and observing it under a nitrogen atmosphere at a magnification of 150 times. it can.
The polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted even if it is in a stationary state, for example. Liquid crystallinity and melting point (liquid crystallinity manifesting temperature) are considered as indices of the processability of the present invention. Whether or not it exhibits liquid crystallinity is deeply related to the fluidity at the time of melting, and it is essential that the copolyester of the present invention exhibits liquid crystallinity in the molten state. A nematic liquid crystalline polymer causes a significant decrease in viscosity above its melting point, so that generally exhibiting liquid crystallinity at or above its melting point is an index of processability. The melting point (liquid crystallinity manifesting temperature) is preferably as high as possible from the viewpoint of heat resistance, but is 350 ° C. or less in consideration of heat deterioration during melt processing of a polymer, processing capability of a molding machine, and the like. It is a good guide. Moreover, the melting point viscosity of the resin is 1 × under the shear rate of 1000 sec ⁻¹ at a temperature of at least 10 ° C. to the melting point.
It is preferably 10 ⁴ poise or less. More preferably
It is less than 10 ³ poise. These melt viscosities are generally realized by having liquid crystallinity.

Next, the copolyester of the present invention may be blended with various fibrous, powdery or plate-like inorganic and organic fillers depending on the purpose of use. As the fibrous filler, glass fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel fiber, aluminum, titanium, Copper, brass, etc.
Inorganic fibrous substances such as metal fibrous substances may be mentioned. A particularly representative fibrous filler is glass fiber. In addition, high-melting-point organic fibrous substances such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used.
On the other hand, as the particulate filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, wollastonite Such as silicates, iron oxides, titanium oxides, zinc oxides, antimony trioxide, oxides of metals such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, Other examples include ferrite, silicon carbide, silicon nitride, boron nitride and various metal powders. Examples of the plate-shaped filler include mica, glass flakes, various metal foils and the like. Examples of organic fillers include heat-resistant and high-strength synthetic fibers such as aromatic polyester fibers, liquid crystal polymer fibers, aromatic polyamide fibers, 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 terms of having mechanical strength, dimensional accuracy, electrical properties and the like. The content of the inorganic filler is 95% by weight or less, preferably 1 to 80% by weight, based on the total amount of the composition. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary.

Further, to the copolymerized polyester of the present invention, other thermoplastic resin may be supplementarily added within a range not impairing the intended purpose of the present invention. Examples of thermoplastic resins used in this case include polyolefins such as polyethylene and polypropylene, aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, and aromatic polyethers and aromatic dicarboxylic acids composed of diols or oxycarboxylic acids. And wholly aromatic polyethers, polyacetals (homo or copolymer), polystyrenes,
Polyvinyl chloride, polyamide, polycarbonate, AB
Examples thereof include S, polyphenylene oxide, polyphenylene sulfide, and fluororesin. Further, these thermoplastic resins can be used as a mixture of two or more kinds.
And antioxidants usually used in thermoplastic polymers (for example, phosphorus compounds such as tridecyl phosphite, or compounds containing hindered phenol, etc.), lubricants (for example, stearyl alcohol, polyethylene wax, etc.),
Use of additives well known in the art such as flame retardants (for example, halogen compounds such as brominated bisphenol A, polymers composed of organic phosphorus compounds, antimony compounds such as antimony trioxide, etc.) should be selected and used according to the purpose. You can

[0011]

INDUSTRIAL APPLICABILITY The copolymerized polyether and its composition which are anisotropic when melted and which consist of the specific constitutional unit obtained in the present invention have good flowability during melting and excellent thermal stability. Anisotropy can be exhibited without using benzoic acid or its ester-forming derivative, and injection molding, extrusion molding and compression molding are possible without using a molding machine having a special structure. It can be processed into three-dimensional molding, fiber, film, etc. In addition, it has a good balance of thermal stability and is superior in heat resistance to polyester that shows anisotropy when melted using polyethylene terephthalate, which is commercially available in the past. It is suitable for connectors, thin-walled parts, and wire coating materials.

