JPS60221420A - Polyester film - Google Patents

Abstract

PURPOSE:To provide the titled film consisting of a novel linear aromatic polyester containing (ethylenedioxy)dinaphthoic acid as an acid component, and having excellent heat resistance, hydrolysis resistance and chemical stability and high strength and Yound's modulus. CONSTITUTION:The objective film can be manufactured by using (A) and acid component composed mainly of 6,6'-(ethylenedioxy)di-2-naphthoic acid and (B) a glycol component composed mainly of a 2-10C glycol having even number of carbon atoms constituting the main chain (preferably ethylene glycol), and having an intrinsic viscosity of >=0.4. The film is manufactured preferably by drying said polyester, melting and extruding at a temperature above its melting point and <=330 deg.C, and quenching by contacting with a rotary drum of a temperature lower than the glass transition temperature of the polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention comprises a novel aromatic polyester 7 1 J
l-L If you have any questions regarding the film, please refer to the novel aromatic polyester film containing 6,6'-(ethylenedioxy)di-2-naphthoic acid as the main acid component, which can be applied to the skin. .

BACKGROUND OF THE INVENTION In recent years, with the advancement of technology, there has been an increasing demand for films with high physical and chemical performance.

For example, polyethylene terephthalate film has a heat resistance of 1
It has excellent strength, Young's modulus, etc., and is either widely used or not sufficient for some applications, and products with even higher performance are being sought.

This polyethylene terephthalate is more aromatic.

Polyester with high molecular rigidity and L7 polyethylene 2
, 6-naphthalate, polyester obtained by condensation polymerization of 4'-(ethylenedioxy) dibenzoic acid and ethylene glycol, etc. are known, but these also have sufficient properties and are still difficult to engineer. It's hard to say that there are.

OBJECT OF THE INVENTION An object of the present invention is to provide a polyester film that has excellent chemical stability such as heat resistance, hydrolysis resistance, and chemical resistance, and has high strength and Young's modulus.

Structure and Effects of the Invention The main features of the present invention are: an acid component mainly consisting of e, e'-(ethylenedioxy)di-2-naphthoic acid, having 2 to 10 carbon atoms, and forming a main chain; This is achieved by a film made of a substantially linear aromatic polyester, which is made up of repeating ester units of a diol component mainly consisting of glycol having an even number of carbon atoms, and has an intrinsic viscosity of 0.4 or more.

Such a film has 2 to 10 carbon atoms and forms a main chain with a bifunctional carboxylic acid mainly consisting of e,e'-(ethylenedioxy)di-2-naphthoic acid and/or its ester-forming derivative. The aromatic polyester obtained by reacting a diol mainly consisting of glycol with an even number of carbon atoms until the intrinsic viscosity of the polymer becomes 0.4 or more can be easily produced by, for example, melt-casting the resulting aromatic polyester. can.

6,6'-(ethylenedioxy)di2 in the present invention
-Naphthoic acid is an aromatic dicarboxylic acid represented by the following structural formula (2).

・・・・・・・・・・・・■ The above s, e'-(ethylenedioxy)di-2-naphthoic acid can be partially replaced with another difunctional carboxylic acid. Other difunctional carboxylic acids have the following structural formula 1. Carboxylic acids represented by I can be mentioned.

HOOC-R' -COOH-・・−・−・・IHOO
C-R'-OH・・・・・・・・・・・・■ R1 above
For example, alkylene having 2 to 10 carbon atoms; substituent (
Phenylene which may be substituted with a nucleus (for example, lower furkyl,...rogen, etc.).

Examples include naphthalene, diphenylene; cycloalkylene having 6 to 12 carbon atoms, and R'' includes, for example, the same meaning as R1 above or a group represented by →→CH, C2, etc. More specifically. Examples include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and oxybenzoic acid.

Examples include cabbonic acid, cepatic acid, and cyclohexanedicarphonic acid.

Preferably, such other difunctional carboxylic acids are present in an amount of less than 50 molti, more preferably less than 30 molti, particularly less than 20 molti, per total acid component.

