JPH0597982A - Aromatic polyester resin - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyester resin containing a specific dicarboxylic acid component, having moldability similar to that of PET and exhibiting excellent barrier properties to ultraviolet ray, oxygen and steam. CONSTITUTION:A polyester obtained by copolymerizing (A) dicarboxylic acid component selected from A1: terephthalic acid or its esterformable derivative and A2: bis(2-hydroxy-2-oxoethoxy)-9, 10anthraquinone of formula I or its ester- formable derivative with (B) a glycol component containing a glycol component selected from a 2-10C straight-chain aliphatic glycol as an essential component and as necessary >=20mol% other copolymerizable component, and composed of 0.1-100%, preferably 0-99.5% recurring units of formula II [(m) is integer of 2--10], 0-99.9%, preferably 0-99.5% recurring units of formula III [(n) is same as (M)], and preferably having >=0.5g/dl intrinsic viscosity (in a solvent in which weight ratio of phenol/tetrachloroethane is 60/40 at 25 deg.C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polyester resin excellent in ultraviolet barrier property and gas barrier property.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter abbreviated as PET) is processed into various containers such as films, sheets, cups, bottles and trays due to its excellent mechanical and chemical properties. Widely used as a packaging material. For example, PET is more excellent in oxygen and carbon dioxide gas barrier properties than polyethylene and polypropylene and is used as a bottle for carbonated drinks. However, in applications where a higher gas barrier property is required, the gas barrier property of PET is not sufficient, and development of a polyester having a better gas barrier property has been desired. Although PET film has excellent transparency, it does not have the ability to block ultraviolet rays and
Ultraviolet rays having the above wavelengths are transmitted. Since ultraviolet rays act on foods and the like and cause deterioration in quality thereof, for example, as a food packaging material, one having an ultraviolet blocking property is desired. As a method of improving the gas barrier property of PET, there is a method of coating or laminating a resin having a barrier property superior to that of PET, for example, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, etc. Has poor adhesion to PET,
It has drawbacks such as complicated molding process. As a method of improving the ultraviolet barrier property, there is a method of adding a low molecular weight ultraviolet absorber, but there are problems such as migration to the contents.

[0003]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found an aromatic polyester resin having excellent ultraviolet barrier property and excellent gas barrier property. Came to complete. That is, the present invention contains the repeating unit represented by the formula (1) 0.1 to 100 mol%, the repeating unit represented by the formula (2) 0-99.9
Aromatic polyester resin having excellent UV barrier properties, characterized by containing mol%, and further formula (1)
Containing 10 to 100 mol% of the repeating unit represented by
An aromatic polyester resin having excellent gas barrier properties in addition to excellent ultraviolet barrier properties, which is characterized by containing 0 to 90 mol% of the repeating unit represented by (2).

[0004]

[Chemical 2]

(In the formula, m and n are integers of 2 to 10.) The aromatic polyester resin of the present invention comprises terephthalic acid or its ester-forming derivative (dimethyl terephthalate, diethyl terephthalate, etc.) (3)

[0006]

[Chemical 3]

From bis (2-hydroxy-2-oxoethoxy) -9,10-anthraquinone or an ester-forming derivative thereof (bis (2-methoxy-2-oxoethoxy) -9,10-anthraquinone, etc.) represented by It is obtained by copolymerizing a selected dicarboxylic acid component and a diol component selected from linear aliphatic glycols having 2 to 10 carbon atoms.
The composition of the dicarboxylic acid component is 0 to 99.9 mol% of terephthalic acid or its ester-forming derivative, preferably 0 to 9
9.5 mol%, 0.1 to 100 mol% of the dicarboxylic acid represented by formula (3) or its ester-forming derivative, preferably
It is 0.5 to 100 mol%. When the latter ratio is less than 0.1 mol%, the ultraviolet barrier property is insufficient and only ultraviolet rays having a wavelength of 320 nm or less can be blocked as in PET. Further, in order to have excellent gas barrier properties, the latter ratio must be 10 mol% or more.