[0012]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 As shown in Table 1, 6-hydroxy-2-naphthoic acid 45.2
g (18.2 mol% as hydroxycarboxylic acid component (1)), terephthalic acid 119.8 g, 1,4-dihydroxybenzene 55.6 g, 4,4'-dihydroxybiphenyl 40.3 g (54.5 mol% as arylate component (2)), 177.1 g of acetic anhydride and 0.05% by weight of potassium acetate with respect to the final charged amount, respectively, were charged into a reactor equipped with a stirrer, a nitrogen introducing pipe and a distilling pipe, and the inside of the reaction vessel was replaced with nitrogen, followed by nitrogen. The mixture was reacted at 140 ° C. for 1 hour under a stream of air. After this
Heated to 230 ° C. for 1.5 hours. At this time, about 90 g of acetic acid was distilled off. Next, 69.3 g of polyethylene terephthalate (27.3 mol% as the polyester component (3)) was added to this reaction system, and the mixture was heated to 350 ° C. for 2 hours and further heated to 350 ° C.
The mixture was stirred at 0 ° C for 0.5 hours. By that time, more than 95% of the theoretical acetic acid distillate had distilled. Next, the pressure inside the reaction vessel was gradually reduced at 350 ° C, and further reduced to 1 mmHg or less in 0.2 hours.
The reaction was carried out at this pressure for 2 hours. During this vacuum, a small amount of acetic acid distilled out. Then, after the reaction is completed, nitrogen is introduced,
The polymer obtained when the contents were taken out was pale yellowish white, and the melting point measured by DSC manufactured by Perkin Elmer was 335 ° C. Further, when the polymer was heated and observed under a crossed Nicol on a hot stage manufactured by Rincom under a polarizing microscope manufactured by Olympus, a nematic liquid crystal pattern was exhibited at a melting point or higher. Next, a tensile test piece was prepared from this polymer using a mini shot type 2 machine manufactured by Yokohama Chemix Co., Ltd., and measured using a tensile tester manufactured by Toyo Baldwin Co., Ltd., the tensile strength was 1480 kg / cm ² , and the tensile elongation was 1.5.
%Met. Next, the following values were used as substitute characteristics in order to evaluate the strength retention below the melting point. That is, according to the Vicat method, the temperature at which a needle of a certain size begins to penetrate through a 0.5 mm thick press sheet under a certain load was defined as the softening temperature. The softening temperature of this polymer was 152 ° C. The higher this value, the better the high temperature characteristics. In addition, the melt viscosity of this polymer was measured by a Capillograph manufactured by Toyo Seiki Co., Ltd.
0 poise (measurement temperature: 345 ℃, shear rate: 1000 sec ^-1 )
Met.

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 at the composition ratios shown in Table 1, and the obtained polymers were evaluated in the same manner. still,
Since the amount of heat transfer is small depending on the composition ratio and the reliability of the data is lacking, the values measured by the melting point measuring device manufactured by Yanagi Headquarters are shown. The resulting polymer was prepared under the same conditions as in Example 1,
A liquid crystalline pattern was exhibited.

Example 6 The polymer obtained in Example 1 was mixed and extruded with 30% by weight of glass fiber by an extruder manufactured by Haake Co., and a test piece was prepared and evaluated by the same method.

Comparative Examples 1 and 2 Polymerization was carried out in the same manner as in Example 1 at the composition ratios shown in Table 1. However, in Comparative Example 1, the viscosity increased remarkably from around 300 ° C. and finally heated to 400 ° C., but it solidified and could not be taken out from the reaction vessel. The above results are summarized in Table 1.

[0016]

[Table 1]

Note) HNA; 6-hydroxy 2-naphthoic acid TPA; terephthalic acid HQ; 1,4-dihydroxybenzene BP; 4,4'-dihydroxybiphenyl EG; ethylene glycol N / A; solidified and taken out from the reaction vessel. No, I could not evaluate.

