JPH08283554A - Polymer alloy of copolyester resin and polycarbonate resin, and packaging material and packaging container made therefrom - Google Patents

Abstract

PURPOSE: To obtain a polymer alloy which can give a food packaging container excellent in heat resistance, hot water resistance, etc., under specified sterilization conditions by blending a copolyester resin with a polycarbonate resin. CONSTITUTION: This polymer alloy comprises a copolyester resin and a polycarbonate resin. The copolyester resin has a solubility parameter [defined by the formula (wherein Δei is the evaporation energy of each atom or each group of atms; and Δvi is its molar vol.)] of 10.8-11.9 and is produced from an acid component comprising 2,6-naphthalenedicarboxylic acid and terephtalic acid or their lower-alkyl esters and a glycol component comprising 1,4- cyclohexanedimethanol and ethylene glycol. The polymer alloy, when molded by a suitable method, gives a food packaging container exhibiting excellent resistances to heat, hot water, and cold impact under thermal sterilization conditions of 85 deg.C×30min and having sufficient gas barrier properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer alloy obtained by blending a copolyester resin and a polycarbonate resin (PC), as well as packaging materials such as sheets and films containing the polymer alloy as a main component, and cups and bottles. Etc. regarding packaging containers.

[0002]

2. Description of the Related Art Conventionally, glass has been mainly used as a material for food packaging because hot water resistance (whitening resistance) and transparency are required, but recently, plastics having improved heat resistance and the like have been used. Is being used. Among them, polyethylene terephthalate resin (PET), which is a type of polyester resin, is widely used as a food packaging material because it has excellent physical and chemical properties and has a recycling system in place. . In addition, polyethylene-2,6-naphthalate resin (PEN) having a naphthalene skeleton has a high molecular weight of PE due to its rigidity and planarity.
Mechanical strength (Young's modulus, breaking strength), heat resistance (long-term thermal stability, dimensional stability), chemical properties (chemical resistance, gas barrier property), etc. are superior to those of T. ing.

By the way, according to Article 7 of the Food Sanitation Law, it is obligatory to sterilize a predetermined food under a predetermined condition. Therefore, a food packaging container has a heat resistance sufficient to withstand the sterilization condition of the food. In many cases, hot water resistance (whitening resistance) is required. Further, in food packaging containers, transparency is required so that the contents can be confirmed.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The packaging material consisting of is generally deformed under high temperature and high humidity.
For example, when used as a food container to be subjected to hot water sterilization, the container is deformed at 65 ° C. and is not suitable for such use. Thermoforming sheets made of polyethylene terephthalate copolymer do not have heat resistance at 87 ° C, and have the drawback of whitening and loss of transparency when kept for several tens of minutes under high temperature and high humidity. There were problems such as not being able to use. On the other hand, PEN
Is heat resistance in sterilization treatment with hot water at 90 to 100 ° C,
Although it is excellent in hot water resistance (whitening resistance), it is inferior in heat sealability with the lid material.

The present invention has been made in view of the above-mentioned problems of the prior art, and its object is heat resistance under heating conditions (cold spot) of 85 ° C. × 30 minutes or sterilization conditions having higher efficacy. With an aluminum closure (a cover material of aluminum foil) that has excellent properties, hot water resistance (whitening resistance), cold shock resistance (cold drop strength), sufficient gas barrier properties, and a polyester adhesive layer as the innermost layer. It is an object of the present invention to provide a polymer alloy having a good heat-sealing property, an excellent transparency and an ultraviolet blocking property, and a packaging material and a packaging container using the same.

[0006]

The polymer alloy of the present invention is a polymer alloy of a copolyester resin and a polycarbonate resin having a solubility parameter in the range of 10.8 to 11.9, wherein the copolyester resin is Is a copolymer composed of 2,6-naphthalenedicarboxylic acid and terephthalic acid or lower alkyl esters thereof as an acid component and 1,4-cyclohexanedimethanol and ethylene glycol as a glycol component.

The above-mentioned solubility parameter (δ) is a measure of the compatibility of polymer materials, and according to Fedors, the following [Equation 1]
Is defined in.