The aromatic polyester resin of the present invention may be copolymerized with a copolymerization component other than the above essential components at a ratio of 20 mol% or less. That is, aromatic dicarboxylic acids and aliphatic dicarboxylic acids other than the above essential components may be copolymerized as the dicarboxylic acid component, and aliphatic diols, aromatic diols, and diphenols other than the above essential components may be copolymerized as the diol component. Further, a hydroxycarboxylic acid component such as an aromatic hydroxycarboxylic acid or an aliphatic hydroxycarboxylic acid may be copolymerized. Further, a small amount of a polyfunctional component having three or more functional groups may be copolymerized within a range capable of being melt-molded. Among these copolymerizable compounds, for example, as the dicarboxylic acid component, 1,5-, 1,6-, 1,7-, 2,6
-, 2,7-naphthalenedicarboxylic acid, phthalic acid, cyclohexanedicarboxylic acid, isophthalic acid, dibromoisophthalic acid, sodium-sulfoisophthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylketone dicarboxylic acid, diphenoxy Aromatic dicarboxylic acids such as ethanedicarboxylic acid, phenylenedioxydiacetic acid, adipic acid,
Examples thereof include aliphatic dicarboxylic acids such as sebacic acid, succinic acid, glutaric acid, piperic acid, suberic acid, azelaic acid, undecadioic acid, and dodecadioic acid, or a mixture of two or more thereof. As the diol component, aliphatic diols such as propylene glycol, neopentyl glycol, diethylene glycol and polyethylene glycol, alicyclic diols such as cyclohexanedimethanol,
Aromatic diols such as o-, p-xylylene glycol, 2,2-bis (4-hydroxyethoxyphenyl) propane and the like, or a mixture of two or more kinds, and diphenols such as hydroquinone, resorcinol, dihydroxydiphenyl and dihydroxydiphenyl ether Can be mentioned. Further, examples of the hydroxycarboxylic acid component include glycolic acid, hydroxybenzoic acid, hydroxynaphthoic acid and the like.

Regarding the method for synthesizing the aromatic polyester resin of the present invention using the above-mentioned monomers, direct polymerization method,
Any method may be used as long as it is a method for synthesizing a general polyester such as a transesterification method. The aromatic polyester resin of the present invention obtained by the above method preferably has an intrinsic viscosity of 0.5 g / dl or more measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 60/40). When the intrinsic viscosity is less than 0.5 g / dl, mechanical properties are deteriorated, which is not preferable.

The aromatic polyester resin of the present invention can be subjected to melt molding such as melt film formation, whereby molded articles such as sheets and films can be obtained. Alternatively, a hollow molded article can be obtained by direct blow molding, injection blow molding, biaxial stretch blow molding, or the like. Further, to the aromatic polyester resin of the present invention, additives such as a colorant, an oxidation stabilizer, an ultraviolet absorber, an antistatic agent and a flame retardant may be added to the extent that moldability is not impaired.

[0011]

EXAMPLES Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, the measurement of the intrinsic viscosity in the examples was carried out at 25 ° C. using a mixed solvent of phenol / tetrachloroethane = 60/40 (weight ratio). The oxygen permeability was measured by using a gas permeation measuring device GPM250 manufactured by Gas Chloro Industry Co., Ltd., and the oxygen permeability coefficient of the film was measured at 23 ° C. and normal pressure (unit: cm ³ · mm / m ² · 24 hr · atm). Water vapor permeability is
It measured at 40 degreeC using Lyssy WATER VAPER PERMIATION TESTER L80-4000 (unit g * mm / m < ² > * day). UV blocking is Shimadzu UV-VISIBLE RECORDING SPECTROPHOT
It was measured using OMETER UV-265FW. Example 1 A separable flask equipped with a stirring blade, a nitrogen inlet, and a pressure reducing port was used as the dicarboxylic acid component of formula (4).

