JPH0848759A - Polyethylene naphthalate resin - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a polyethylene naphthalate resin having improved crystallinity without impairing heat resistance. [Structure] A dicarboxylic acid component containing naphthalenedicarboxylic acid as a main component and a diol component containing ethylene glycol as a main component, and 0.1 to 3 mol of an ethylene oxide adduct of a bisphenol compound or its derivative in all alcohol components. % Polyethylene naphthalate resin blended.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene naphthalate resin used for various molded articles, and more particularly to a polyethylene naphthalate resin having high crystallinity.

[0002]

2. Description of the Related Art Polyethylene terephthalate resin and polybutylene terephthalate resin are mainly used as a polyester resin for molding materials at present, and the amount thereof is increasing due to both excellent mechanical properties and low pollution. There is. In particular, polyethylene terephthalate resin is widely used in the fields of various beverage bottles and food containers by taking advantage of its excellent transparency and hygiene.

However, the polyethylene terephthalate resin cannot be used in a crystallized state in order to make the most of its transparency, and it is formed by stretching orientation under the condition that crystallization does not proceed, and the necessary mechanical properties are required. Manufactured to exert strength. However, since the polyethylene terephthalate resin has a glass transition temperature (Tg) in the vicinity of 75 ° C., it cannot be used in a temperature range (for example, 100 ° C.) that greatly exceeds the glass transition temperature.

Polyethylene naphthalate resin having a glass transition temperature of about 110 ° C. is known as a polyester resin which can be used while maintaining transparency in this temperature range, and its amount is gradually increased. It is increasing.

[0005]

However, the polyethylene naphthalate resin has very poor crystallinity, and when the crystallization drying is attempted, the polyethylene naphthalate resin chips are fused to each other before being crystallized. As a result, a so-called "boiler" is made, which causes troubles such as a bite failure when it is put into a molding machine. An object of the present invention is to provide a polyethylene naphthalate resin having improved crystallinity so that crystallization drying can be performed.

[0006]

In view of such a situation, the inventors of the present invention have made earnest studies on the crystallinity of polyethylene naphthalate resin, and as a result, have found that polyethylene naphthalate resin can be prepared by blending specific components with polyethylene naphthalate resin. They have found that the crystallinity of the phthalate resin can be remarkably improved and have reached the present invention.

The present invention comprises a dicarboxylic acid component containing naphthalenedicarboxylic acid as a main component and an alcohol component containing ethylene glycol as a main component, and the bisphenol compound or an ethylene oxide adduct of its derivative is 0 in all alcohol components. The polyethylene naphthalate resin is characterized by being blended in an amount of 1 to 3 mol%.

In the present invention, the dicarboxylic acid component used as the acid component is mainly composed of 2,6- or 1,4-naphthalenedicarboxylic acid and their ester-forming derivatives, and preferably the total acid component. The naphthalenedicarboxylic acid and its ester-forming derivatives account for 8%
It is 0 mol% or more, more preferably 90 mol% or more. This is because when the content of naphthalenedicarboxylic acid and its ester-forming derivative is low, the glass transition temperature tends to be low and it cannot be used in a high temperature range, or the mechanical strength of the resulting molded article tends to be low. This is because.

Further, other dicarboxylic acid components, for example,
Aromatic dicarboxylic acids such as terephthalic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and ester-forming derivatives thereof within the range not impairing the effect of the present invention, for example, 2
You may copolymerize in the range of 0 mol% or less. Examples of ester-forming derivatives of these acid components used include dialkyl esters and diaryl esters.

The diol component contains ethylene glycol as a main component, and preferably 80 mol or more, more preferably 90 mol% or more, of ethylene glycol in the total diol component. As a diol component other than ethylene glycol, cyclohexanedimethanol, butanediol, diethylene glycol or the like is used within a range not impairing the effects of the present invention, for example, 20 mol%.
It is also possible to copolymerize within the following range.

In the polyethylene naphthalate resin of the present invention, it is necessary that an ethylene oxide adduct of a bisphenol compound or its derivative is blended in all alcohol components within a specific range, and the presence of this component results in crystallinity. improves.

The ethylene oxide adduct of a bisphenol compound or its derivative is represented by the following general formula (1)
And those having a structure represented by the general formula (2).

[0013]

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[0014]

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Among the compounds represented by the above general formula (1) exemplified as the ethylene oxide adduct of a bisphenol compound or its derivative, X has the structure of the following general formula (3), wherein C (CH ₃ ) ₂ is present. Ethylene oxide adducts of bisphenol A are preferred.

