JP2843214B2 - Polyester polymer and molded product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polymer, and more particularly to a polyester copolymer having excellent transparency, heat resistance, small optical anisotropy and excellent moldability. , 9-bis- (4-hydroxyethoxyphenyl) -fluorene.

[0002]

In recent years, for improving the heat resistance of the polyether scan ether, or by copolymerizing various components, also polyarylates - be the total aromatics as bets have been made. 9,9
Various proposals have been made for polyesters using -bis- (4-hydroxyphenyl) -fluorene, but those relating to polyester copolymers using 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene. Is not yet seen.

That is, it is disclosed in US Pat. No. 3,546,165 that a polymer of 9,9-bis- (4-hydroxyphenyl) -fluorene and terephthalic acid and isophthalic acid can be obtained from the acid chloride method. It is shown. To improve the formability of this product, Japanese Patent Publication No. 4-22931
Discloses a heat-resistant polyester using a mixture of 9,9-bis- (4-hydroxyphenyl) -fluorene and terephthalic acid, isophthalic acid and fatty acid at a specific ratio. A method for producing a soluble heat-resistant polyarylate is disclosed in JP-A-63-152622.
JP-A-57-192432 discloses a material having a specific viscosity of a copolymer of (4-hydroxyphenyl) -fluorene and a specific composition ratio of terephthalic acid and isophthalic acid. Also disclosed is a polyester using the 9,9-bis- (4-hydroxyphenyl) -fluorene and a mixture of terephthalic acid, isophthalic acid, and aliphatic dicarboxylic acid.

However, these are all 9,9-bis- (4
-Hydroxyphenyl) -fluorene is used, and the polymerization method at that time also requires special conditions. That is, unlike aliphatic alcohols, 9,9-bis- (4-hydroxyphenyl) -fluorene has a phenolic group at both ends, so that it is very difficult to react. The reaction conditions at a higher temperature are required, and the resulting polymer is liable to be thermally decomposed, colored, and deteriorated in quality. In addition, under the conditions of using a polymerization method of dehydrochlorination in a solvent after the terminal group on the side of the dicarboxylic acid is converted into an acid chloride, a uniform reaction is difficult, and therefore, one having a large molecular weight distribution is generally obtained. In addition, it is necessary to carry out a large amount of post-treatment of the catalyst compound, which complicates the production method and increases the cost. Also, despite various improvements, the moldability of the resulting material is still not satisfactory. Further, the polyester material disclosed in Japanese Patent Publication No. 4-22931 is liable to be hydrolyzed under high-temperature and humidified conditions because a phenolic hydroxyl group and a carboxyl group are directly bonded, and the moisture resistance is sufficient. I can't say.

[0005]

An object of the present invention is to provide a polyester polymer having excellent transparency, heat resistance, small optical anisotropy, and excellent moldability and dimensional stability. It is in.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, the specific polyester polymer is transparent, heat-resistant, and has a low optical anisotropy. They were found to be small and excellent in moldability and dimensional stability, and completed the present invention.

That is, the present invention relates to an aromatic dicarboxylic acid or a diester derivative thereof and a compound represented by the general formula (1):

Embedded image (R ₁ is an alkyl group having 2 to 4 carbon atoms, R ₂ , R ₃ , R
_4, and R ₅ are those dihydroxy compounds with number of carbon atoms represented by independently hydrogen or C 1 -C 4 alkyl) provides a reportage Riesuteru polymers such aliphatic glycols from 2 4.

Hereinafter, the present invention will be described in detail. The polyester polymer of the present invention comprises an aromatic dicarboxylic acid or a diester derivative thereof and a compound represented by the general formula (1):

Embedded image (R ₁ is an alkyl group having 2 to 4 carbon atoms, R ₂ , R ₃ , R
₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms) and a polyester polymer comprising an aliphatic glycol having 2 to 4 carbon atoms.
The dihydroxy compound represented by the general formula (1)
The polyglycol component is at least 10 mol% of the total glycol components in the fat.
Esteriester polymer or intrinsic viscosity (phenol
60% by weight, 1,1,2,2-tetrachloroethane 4
0% by weight in a mixed solution at 20 ° C.)
One such polyester polymer.