[0008]

## EQU1 ## δ = (E _v / v) ^1/2 = (ΣΔe _i / ΣΔv _i ) ^1/2

Here, Δe _i and Δv _i are the evaporation energy and molar volume of each atom or atomic group. However, the Tg is above 25 ° C. compound, 4n when the main chain skeleton atoms n in the minimal repeating unit of the polymer is less than 3, n is 3 or more 2n when each said molar volume Delta] v _i to add.

In the polymer alloy of the present invention, the solubility parameter (δ) of the copolyester resin is 10.8 to 1
Although it is limited to the range of 1.9, the range of 11.1 to 11.9 is more preferable. The reason is that when δ is less than 10.8, the ultraviolet ray blocking property and the gas barrier property are insufficient, and δ
Is more than 11.9, transparency decreases.

The copolymerized polyester resin has an intrinsic viscosity at 35 ° C. in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (details of the measuring method will be described later).
However, 0.5 to 1.2 is preferable, and the intrinsic viscosity is 0.5.
Those of 5 to 0.7 are more preferable. The polycarbonate resin has an average molecular weight of 10,000 to 100,
000 is preferable. When the intrinsic viscosity of the copolyester resin exceeds 1.2 and the average molecular weight of the polycarbonate resin exceeds 100,000, the melt viscosity of the polomer alloy becomes too high and molding becomes difficult. On the contrary, when the intrinsic viscosity of the copolyester resin is less than 0.5 and the average molecular weight of the polycarbonate resin is less than 10,000, the molded product becomes brittle.

In the copolymerized polyester resin, the molar ratio of 2,6-naphthalene naphthalene dicarboxylic acid and terephthalic acid or their lower alkyl ester (2,6-naphthalene dicarboxylic acid or its lower alkyl ester / terephthalic acid or The lower alkyl ester) is 5/95 to 95/5, and the molar ratio of 1,4-cyclohexanedimethanol and ethylene glycol (1,4-cyclohexanedimethanol / ethylene glycol) is 53/47 to 95/5. Yes, and 1,4-
Cyclohexane dimethanol has a molar ratio of cis isomer to trans isomer (cis isomer / trans isomer) of 0/100 to 40/6.
It is more preferably 0 (claim 2). The reason is that the proportion of 2,6-naphthalenedicarboxylic acid is 5 mol%.
When the content of terephthalic acid is less than 95 mol%, the heat resistance and hot water resistance (whitening resistance) of the polymer alloy are lowered,
This is because when the proportion of 2,6-naphthalenedicarboxylic acid exceeds 95 mol% and terephthalic acid is less than 5 mol%, the transparency and heat sealability of the polymer alloy are deteriorated. When the ratio of 1,4-cyclohexanedimethanol is less than 53 mol% and the amount of ethylene glycol exceeds 47 mol%, the transparency and heat sealability of the polymer alloy are deteriorated, and the ratio of 1,4-cyclohexanedimethanol is Is more than 95 mol% and ethylene glycol is less than 5 mol%, the whitening resistance of the polymer alloy in hot water is deteriorated. Further, in the molar ratio of cis- and trans-forms of 1,4-cyclohexanedimethanol,
If the proportion of the cis isomer exceeds 40 mol%, that is, if the proportion of the trans isomer is less than 60 mol%, the heat resistance decreases and it becomes unsuitable as a packaging container.

The blend ratio of the copolymerized polyester resin and the polycarbonate resin (weight of copolymerized polyester resin / weight of polycarbonate resin) is 2/98 to 95.
/ 5 is more preferable (Claim 3). The reason is that if the blend ratio is within the above range, all of the transparency, heat resistance, hot water resistance, UV blocking property (weather resistance), and moldability of the polymer alloy will be excellent.

The blend ratio of the copolyester resin and the polycarbonate resin (weight of copolyester resin / weight of polycarbonate resin) is 50/50 to 8
It is more preferably 0/20 (claim 4). The reason is that if the blend ratio is within the above range, the polymer alloy will be excellent in transparency, heat resistance, hot water resistance, UV blocking property (weather resistance), and moldability, as well as cold impact resistance. , Less than 4 times the gas barrier property of PET, and PE
This is because a polymer alloy having excellent heat sealability with T can be obtained.