[Procedure amendment]

[Submission date] May 9, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Next, the arylate component (2) is composed of a dicarboxylic acid and a diol, and the dicarboxylic acid component Ar ₂ is 1,3-
Phenylene, 1,4-phenylene, 4,4'-biphenylene,
One or more selected from 2,6-naphthalene. The diol component Ar ₃ is 1,3-phenylene, 1,4-
Phenylene, 2,6-naphthalene, and a residue of a compound having a phenylene number of 2 or more connected at the para position (for example, 4,4'-biphenylene) and -O- between the phenylene at the para position (for example, 4,4 ').
-Dihydroxydiphenyl ether and the like),
-CH _2- (e.g. 4,4'-dihydroxydiphenylmethane), -CO- (e.g. 4,4'-dihydroxydiphenylketone), -S- (e.g. 4,4'-dihydroxydiphenylsulfide), -SO- (e.g. 4,4'-dihydroxydiphenyl sulfoxide), - SO ₂ - (e.g. 4,4'-dihydroxydiphenyl _{sulfone), - C (CH 3)} 2 - ( e.g. 4,4'-isopropylidenediphenol), - C (CF ₃ ) _2- (eg 4,4 '
-Hexafluoroisopropylidenediphenol) and -O
-(CH ₂ ) _m -O- {m = 2 to 6} (for example, 4,4 '-(ethylenedioxy) diphenol) by one kind or two or more kinds selected from the residue of the compound bonded It may be.
The amounts of the dicarboxylic acid and the diol are substantially the same, and the total amount thereof is 1 to 95 with respect to all the constituent units.
Mol%, and preferably 1 to 90 mol%. Outside of these ranges, the melting point of the produced polymer remarkably rises and the molecular weight decreases, which is not preferable. In order to introduce the above dicarboxylic acid and diol units into the polymer, a diester-forming derivative other than the dicarboxylic acid or diol can be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Note) HNA; 6-hydroxy-2-naphthoic acid TPA; terephthalic acid HQ; 1,4-dihydroxybenzene BP; 4,4'-dihydroxybiphenyl PET; polyethylene terephthalate N / A; solidified and taken out from the reaction vessel No, I could not evaluate.

Claims (2)

[Claims] 1. A compound represented by the following general formula (1) as an essential constituent component:
, (2), including the structural unit represented by (3), with respect to all the structural units, the constituent component of (1) is 1 to 90 mol%, the constituent component of (2) is 1 to 95 mol%, A copolymerized polyester exhibiting optical anisotropy when melted, wherein the constituent component of (3) is 1 to 80 mol%. (1) -OC-Ar ₁ -O- (2) -OC-Ar ₂ -COO-Ar ₃ -O- (3)-{OC-Ar ₄ -COO- (CH ₂ ) _n O} _l- (here , Ar ₁ is 2,6-naphthalene, Ar ₂ is 1,3-
Phenylene, 1,4-phenylene, 4,4'-biphenylene,
One or more selected from 2,6-naphthalene,
Ar ₃ is 1,3-phenylene, 1,4-phenylene, 2,6-
-O-, -CH _2- between the residue of naphthalene, compound of phenylene number 2 or more connected at para position, and phenylene at para position
, -CO-, -S-, -SO-, -SO _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2-
And -O- (CH ₂ ) _m -O- {m = 2 to 6}, one or more kinds selected from the residues of the compound, Ar,
₄ is one or more selected from 1,3-phenylene, 1,4-phenylene, 4,4′-biphenylene and 2,6-naphthalene, l is 2 to 200, and n is 2 to 2 It is an integer of 6. ) 2. A copolymerized polyester resin composition obtained by blending the copolymerized polyester according to claim 1 with an inorganic filler in an amount of 95% by weight or less (based on the total amount of the composition).