JPH06329886A - Polyester composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition consisting of a polyester having a nitrogen-containing heterocyclic ring at the side chain, small in lowering of intrinsic viscosity before and after melt extrusion, excellent in resistance to hydrolysis, resistance to deterioration due to oxidation and oxygen barrier properties and useful for fibers, coating films, etc. CONSTITUTION:The objective composition comprises a polyester having one ore more nitrogen-containing heterocyclic rings selected from the group consisting of pyridine, pyridazine, pyrimidine, pyrazine, quinoline, piperidine, phenazine, pyrol, pyroline, pyrrolidine, pyrazole, imidazole, piperidine, piperazine, indole, carbazole and their derivatives [e.g. pyridinyl-alkylene diol (derivative)] at the side chain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition having excellent hydrolysis resistance and oxidative deterioration resistance, as well as excellent oxygen barrier properties.

[0002]

2. Description of the Related Art Since polyester has an ester bond in its main chain, it is relatively easy to undergo hydrolysis and oxidative deterioration.
For this reason, measures such as adding a heat stabilizer, increasing the crystallinity and the degree of orientation, and reducing the water content in the polyester as much as possible have hitherto been taken.

[0003]

However, in order to prevent hydrolysis that occurs during melt extrusion, the water content in the polyester should be made as small as possible, for example, in the case of polyethylene terephthalate, it should be 20 ppm or less. However, hydrolysis was not avoided during melt extrusion, and a decrease in intrinsic viscosity [η] of 0.015 or more before and after extrusion was unavoidable. Further, hydrolysis in a sheet form or the like is slightly effective in increasing the crystallinity and the degree of orientation, but it is not a significant improvement in practical use. Furthermore, there is no effective additive for hydrolysis,
Further, it has a drawback that the additive bleeds out on the surface.

That is, there was no polyester composition having excellent hydrolysis resistance and oxidation deterioration resistance.

[0005]

The polyester composition of the present invention which meets the above-mentioned object is characterized in that it is a polyester composition comprising a polyester having a nitrogen-containing heterocycle in its side chain.

Polyester is a polymer having an ester group in the main chain formed by condensation polymerization of dicarboxylic acid and diol. The dicarboxylic acid component includes aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid and heterocyclic ring. Formula dicarboxylic acid, polyfunctional acid, etc. are mentioned. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenic acid,
And their derivatives, and the like, as the alicyclic dicarboxylic acid, there are 1,4-cyclohexanedicarboxylic acid and its derivatives, and as the aliphatic dicarboxylic acid,
Adipic acid, sebacic acid, dodecanedioic acid, eicoic acid, dimer acid and their derivatives, etc., Heterocyclic dicarboxylic acids include pyridinedicarboxylic acid and their derivatives, etc., and polyfunctional acids include trimellitic acid. Pyromellitic acid and its derivatives are typical. Examples of the alcohol component include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, bisphenol, pyridinedimethanol and their derivatives. Is a typical one. Further, the polyester used in the present invention includes a block copolymer with a polyester ether obtained by copolymerizing a polyether such as polyethylene glycol or polytetramethylene glycol, a polyester amide obtained by copolymerizing a polyamide, or an aliphatic polyester such as polycaprolactone. It also includes coalescence.

Among these polyesters, polyethylene terephthalate (PET) is the main component, preferably from the viewpoints of film-forming properties such as stretching properties, mechanical properties, heat resistance, chemical resistance, low cost and the like. Polyester, in which 50 mol% or more of each of the acid component and the alcohol component of the polyester is terephthalic acid, ethylene glycol or a derivative thereof, is preferably used in the polyester of the present invention.

Pyridine and piperidine are 6-atom heterocyclic compounds containing one nitrogen atom,

[Chemical 1]

[Chemical 2] It is represented by.

Pyridazine, pyrimidine, pyrazine and piperazine are each a 6-atom heterocyclic compound containing two nitrogen atoms,

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6] Is a compound represented by.

Further, quinoline, bipyridine, and phenazine are respectively

[Chemical 7]

[Chemical 8]

[Chemical 9] Is a compound represented by.

Pyrrole, pyrroline, and pyrrolidine are 5-atom heterocyclic compounds containing one nitrogen atom.

[Chemical 10]

[Chemical 11]

[Chemical 12] Is a compound represented by.

Pyrazole and imidazole are 5-atom heterocyclic compounds containing two nitrogen atoms.

[Chemical 13]

[Chemical 14] Is a compound represented by.

Indole and carbazole are 9 and 13 atom heterocyclic compounds containing one nitrogen atom, respectively.

[Chemical 15]

[Chemical 16] Is a compound represented by.