[0012]

[Chemical 4]

3.84 g (0.01 mol) of the compound represented by
And dimethyl terephthalate 192.2 g (0.99 mol), ethylene glycol 124.2 g (2.0 mol) as a diol component,
As catalysts, 0.1 g each of Zn (CH ₃ COO) ₂ .2H ₂ O and GeO ₂ are charged. Heat to 180-230 ℃ under nitrogen stream to carry out transesterification and distill off methanol. After 4 hours, the theoretical amount of methanol was distilled off.
Raise the temperature to 0 to 270 ℃ and gradually reduce the pressure to 3 at 0.1 to 0.3 Torr.
Polymerize for hours. The obtained polymer has an intrinsic viscosity of 0.78 g /
It was dl. Further, the obtained polymer was melt-pressed at 280 ° C. and rapidly cooled to obtain a polyester film having a thickness of about 0.2 mm. This film was used to measure oxygen and water vapor permeability and ultraviolet ray blocking ability. The results are shown in Table 1.

Example 2 A compound represented by the above formula (4) was used as a dicarboxylic acid component.
76.8g (0.2mol), 155.3g of dimethyl terephthalate
(0.8 mol) A polymer was obtained in the same manner as in Example 1 except that it was used. The intrinsic viscosity of the obtained polymer is 0.77 g / dl.
Met. Table 1 shows the oxygen and water vapor transmission rates and the ultraviolet blocking ability measured in the same manner as in Example 1.

Example 3 A compound represented by the above formula (4) was used as a dicarboxylic acid component.
192.1 g (0.5 mol) and dimethyl terephthalate 97.1 g
(0.5 mol) A polymer was obtained in the same manner as in Example 1 except that it was used. The intrinsic viscosity of the obtained polymer is 0.74 g / dl
Met. Table 1 shows the oxygen and water vapor transmission rates and the ultraviolet blocking ability measured in the same manner as in Example 1.

Example 4 Compound 3 represented by the above formula (4) as a dicarboxylic acid component
A polymer was obtained in the same manner as in Example 1 except that only 84.3 g (1.0 mol) was used. The intrinsic viscosity of the obtained polymer was 0.70 g / dl. Table 1 shows the oxygen and water vapor transmission rates and the ultraviolet blocking ability measured in the same manner as in Example 1.

Comparative Example 1 194.2 g of dimethyl terephthalate as a dicarboxylic acid component
A polymer was obtained in the same manner as in Example 1 except that only (1.0 mol) was used. The intrinsic viscosity of the obtained polymer is 0.78.
It was g / dl. Table 1 shows the oxygen and water vapor transmission rates and the ultraviolet blocking ability measured in the same manner as in Example 1.

Comparative Example 2 A compound represented by the above formula (4) was used as a dicarboxylic acid component.
0.19 g (0.0005 mol), dimethyl terephthalate 194.07 g
(0.9995 mol) A polymer was obtained in the same manner as in Example 1 except that it was used. The obtained polymer has an intrinsic viscosity of 0.74 g /
It was dl. Table 1 shows the oxygen and water vapor transmission rates and the ultraviolet blocking ability measured in the same manner as in Example 1.

[0019]

[Table 1]

Note) * 1: Oxygen permeability unit cm ³ · mm / m ² · 24 hr · atm * 2: Water vapor permeability unit g · mm / m ² · day

[0021]

The aromatic polyester resin of the present invention has P
It has the same molding processability as ET, and exhibits superior ultraviolet barrier properties, oxygen barrier properties, and water vapor barrier properties than PET. Therefore, it is useful in the application of films, bags, containers, etc. when it is necessary to block ultraviolet rays, water vapor and oxygen. By using the aromatic polyester resin of the present invention, it is possible to obtain ultraviolet barrier properties and gas barrier properties by blow molding. It is possible to obtain a hollow container having excellent properties and impact resistance.

Claims (2)

[Claims] 1. The repeating unit represented by the formula (1) is 0.1 to
Containing 100 mol% of the repeating unit represented by the formula (2)
An aromatic polyester resin characterized by containing ~ 99.9 mol%. [Chemical 1] (In formula, m and n show the integer of 2-10.) 2. The repeating unit represented by the formula (1) is 10
Aromatic polyester resin containing 100 to 100 mol% of the repeating unit represented by the formula (2) and 0 to 90 mol% of the repeating unit.