[0016]

[Chemical 3]

In the present invention, the ethylene oxide adduct of the bisphenol compound or its derivative in the resin is
It is necessary to be blended in the range of 0.1 to 3 mol% in all alcohol components, preferably 0.5 to 2.5 mol%, more preferably 1 to 2.5 mol%. If the amount is less than this range, there is no effect on the improvement of crystallinity, and conversely, if the amount is more than this range, the glass transition point (Tg) of the resin decreases, and the crystallinity deteriorates adversely. It is not preferable because the properties are lowered and the crystallization and drying become difficult.

The polyethylene naphthalate resin of the present invention has a glass transition temperature (Tg) from the solid state measured by a differential scanning calorimeter (DSC) of 110 ° C. or higher, preferably 110 to 130 ° C. It is necessary that the difference between the crystallization temperature (Tc ⁺ ) and the glass transition point (Tg) is 80 ° C or lower and the Tc ⁺ is 200 ° C or lower.
The difference between Tc ⁺ and Tg is greater than 80 ° C and Tc ⁺ is 200
If the temperature is higher than 0 ° C, fusion tends to occur during crystallization, which is not preferable. If the Tg is less than 110 ° C, the molded product may be softened when treated with hot water or the like, which is not preferable.

The polyethylene naphthalate resin of the present invention preferably has a viscosity average molecular weight of 10,000 to 70,000. This has a viscosity average molecular weight of 1000.
This is because if it is less than 0, the mechanical strength of the obtained molded product tends to be impaired, and conversely if it exceeds 70000, the moldability tends to decrease.

The intrinsic viscosity [η] of the polyethylene naphthalate resin of the present invention is not particularly limited, but is preferably 0.4 or more in view of moldability and mechanical properties of a molded product. The intrinsic viscosity [η] is a value measured at 25 ° C. in an equal weight mixed solvent of phenol and 1,1,2,2-tetrachloroethane. The viscosity average molecular weight was calculated by the following formula. Mv = [η] ^1.47 × 3.92 × 10 ⁴

The polyethylene naphthalate resin of the present invention may be added with an antioxidant, a heat stabilizer, an ultraviolet absorber, a dye, etc. within a range that does not impair the characteristics thereof.

The polyethylene naphthalate resin of the present invention can be produced by a known polymerization method such as a transesterification method or an esterification method. In the transesterification method, an ester-forming derivative of naphthalenedicarboxylic acid, ethylene glycol, and a predetermined amount of a bisphenol compound or an ethylene oxide adduct of the derivative are charged in a reaction vessel and reacted at 150 to 250 ° C. in the presence of a transesterification catalyst. Then, stability, a polymerization catalyst, etc. are added and it can be obtained by heating at 260-300 degreeC under reduced pressure of 5 mmHg or less, and making it react for 3 to 5 hours.

In the esterification method, naphthalenedicarboxylic acid, ethylene glycol, an ethylene oxide adduct of a bisphenol compound or a derivative thereof is charged into a reaction vessel, and the esterification reaction is carried out at 150 to 260 ° C. under nitrogen pressure to complete the esterification reaction. After that, a stabilizer, a polymerization catalyst, etc. are added, and the pressure is reduced to 5 mmHg or less at 260 ° C. to 300 ° C.
It can be obtained by heating to room temperature and reacting for 3 to 5 hours.

The transesterification catalyst used in the production of the polyethylene naphthalate resin of the present invention includes zinc acetate, manganese acetate, magnesium acetate, titanium tetrabutoxide, and the like, and the polymerization catalyst is trioxide. Examples thereof include antimony and germanium dioxide.

The polyethylene naphthalate resin of the present invention can be made into various resin molded products by using known molding methods such as extrusion molding, blow molding, vacuum molding and injection molding.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples. The method for measuring the thermal characteristics of the resin used in the present invention is as follows. The glass transition temperature (Tg) and the crystallization temperature (Tc ⁺ ) from the fixed state were measured with a differential scanning calorimeter (DSC) (manufactured by Shimadzu Corporation) at 5 ° C./min for a sample melt-quenched at 280 ° C. in a nitrogen stream. The temperature was raised to 280 ° C., and further cooled from this state at 5 ° C./min for measurement. Tg was the shoulder value and Tc ⁺ was the peak value.

In the following examples, as the ethylene oxide adduct of the bisphenol compound or its derivative, the bisphenol A ethylene oxide adduct of the general formula (3) with n + m = 2 was used.