It is important that the above-mentioned compounds are copolymerized not in the main chain of the polyester but in the side chain. This is because when it is copolymerized in the main chain, the crystal melting point becomes too high, and thermal decomposition easily occurs during melt extrusion molding,
As a result, unmelted substances and carbides are mixed in, and the gas barrier property is deteriorated, which is not suitable for the purpose of the present invention. However, when copolymerized to the side chain, unlike the case of the main chain, the glass transition point and melting point are low, and it is possible to mold into a uniform sheet without thermal decomposition during melt extrusion molding, so if only gas barrier property Instead, the polyester composition is excellent in hydrolysis resistance and oxidation deterioration resistance.

The polyester having a nitrogen-containing heterocycle in its side chain is typically as follows.

[0016]

[Chemical 17]

[Chemical 18] Here, G represents a glycol residue, R represents a dicarboxylic acid residue such as an alkyl group, an allyl group or a phenyl group, and X represents a nitrogen-containing heterocyclic residue.

For example, as a typical polyester composition,

[Chemical 19] For example, in the case of 2- (2pyrudinyl) 1,3 propanediol,

[Chemical 20] When a compound containing a nitrogen-containing heterocycle such as pyridine, pyridazine, pyrimidine, or pyrazine is copolymerized with another polyester, the copolymerization ratio is 0.1 mol% or more,
It is preferably copolymerized in an amount of preferably 1 mol% or more, more preferably 5 mol% or more. If less than this,
This is because there is little effect in improving the hydrolysis resistance and the oxidation deterioration resistance, which are the objects of the present invention. When importance is attached to the oxygen barrier property, the heterocyclic compound containing nitrogen is 50 mol%.
It is preferable to copolymerize at least 60 mol%, preferably at least 60 mol%.
Further, particularly in order to prevent oxidative deterioration, it is preferable that the terminal of the polyester is a nitrogen-containing heterocyclic compound such as pyridine.

In order to impart water solubility to the polyester of the present invention, it is preferable to copolymerize the above nitrogen-containing compound with the polyester in an amount of 30 mol% or more. If this aqueous solution is used as a coating liquid for coating, easy adhesion and antistatic property Such characteristics can be added. Compared with other coating liquids, this coating liquid is particularly effective for nylon and polyester, and not only has excellent adhesiveness with the base film, but it also has stable extrusion heat even when the coating film is collected in the base layer. It has excellent properties and can be uniformly mixed with the base layer, and has excellent recoverability.

In the polyester composition of the present invention, optional additives such as heat stabilizers, antioxidants, crystal nucleating agents, weathering agents, UV absorbers, pigments, dyes, slip agents, viscosity reducing agents, inert particles. Etc. can be added. Here, as the inert particles, silicon oxide, titanium oxide, barium sulfate, aluminum oxide, zirconium oxide, calcium carbonate,
Inorganic compounds such as magnesium carbonate, or crosslinked polystyrene, crosslinked divinylbenzene, benzoguanamine,
Examples include non-melting organic compounds such as silicone. Colloidal silica, pulverized silica, crosslinked polystyrene, silicone and the like are particularly preferable in terms of transparency. The average particle size is preferably 0.01 to 10 μm, and more preferably 0.1 to 8 μm, as a preferable particle size for improving the slipperiness of the film.
Is. The addition amount is 0.001 to 10% by weight, preferably 0.01 to 5% by weight.

The polyester composition of the present invention may be formed into an extrusion molded product, or may be molded into a fiber, a coating film, a film, a sheet or a foam. If necessary, surface irregularity processing such as embossing or sand matting, or surface treatment such as corona discharge treatment, plasma treatment, or alkali treatment may be performed. Furthermore, an easy-adhesion treating agent, an antistatic agent, a water vapor / gas barrier agent (such as polyvinylidene chloride), a release agent, a pressure-sensitive adhesive, an adhesive, a flame retardant, and an ultraviolet absorbing agent are applied to the above-mentioned various molded products made of the polyester composition of the present invention. Surface coating and printing of agents, matting agents, pigments, dyes and the like may be performed, and the purpose and method thereof are not particularly limited.

Since the polyester of the present invention exhibits a cationic property, Cl ⁻ , Br ⁻ , 1/2 SO ₄ ^-2 , 1/3 PO ₄
Inorganic acid residue such as _{^{-3, CH 3 SO 4 -,}} C 2 H 5 SO 4
_{^{-, C l H 21 + 1}} COO - ( natural number l = 1 to 6), an organic sulfonic acid residue or a carboxylic acid residue and may form a complex.