A glass transition temperature (Tg) of 90 ° C. to 155
° C., the intrinsic viscosity of Ru 0.3 or more degree of polymerization der, fluidity of the melt is particularly excellent. By changing the composition of 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene depending on the use, an appropriate molded article can be obtained.

When the amount of the dihydroxy compound represented by the general formula (1) in the polyester is less than 10 mol%, the molded article is easily deformed by heat, the heat resistance is insufficient, and the optical anisotropy is large. , Also reduces the stability of the molded body
Therefore, the content is preferably 10 mol% or more.

[0011] Poriesueru polymers of the present invention, 60% by weight phenol, 1,1,2,2, - mixed solution of 40% by weight tetrachloroethane, with an intrinsic viscosity measured at 20 ° C. of 0.3 or more preferably Rukoto Oh, and more preferably from 0.4 to 0.8. If the value is 0.3 or more,
Excellent mechanical strength, and below 0.8, the molecular orientation during molding
This is because the flow rate of the molded product is small and the flowability of the molded product is good.

In the present invention, the aromatic dicarboxylic acid is
Examples thereof include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and terephthalic acid is particularly preferable.

In the present invention, the dihydroxy compound represented by the general formula (1) is 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene, 9,9-bis-
(4-hydroxypropoxyphenyl) -fluorene,
9,9-bis- (4-hydroxybutoxyphenyl)-
There are fluorene and the like, and 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene is particularly preferable.

9,9-bis- (4-hydroxyethoxyphenyl) -fluorene is, for example, 9,9-bis-
It is obtained by adding ethylene oxide (hereinafter referred to as EO) to (4-hydroxyphenyl) -fluorene. On this occasion,
In addition to the 2EO adduct (9,9-bis- (4-hydroxyethoxyphenyl) -fluorene) in which ethylene oxide is added one molecule at a time to both hydroxyl groups of phenol, a 3EO adduct, which is further added in a few molecule excess, 4EO Impurities such as adducts may be included. When impurities such as 3EO and 4EO are increased, the heat resistance of the polyester polymer is lowered. At this time, the purity of the 2EO adduct was 85.
% Or more, but preferably 95% or more.

9,9-bis- (4-hydroxypropoxyphenyl) -fluorene and 9,9-bis- (4-hydroxybutoxyphenyl) -fluorene are, for example,
It can be obtained by reacting 9,9-bis- (4-hydroxyphenyl) -fluorene with 3-chloro-propan-1-ol and 4-chloro-propan-1-ol, respectively, under alkaline conditions. The purity at this time may be 85% or more, preferably 95% or more.

In the present invention, the aliphatic glycol is ethylene glycol, 1,3-propanediol,
-Propanediol, 1,4-butanediol 1,2-
Examples thereof include butanediol and 1,3-butanediol. Among them, ethylene glycol and 1,4-butanediol are preferable, and ethylene glycol is particularly preferable.

The polyester polymer of the present invention is, for example,
It can be produced by selecting an appropriate method from known methods such as a melt polymerization method such as a transesterification method and a direct polymerization method, a solution polymerization method, and an interfacial polymerization method. The reaction conditions for the polymerization catalyst and the like at this time may be the same as those in the related art, and a known method can be used.

When a solution polymerization method, an interfacial polymerization method, or the like is employed for producing the polyester polymer of the present invention, an acid chloride is generally used as an active species of an acid component, or methylene chloride or chloroform is used as a solvent. Etc. are used, but chlorides and catalyst compounds as by-products remain in the polymer, which are generally inferior in terms of product quality. . These are sheets, films, plates,
It reduces the operability in the molding process of fibers and the like, and also reduces the quality of the obtained molded body. For example, a large amount of thermal decomposition occurs during high-temperature heating. When used as an optical material, a metal thin film such as a reflective film or a recording film is fixed to a plate or a substrate by a method such as evaporation or sputtering. Therefore, it is necessary to perform a sufficient process of removing residual foreign substances such as washing and filtration, since the corrosion and the life of the product are reduced.