Example 1 100 parts by mol of dimethyl naphthalene dicarboxylate, 200 parts by mol of ethylene glycol,
0.5 mol part of bisphenol A ethylene oxide adduct was charged into a reaction vessel, 500 ppm of manganese acetate was added as a transesterification catalyst to the weight of the acid component, and the temperature was gradually raised to 240 ° C. to conduct a transesterification reaction.

After completion of the esterification reaction, trimethyl phosphate as a stabilizer was added at 400 ppm to the acid component weight, and antimony trioxide was added as a polymerization catalyst at 600 ppm to the acid component weight, and the pressure was gradually reduced to 5 mmHg or less.
The temperature was raised to 90 ° C. and the reaction was carried out for 4 hours to obtain a polyethylene naphthalate resin.

[Example 2] A polyethylene naphthalate resin was obtained in the same manner as in Example 1 except that 1 part by mole of the bisphenol A ethylene oxide adduct was used.

[Example 3] Naphthalene dicarboxylic acid 10
0 mol part, 140 parts by mol of ethylene glycol, and 2 parts by mol of bisphenol A ethylene oxide adduct were charged into a reaction vessel, and the temperature was gradually raised to 260 ° C. under nitrogen pressure to carry out an esterification reaction.

After completion of the esterification reaction, 300 pppm of trimethyl phosphate as a stabilizer and the weight of the acid component,
As a polymerization catalyst, 600 ppm of antimony trioxide was added to the weight of the acid component, and the temperature was raised to 290 ° C. while gradually reducing the pressure to 5 mmHg or less and reacted for 4 hours to obtain a polyethylene naphthalate resin.

[Example 4] Naphthalenedicarboxylic acid 10
0 mol part, 140 mol part of ethylene glycol, and 3 mol part of bisphenol A ethylene oxide adduct were charged into a reaction vessel, and the temperature was gradually raised to 260 ° C. under nitrogen pressure to carry out an esterification reaction. Thereafter, the same operation as in Example 3 was performed.

Comparative Example 1 100 mol parts of dimethyl naphthalene dicarboxylate and 200 mol parts of ethylene glycol were charged into a reaction vessel, 500 ppm of manganese acetate as an ester exchange catalyst was added to the weight of the acid component, and the temperature was gradually raised to 240 ° C. A transesterification reaction was performed.

After completion of the transesterification reaction, trimethyl phosphate was added as a stabilizer in an amount of 400 ppm relative to the weight of the acid component,
400 ppm of germanium dioxide as a polymerization catalyst was added to the weight of the acid component, the temperature was raised to 290 ° C. while gradually reducing the pressure to 5 mmHg or less, and the reaction was carried out for 5 hours to obtain a polyethylene naphthalate resin. The resin has a large difference between the Tc ⁺ and Tg, were those poor crystallinity for high Tc ^+.

Comparative Example 2 Naphthalenedicarboxylic acid 10
0 mol part, 140 parts by mol of ethylene glycol, and 10 parts by mol of bisphenol A ethylene oxide adduct were charged into a reaction vessel, and the temperature was gradually raised to 260 ° C. under nitrogen pressure to carry out an esterification reaction. Thereafter, the same operation as in Example 3 was performed. This resin was poor in crystallinity because Tc ⁺ was broad.

With respect to the polyethylene naphthalate resins obtained in each of the examples and comparative examples, the intrinsic viscosity [η],
The molecular weight, melting point and thermal property values were measured. These are collectively shown in Table 1.

[0038]

[Table 1]

[0039]

INDUSTRIAL APPLICABILITY The polyethylene naphthalate resin of the present invention impairs heat resistance due to the fact that the ethylene oxide adduct of the bisphenol compound or its derivative is blended in a specific amount in all the alcohol components constituting the polyethylene naphthalate. The crystallinity is improved without any trouble, and it is suitable for various beverage bottles, food containers, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seisuke Tanaka 2-4-1, Ushikawa-dori, Toyohashi-shi, Aichi Sanryo Rayon Co., Ltd. Toyohashi Plant

Claims (2)

[Claims] 1. A dicarboxylic acid component containing naphthalenedicarboxylic acid as a main component and an alcohol component containing ethylene glycol as a main component, wherein the ethylene oxide adduct of the bisphenol compound or its derivative is 0.1 in all alcohol components. A polyethylene naphthalate resin characterized by being mixed in an amount of up to 3 mol. 2. The glass transition temperature (Tg) from the solid state measured by a differential scanning calorimeter is 110 ° C. or higher, and the crystallization temperature (Tc ⁺ ) from the solid state is 200 ° C. or lower.
⁺ -Tg is 80 ° C. or lower.
The polyethylene naphthalate resin described.