Further, in the present invention, glycols having 2 to 10 carbon atoms and an even number of carbon atoms forming the main chain include, for example, ethylene glycol, imp pyrene glycol, tetramethylene glycol, hexamethylene glycol,
Examples include octamethylene glycol. Among these, ethylene glycol and tetramethylene glycol are preferred, and ethylene glycol is particularly preferred.

The above-mentioned glycol having 2 to 10 carbon atoms and an even number of carbon atoms forming the main chain can be partially substituted with another diol. Other diols include diols represented by the following structural formula (2).

HO-R”-OH・・・・・・・・・・・・■Rs above
Preferred examples include trimethylene, pentamethylene, optionally substituted phenylene, naphthalene, diphenyl, and cycloalkylene having 6 to 12 carbon atoms.

Preferably, the amount of such other diols is less than 50 molti, even less than 30 molti, especially less than 20 molti, per total diol component.

In the present invention, the aromatic polyester is composed of an ester of the above acid component and diol component, and a, s' = (
Ethylenedioxy)di-2-naphthoic acid component and a glycol component having 2 to 10 carbon atoms and an even number of carbon atoms forming the main chain have ester units of 50 of the total repeating units.
% or more, more preferably 70% or more, particularly 80% or more. This aromatic polyester has an intrinsic viscosity of 0.
It is preferably 4 or more, more preferably 0.5 or more.

The aromatic polyester of the present invention can be produced according to conventionally known polyester polycondensation methods, but a preferred method is to use 6,6'-(ethylenedioxy)di-2-naphthoic acid and/or its The ester-forming derivative and the glycol having 2 to 10 carbon atoms and an even number of carbon atoms forming the main chain are optionally combined with other acid components such as dicarboxylic acid, hydroxycarboxylic acid and/or
Alternatively, there may be a method in which a reaction is carried out using ester-forming derivatives of these or dihydroxy compounds serving as other diol components, preferably in the presence of a catalyst.

Examples of the ester-forming derivatives of the carboxylic acids include lower furkyl esters such as methyl, ethyl, and propyl, and aryl esters such as phenyl. It is preferable to use diol in an amount of 1.1 to 3 moles based on the total acid components (5%). Examples of catalysts include sodium, potassium, and lithium.

Calcium, magnesium, barium, tin, stopuntium, zinc, iron, aluminum, cobalt, lead, nickel, titanium, manganese.

Elements such as antimony, oxides, hydrides, hydroxides, etc.
- Examples include p-gyanides, inorganic and organic acid salts, complex salts, double salts, alcoholades, phenolates, etc., and two or more of these may be used in combination. In particular, antimony compounds, germanium compounds, titanium compounds, etc. are preferably used as polycondensation catalysts. The amount of the catalyst is preferably about 0.005 to 0.5 molti based on the polymer. The preferred polymerization temperature is above the melting point of the obtained polymer and below 350°C, more preferably above the melting point +5°C and below 330°C. However, when a particularly high degree of polymerization is desired, relatively low polymerization obtained by melt polymerization is preferred. It is also possible to employ a so-called solid phase polymerization method in which the degree of polymerization is increased by pulverizing the polymer and heating it to a temperature lower than the contact point of the polymer under reduced pressure and/or in a stream of inert gas.

Aromatic polyesters include compounds having one ester-forming functional group, such as benzoic acid and benzoylbenzoic acid, within the range where the polymer is substantially linear; The aromatic polyester may contain residues of a compound having three or more ester-forming functional groups such as mellitic acid. It can be obtained by adding it to a reaction system and causing a reaction.

The polyester film of the present invention can be produced by extruding the aromatic polyester thus obtained, preferably under melting of the core polyester, and immediately rapidly cooling it to a temperature below the glass transition temperature of the polyester. At that time, after drying the aromatic polyester, the polymer melting point (Tm
:C) melted at a temperature above 350°C, more preferably below 330°C, extruded through a film forming die, and subsequently contacted on a rotating drum kept at a temperature below the polymer glass transition temperature (Tg:'C) It is preferable to let it cool down rapidly. Although the film of the present invention has excellent performance in heat resistance, hydrolysis resistance, etc. even in the unstretched state obtained in this manner, in order to further improve other properties, the film in the unstretched state is Alternatively, it may be stretched in two axial directions, and stretching is preferred depending on the application. Stretching is from (Tg-10)℃ to ('rg+50)
It is preferable to carry out the treatment at a temperature of about 0.degree. C. so that the area magnification is 1-2 times or more, more preferably 5 times or more, particularly 8 times or more. In the case of biaxial stretching, the stretching method may be sequential or simultaneous.