By molding the polymer alloy of the present invention, particularly the resin containing the polymer alloy as a main component according to claim 4, the above-mentioned various properties such as heat resistance and hot water resistance (whitening resistance) are satisfied. Packaging materials such as films and sheets and packaging containers such as cups and bottles can be obtained. in this case,
The packaging material is obtained by extruding a resin containing the polymer alloy as a main component, and the packaging container is formed by vacuum forming or pressure forming the packaging material such as a film or a sheet, or mainly using the polymer alloy. The resin as a component can be produced by direct blow molding, injection molding, injection blow molding or injection biaxial stretch blow molding.

In the production of the copolyester resin according to the present invention, 2,6-naphthalenedicarboxylic acid and terephthalic acid or their lower alkyl esters,
A high molecular weight polyester is obtained using ethylene glycol and 1,4-cyclohexanedimethanol as main starting materials. In this case, first, bis-β-hydroxyethyl-2,6-naphthalate and dimethylcyclohexane terephthalate or bis-β-hydroxycyclohexane-2,6-naphthalate and dihydroxyethyl terephthalate are mainly used, or a transesterification of a combination thereof is performed. It is customary to divide it into a first step of obtaining a reaction product and a second step of further polycondensing it.

In the first step, the dicarboxylic acid component and the glycol component are esterified or the lower alkyl ester of the dicarboxylic acid and the glycol component are transesterified. In the present invention, either of these reactions is adopted. May be. In the esterification reaction, 2,6-naphthalenedicarboxylic acid and terephthalic acid and about 0.8 times or more the total number of moles of these acids, preferably 1 to 5
React with twice the number of moles of glycol component. The transesterification reaction product in the first step may be synthesized according to a known method.

Any transesterification catalyst may be used as long as it can be used for synthesizing polyester such as polyethylene terephthalate. For example, Li, Na, K, Mg, Ca, Sr,
Ba, Zn, Cd, Al, Ge, Sn, Pb, Ti, C
Mention may be made of salts of carboxylic acid alcoholates, oxides or acetates of metals selected from the group consisting of r, Mn, Fe, Ni, Sb and Co. As the transesterification catalyst, one may be selected from these and used, or a plurality of them may be used in combination. The amount of these catalysts used is 10 to 10 relative to the dicarboxylic acid component.
It is preferably about 00 mmol%. The temperature of the transesterification reaction is usually in the range of 150 to 260 ° C, preferably 220 to 240 ° C. The reaction time is up to a predetermined reaction rate or higher, usually 80% or higher, and it may be carried out until the lower alcohol produced as a result of the reaction is almost completely distilled.

In the second step, the low polymer obtained in the first step is heated under reduced pressure to carry out a polycondensation reaction. In the present invention, before and after the second step is started, specifically, After one step is substantially completed and when the intrinsic viscosity does not exceed 0.2, a polycondensation catalyst such as Mn, Ge, Sn,
A carboxylic acid of a metal selected from the group consisting of Ti and Sb,
A polycondensation reaction is carried out by adding one or more of alcoholates or oxides. The amount of the catalyst used may be about 10 to 1000 mmol% with respect to the dicarboxylic acid component. At this time, various additives such as a light-resistant agent, a weather-resistant agent, an antistatic agent, a heat stabilizer, a light-shielding agent, and a pigment can be added individually or in combination of two or more kinds, if necessary. Further, some of these additives can be blended in the middle stage or the latter stage of the first step and / or the second step, or immediately before the film formation. Resin 100 is added
1 to 1200 mmol%, preferably 5 to 5 mol, based on mol
It is 1000 mmol%.

After adding the polycondensation catalyst, a second step for obtaining a copolymer having a high degree of polymerization by a deglycol reaction is started. In the second step, the system is heated as the reaction progresses, and the reaction temperature is gradually raised. In other words, when the reaction starts,
At 250 ° C., it is finally heated to about 270 to 310 ° C. The pressure inside the reaction system is gradually reduced, and when the reaction is disclosed, the pressure is normal pressure and finally 10 mmHg or less, preferably 1 m.
It is preferable to set it to mHg or less. Further, the time of the polymerization reaction by this dissolution method is determined by the intrinsic viscosity of the obtained product, but if it is too long, it is economically disadvantageous and the thermal decomposition reaction proceeds at the same time. The time is preferably 1 to 4 hours. After the completion of the polymerization by the melting method, the polymer is usually pressurized with an inert gas, particularly nitrogen gas, discharged from the reaction vessel, cooled and cut to have a desired shape and size.