The polyester polymer of the present invention is particularly good when a melt polymerization method is used. That is, the compound of 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene has a property in which the terminal group is very similar to that of the aliphatic glycol and has high reactivity. This is significantly different from 9,9-bis- (4-hydroxyphenyl) -fluorene. For this reason, it is not necessary to use a raw material called acid chloride, and therefore, a production method in which chlorine is not essentially mixed is possible, and the amount of catalyst used can be reduced under high-temperature reaction conditions, and a method of reducing residual foreign substances is possible. It became.

In order to produce the polyester polymer of the present invention by a transesterification method of a melt polymerization method, the dihydroxy component represented by the general formula (1) is the same as the glycol component in the resin.
To 95 mol%. If this is more than 95 mol%, the melt polymerization reaction does not proceed,
Since it is difficult to reach a sufficient degree of polymerization, it is produced by a solution polymerization method or an interfacial polymerization method.

[0021]

As described above, the polyester polymer of the present invention can provide a molding material having good transparency, heat resistance, excellent moldability, dimensional stability, and chemical resistance.
It is industrially useful for film applications, sheet applications, and the like.

[0022]

The present invention will be specifically described below with reference to examples. The intrinsic viscosity, glass transition temperature, birefringence, and NMR of the copolymer in the examples were measured by the following methods.

(1) Intrinsic viscosity The copolymer 0.1 was added to 50 ml of a mixed solution of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane.
After dissolving 15 to 0.5 g at 80 ° C, the viscosity was measured and determined at 20 ° C.

(2) Glass Transition Temperature About 10 mg of a sample was measured with a differential scanning calorimeter (Rigaku Denki DSC-8230) at a heating rate of 10 ° C./min. The glass transition temperature Tmg and the extrapolated glass transition temperature end temperature Teg were determined as defined in JIS K ^7121-1987 .

(3) Birefringence A Clarmont, Berek, and Brace Keller compensator were mounted on a Carl Zeiss polarizing microscope.
The measurement was performed using monochromatic light of 46 nm. Measurement piece is 260 ~
Melting at 300 ° C. and extrusion molding to produce a disc-shaped test piece having a diameter of 30 mm and a thickness of 1 mm, and press-forming the formed test piece at 160 to 240 ° C.
A 0μ film was obtained. The obtained film is 4 × 40 m
m to obtain a measurement test piece. Extrapolated glass transition end temperature 10 test specimens at a temperature of Teg + 1 ° C
After being stretched at 40% at 40% / sec, the film was rapidly cooled to obtain a stretched film. The birefringence of these films was measured.

(4) NMR The novel polyester copolymer was measured using an FT-NMR apparatus manufactured by Varian (300MG). As a solvent, the sample is dissolved in a mixed solvent of trifluoroacetic acid and chloroform (1: 1), and tetramethylsilane is mixed as a standard,
The proton NMR spectrum was measured.

Hereinafter, "parts" in the examples means parts by weight. Example 1 38 parts of dimethyl terephthalate, 9,9-bis- (4-
(Hydroxyethoxyphenyl) -fluorene 35 parts,
Using 27 parts of ethylene glycol as a raw material, as a catalyst,
Using 0.042 parts of calcium acetate, these were charged into a reaction vessel, and stirred at 190 ° C. to 23 ° C. according to a conventional method.
The ester exchange reaction was performed by gradually heating to 0 ° C. After extracting a predetermined amount of methanol out of the system, 0.012 part of germanium oxide as a polymerization catalyst and 0.033 part of trimethyl phosphate to prevent coloring are added, and the temperature is increased and the pressure is gradually reduced. The temperature of the heating tank was set to 280 ° C and the degree of vacuum was set to 1 Torr while removing ethylene glycol generated.
r or less. While maintaining these conditions, waiting for the viscosity to rise, the reaction was terminated after 2 hours, and the reaction product was extruded into water to obtain pellets.

This copolymer had an intrinsic viscosity of 0.55 and a glass transition temperature of 124 ° C. The resin was melt molded at 290 ° C. to obtain a sample on a disk, and then pressed at 220 ° C. to obtain a 120 μm thick film. When stretched at 136 ° C., the birefringence was 41 × 10 ⁻⁴ .