The stretched film A is preferably stretched or heat-treated at a stretching temperature of (Tm-, 10)°C.

The aromatic polyester film of the present invention may contain other thermoplastic polymers, stabilizers such as ultraviolet absorbers, antioxidants, plasticizers, lubricants, and flame retardants.

A release agent, pigment, nucleating agent, filler, etc. may be added as necessary.

Example The present invention will be explained below with reference to Examples.

The intrinsic viscosity was determined using a mixed solvent of p-chlorophenol/tetrachloroethane (40/g o weight ratio) at 35°C.
The glass transition temperature and melting point were measured by DSC at a heating rate of 20° C./min. In addition, “department” in the example is “
Parts by weight.

Reference Example A reactor equipped with a rectification column was charged with 4ss parts of diethyl 6.6'-(ethylenedioxy)di-2-naphtonite (melting point 193°C), 130 parts of ethylene glycol, and 0.1 part of titanium tetrabutoxide. The reaction mixture was heated to 0.degree. C., and the ethanol produced by the reaction was distilled out of the system. After y theoretical amount of ethanol has been distilled off, the reactant is stirred,
Transfer to a reactor equipped with a nitrogen gas inlet and a distillation outlet, and
The reaction was carried out at 0°C for 30 minutes at normal pressure in a nitrogen gas stream, and then the reaction temperature was raised to 310°C, and the pressure inside the system was gradually reduced, and after 15 minutes the absolute pressure was about 0, 2 mH9 and 17, and then 1
React for 0 minutes. The obtained polymer is transparent when melted, but crystallizes even when rapidly cooled, and has an intrinsic viscosity of 0.63.
The glass transition point was 129°C and the melting point was 294°C.・
Examples 1 to 4 The polyester obtained in the reference example was pulverized and dried 1-32
It was melted at 0°C, extruded through a T-die at intervals of 0.5 parts, brought into close contact with a rotating drum at about 80°C, and rapidly cooled to obtain an unstretched film. This film was milky white and translucent, and had the physical properties shown in Example 1 in Table 1.

Next, this film was uniaxially stretched at 140°C, and further stretched at 150°C in a direction perpendicular to the uniaxial stretching direction by the ratio shown in Table 1 (7) to obtain sequentially biaxially stretched films (Examples 2 to 3).
4).

The physical properties of these films are summarized in Table 1.

Example 5 and Comparative Examples One ton of the film obtained in Example 1 was immersed for 10 hours in a 20% caustic soda aqueous solution heated to 80° C. During this time, the polymer did not completely decompose and no weight loss was observed.

On the other hand, for comparison, when an unstretched film of polyethylene terephthalate was treated in the same manner as above, the weight retention rate was 39% 10 hours after decomposition from the film surface.

This shows that the film of the present invention has extremely excellent hydrolysis resistance.

Example 6 The film obtained in Example 4 was heat-treated at 280° C. in an air atmosphere for 3 minutes at a constant length 1-. The physical properties of the obtained heat-treated film in the second-axis stretching direction were as follows.

Strength: 30.7 Kg/gj Young's modulus: 1370 edge/- Elongation: 5t16 - Also, the heat-treated film was immersed in silicone oil at the temperature shown in Table 2 for 30 seconds in a free state. The film shrinkage rates at this time are shown in Table 2.

Table 2

Claims (1)

[Claims] 1.6.6'-(Ethylenedioxy)di-2-naphthoic acid as the main acid component and glycol as the main chain containing glycol having 2 to 10 carbon atoms and an even number of carbon atoms forming the main chain A film made of a substantially linear aromatic polyester consisting of repeating ester units with a component and having an intrinsic viscosity of 0.4 or more. 2 Aromatic polyester is poly(ethylene 6.6'-(
2. The film according to claim 1, which is ethylenedioxy)di-2-7toate).