Then, this polyester copolymer is subjected to a drying step. This is because the polyester copolymer undergoes hydrolysis when melt-extruded in the presence of water, resulting in an extremely low molecular weight. In this drying step, the water content of the dried polyester copolymer needs to be 100 ppm or less, preferably 50 ppm or less. As the conditions and equipment for this drying step, those used for drying ordinary thermoplastic polymers, especially polyester resins, can be applied. The drying temperature is 120
C. or less is preferable.

Next, the polycarbonate resin according to the present invention will be described. The polycarbonate resin used in the present invention is a polycarbonate resin having a diphenylalkane as a skeleton, specifically, a polycarbonate obtained from a 4,4′-dioxyphenylalkane compound and phosgene or diphenyl carbonate. 4,
As the 4'-dioxyphenylalkane compound, 2,
2-bis (4-hydroxyphenyl) propane is typical. The average molecular weight of these polycarbonate resins used in the present invention is usually 10,000 to 100,000.
It is about 00, and for example, those of 21,000 to 23,000 or those of 23,000 to 25,000 are used. Such a polycarbonate resin has excellent physical properties such as heat resistance and transparency, and further, the polyester copolymer according to the present invention has a molar ratio of 2,6-naphthalenedicarboxylic acid as an acid component to terephthalic acid of 5 /. 95-9
5/5, the molar ratio of glycol component 1,4-cyclohexanedimethanol and ethyne glycol is 53 / 47-
When it is 95/5, there is no problem in compatibility with the polyester copolymer.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, the measuring method and test method of each physical property in the following examples are as follows.

[Measurement of Intrinsic Viscosity of Copolyester Resin] A sample resin was mixed with a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 60/40) to 100%.
Dissolve at a concentration of 0.2 to 1.0 g / dl in 1 hour at 35 ° C. using an Ubbelohde-type capillary viscometer.
The solution viscosity was extrapolated to a value of 0 g / dl to determine the intrinsic viscosity.

[Measurement of Composition Ratio of Copolyester Resin] A sample resin is hydrolyzed in a basic solution, and the hydrolyzate is subjected to gas chromatography by 2,6-naphthalenedicarboxylic acid / terephthalic acid, 1,4- Cyclohexanedimethanol / ethylene glycol each component was quantified to determine the composition ratio.

[Heat resistance by heat treatment (heat distortion resistance),
Hot water resistance (whitening resistance) test] pH of less than 4.0 Water activity (Aw) F value of food less than 0.94 (at the time of lethal heat sterilization)
Is F (5 ° C / 65 ° C), and the F value (at the time of killing by heat sterilization) of food having a pH of 4.0 or more and less than 4.6 and a water activity (Aw) of less than 0.94 is indicated by F (8 ° C / 85 ° C). . The relationship between the sterilization temperature of food itself and time is shown in [Table 1] below. [Table 1]
The heat resistance of the container is experimentally sought, and a 100cc container requires heat resistance of 87 ° C for 20 minutes.
Heat resistance of 12 minutes is required.

[0027]

[Table 1]

F (Z / reference temperature) value (heat lethal time):
Heating time (minutes) required to reduce the number of bacteria from N ₀ to N when heated at a reference temperature Z value: Temperature change corresponding to 10 times or 1/10 times the D value (of the bacteria to be sterilized) (Applied from the measured value) (Generally 10
℃, 18 ° F) D value: When a microorganism is heated at a constant temperature, its survival number is 1
Time required to reduce to / 10 (min) Standard temperature: Highly acidic food ………… 65.0 ° C (149 ° F) Acidic food ………… 85.0 ° C (185 ° F) Low acidic food …… 121. 1 ° C. (250 ° F.) F ₀ value: Reference temperature 121.1 ° C. Z = 10 ° C. F value

In the following examples and comparative examples, the heat resistance and hot water resistance (ignition resistance) of the cup-shaped molded articles produced by molding have a water activity (A) of pH 4.0 to less than 4.6.
w) Heating at 85 ° C., which is a heat sterilization condition of food of less than 0.94, for 30 minutes (cold spot), pH 4.0 less than water activity (Aw), which is heat sterilization condition of food of less than 0.94, for 10 minutes at 65 ° C. As a means of heating (cold spot), use a 100 cc capacity container at 87 ° C for 20 minutes or 89 ° C.
The container was immersed in a constant temperature bath for 12 minutes, and changes in the container volume and whitening due to crystallization were examined and evaluated. The evaluation method is shown below.