In addition, the composition of the present invention comprises a urea-based, melamine-based or guanamine-based resin which is methylolated or alkylolated as a cross-linking agent in order to improve water resistance, solvent resistance, blocking resistance and mechanical strength. , Acrylamide type,
A compound such as a polyamide-based compound, an epoxy compound, an aziridine compound, a block polyisocyanate, a silane coupling agent, a titanium coupling agent, a peroxide, a photoreactive vinyl compound, and a photosensitive resin may be contained.

The polyester of the present invention can be polymerized by a known polycondensation method.

[0024]

[Measurement / Evaluation Method of Physical Properties and Characteristics] The measurement / evaluation method of characteristics used in the description of the present invention will be described below.

(1) Oxygen permeability According to ASTM-D-3985, it was measured under the conditions of 20 ° C. and 65 RH% using an oxygen permeability / measuring device of OX-TRAN100 manufactured by Modern Control.

(2) Intrinsic viscosity: Measured in ortho-chlorophenol at 25 ° C. according to ASTM-D-1601 and expressed in dl / g.

(3) Breaking elongation Measured according to ASTM-D-882-81 (method A).

[0028]

EXAMPLES The effects of the present invention will be shown below by examples.

Examples 1 to 4 and Comparative Example 1 Ethylene glycol and 2 (2pyridinyl) 1,3pyropandiol were used as diol components, and terephthalic acid was used as a dicarboxylic acid by varying the copolymerization ratio and polymerized by a known method. Then, a nitrogen-containing heterocyclic side chain copolymerized polyethylene terephthalate was obtained. The polyester was dried by a conventional method at 180 ° C. under 1 mmHg for 4 hours and then fed to an extruder of 250 mm, and after a residence time of 15 minutes at 285 ° C., it was extruded into a sheet form from a die, and an electrostatic charge was applied thereto to cool the drum. And then rapidly cooled to obtain a cast film having a thickness of 40 μm. The properties of the films thus obtained are listed in Table 1.

[0030]

[Table 1] As described above, when the copolymerization ratio is preferably 0.1 mol% or more, more preferably 1 mol% or more, it can be seen that excellent properties are exhibited in hydrolysis resistance, oxidation deterioration resistance, and heat decomposition resistance. .

Examples 5 to 8 and Comparative Example 2 Polymerization was carried out by increasing the copolymerization amount of the nitrogen-containing heterocyclic diol used in Examples 1 to 4 to 30 to 100 mol%, and the intrinsic viscosity was 0.6.
The polymer was 8 to 0.70. The polymer was supplied to a twin-screw vent extruder, extruded under reduced pressure at 285 ° C., a molten sheet was discharged from a die, and was adhered to a cooling drum and solidified by cooling while applying an electrostatic charge. 9 in the longitudinal direction
After stretching 4 times on a roll heated to 0 ° C, 4 times stretched in a width direction with a tenter heated to 95 ° C.
The film was heat set at 0 ° C. to obtain a film having a thickness of 12 μm.

[0032]

[Table 2] It can be seen that the oxygen barrier property is significantly improved by increasing the copolymerization amount.

Example 11 The polymer used in Example 6 was dissolved in water to obtain a coating liquid (solid content: 5%).

A cast sheet of polyethylene terephthalate was stretched 4.5 times in the longitudinal direction at 95 ° C. to one side of a uniaxially stretched film, which was coated with the above coating solution, dried in a transverse stretching zone, and then transversely stretched 4 times at 100 ° C. Subsequently, it was heat set at 210 ° C. The film thus obtained had a thickness of 38 microns with a 0.01 micron coating coating deposited thereon.

The coating surface of the film is not only excellent in various adhesive properties, but also has a surface specific resistance of 10 ⁸ ohm /
It also had excellent □ and antistatic properties.

[0036]

Since the polyester of the present invention contains a specific nitrogen compound in the side chain, it exhibits the following excellent properties.

It has excellent hydrolysis resistance, and the decrease in intrinsic viscosity before and after melt extrusion is small.

Oxidative deterioration is less likely to proceed even by heat treatment near the melting point of the polyester, for example, at a temperature of 40 ° C. or lower lower than the melting point, and the breaking spread is large.

Excellent oxygen barrier property, 1 cc / m ²
It shows an excellent value of 24 hrs / 100 μ or less.

Claims (3)

[Claims] 1. A polyester composition comprising a polyester having a nitrogen-containing heterocycle in its side chain. 2. A group in which the nitrogen-containing heterocycle comprises pyridine, pyridazine, pyrimidine, pyrazine, quinoline, bipyridine, phenazine, pyrrole, pyrroline, pyrrolidine, pyrazole, imidazole, piperidine, piperazine, indole, carbazole, and derivatives thereof. 2. The polyester composition of claim 1 which is at least one selected from the more selected. 3. The polyester composition according to claim 2, wherein the pyridine derivative is at least one selected from pyridinyl alkylene diol and its derivatives.