Example 2 The raw material composition was 26 parts of dimethyl terephthalate, 56 parts of 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene and 18 parts of ethylene glycol, 0.028 parts of calcium acetate, and 0 parts of germanium oxide. .009
Parts and trimethyl phosphate were changed to 0.022 parts, and the process was carried out in the same manner to obtain pellets. The intrinsic viscosity of this polymer was 0.43 and the glass transition temperature was 150 ° C.

Using a small injection molding machine, the polymer
Melt molding was performed at 90 ° C. to obtain a sample on a disk. The resulting plate was uniform and transparent. It was pressed at 250 ° C to obtain a film with a thickness of 130μ.
When the film was stretched at, the obtained film was uniformly transparent. When the optical evaluation was performed, the birefringence was 12 ×
It was 10 ^-4 .

Examples 3 to 6 Table 1 shows the results measured in the same manner as in Example 1 except that the raw material composition ratio was changed. In each case, a uniform transparent product was obtained. The NMR spectrum of the sample of Example 5 is shown in FIG.
It was shown to.

Comparative Example 1 9,9-bis- (4-hydroxyethoxyphenyl)-
Table 1 also shows the results of pellets obtained in the same manner as in Example 1 except that fluorene was used in an amount of 0 part. As is clear from Table 1 , Comparative Example 1 is not preferable because of low heat resistance. Further, when the film was formed, it was uneven and varied depending on the sample. In addition, when the optical evaluation was performed, it was impossible to measure due to cloudiness.

Comparative Example 2 The dihydroxy compound of the present invention represented by the general formula (1)
Alternatively , 9,9-bis- (4-hydroxyphenyl)
-The reaction was started in the same manner as in Example 1 except that 35 parts of fluorene was used , the generated methanol was removed, and after the transesterification reaction was completed, the polymerization catalyst was charged in the same manner as in Example 1, The reaction proceeded, but no increase in viscosity was observed.
After the lapse of time, the viscosity of the polymer did not increase. The reaction was poured into water but did not form a pellet.

From the above, it was found that the polyester polymer of the present invention is rich in polymerizability, and the obtained polyester polymer has good transparency, heat resistance, and excellent moldability.

[0035]

[Table 1]

[Brief description of the drawings]

Figure 1 is, NMR of sample obtained in Example 5
It is a spectrum diagram.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 67:02 Examiner Satoshi Morikawa (56) References JP-A-63-152622 (JP, A) JP-A-57-192432 (JP) JP-A-3-281524 (JP, A) JP-A-3-73902 (JP, A) JP-B-4-22931 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08G 67/12-63/676

Claims (8)

(57) [Claims] An aromatic dicarboxylic acid or a diester thereof.
Le derivative with the general formula (1) ## STR1 ## (R ₁ is an alkyl group having 2 to 4 carbon atoms, R ₂ , R ₃ , R
₄ and R ₅ are independently hydrogen or an alkyl having 1 to 4 carbons.
A dihydroxy compound represented by the formula:
Is a polyester comprising an aliphatic glycol of 2 to 4
Coalescing. 2. Dihydroxylation represented by the general formula (1)
The compound is at least 10 mol% of the total glycol components in the resin.
The polyester polymerization according to claim 1, wherein
body. 3. Intrinsic viscosity (phenol 60% by weight, 1,
Mixed solution of 40% by weight of 1,2,2-tetrachloroethane
(Measured in liquid at 20 ° C.) is 0.3 or more
The polyester polymer according to claim 1 or 2, wherein 4. A polyester polymer according to any one of claims 1 to 3 in which the aromatic dicarboxylic acid is characterized in that the terephthalic acid. 5. The method according to claim 1, wherein the dihydroxy compound represented by the general formula (1) is 9,9-bis- (4-hydroxyethoxyphenyl) -fluorene.
The polyester polymer according to any one of the above . 6. The polyester polymer according to any one of claims 1 to 5, wherein the aliphatic glycol is ethylene glycol. 7. to general formula (1) dihydroxy compound represented by the molar ratio of the resin of the aliphatic glycols having 2 to 4 carbon atoms is 10:90 95: claim 1, characterized in that the 5 7. The polyester polymer according to any one of items 1 to 6 . 8. A polyester polymer molded article comprising the polyester polymer according to claim 1 .