[Evaluation Criteria] (i) Heat resistance ◯: Capacity change is less than 2% (no deformation) Δ: Capacity change is 2% or more and less than 3% (slightly deformed) ×: Capacity change is 3% or more (Large deformation) (ii) Hot water resistance (whitening resistance): Visually ○: No whitening △: Some whitening ×: Complete whitening

[Heat Sealing Test] A cup-shaped molded product produced by molding and an aluminum closure having a polyester adhesive as the innermost layer are heat-sealed at 190 ° C. × 1 second × load 20 kg / cm ^2. It was Heat sealing strength is 180 to 2200g / 15m with peeling of 180 degrees
m was good (◯), and less than 1200 g / 15 mm was bad (x).

[Cold impact resistance (cold drop strength) test] A cup-shaped molded product (φ80 mm, depth 2) manufactured by molding.
(7 mm, thickness 0.3 mm) was filled and sealed with 95 g of 4 ° C. sake, kept cool at 0 ° C., and dropped vertically twice in succession so that the bottom surface hits the concrete floor from a height of 100 cm. The sample with neither cracking nor leakage was rated as ◯. In this case, the bottom of the cup-shaped molded article collided with the P tile. The conditions for the food standard drop test are: food filling material into container x drop distance = less than 100 g x 8
It is 0 cm.

[Gas Barrier Test (Measurement of Oxygen Permeability Coefficient)] GL Science Co., Ltd., trade name "GPM-"
The gas barrier property of the molded polymer alloy sheet was measured using pure oxygen as a measurement gas by a gas chromatography method at 23 ° C. and normal pressure using a “250 type gas permeation tester”. In this case, the oxygen permeability coefficient is 2.0.
× 10 ^-11 (cm ³ · cm / cm ² · sec · cmH
Less than g), that is, less than 4 times the oxygen transmission coefficient of PET is good (◯), and the oxygen transmission coefficient is 2.0 × 10.
Those having a value of ^-11 or more were regarded as defective (x).

[Transparency Test] Using a direct-reading haze meter manufactured by Toyo Seiki Seisakusho Co., Ltd., JIS K-6714,
According to 6717, a sheet having a thickness of 500 μm was used, and the haze value (cloudiness) obtained by the following [Equation 2] was used for evaluation. In this case, a haze value of less than 5% was marked with ⊚, 5% or more and less than 20% was marked with ◯, and 20% or more was marked with x.

[0035]

## EQU2 ## Haze value (%) = (diffuse transmittance / total light transmittance) × 100

[UV blocking property (280 nm to 350 n
m)] Using a spectrophotometer UVEST manufactured by JASCO Corporation, a sheet having a thickness of 500 μm was irradiated with light having a wavelength of 200 to 900 nm, and the transmittance of ultraviolet rays having a wavelength of 280 to 350 nm was evaluated. In this case, the transmittance of less than 1% is ◯ and 1%
The above is marked with x.

[Preparation of Copolymerized Polyester Resin (Examples 1 to 35)] Example 1 A dicarboxylic acid raw material consisting of 5 mol% of 2,6-dimethylnaphthalate (A) and 95 mol% of dimethyl terephthalate (B), The molar ratio of cis and trans isomers is 0/10
0, a glycol raw material composed of 53 mol% of 1,4-cyclohexanedimethanol (C) and 47 mol% of ethylene glycol (D), 0.02 mol% of titanium tetrabutoxy monomer, and 0.02 mol% of manganese oxide. The mixture was placed in a reaction vessel, the temperature was raised to 180 to 240 ° C., and a transesterification reaction was carried out until the distillate disappeared to obtain a low polymer. Next, 0.04 mol% of trimethyl phosphate and 0.02 mol% of antimony trioxide were added in this order from 240 ° C. to 29%.
The temperature was raised to 0 ° C. and the pressure was reduced to 1 torr to form a high vacuum. While maintaining this temperature and pressure, polycondensation was performed to prepare a copolyester resin having an intrinsic viscosity of 0.6.

The dicarboxylic acid component ratio A / of this copolymer
B and glycol component ratios C / D were 5/95 and 53/47, respectively, from ¹ H-NMR using deuterated trifluoroacetic acid as a measurement solvent, and after alkaline hydrolysis to monomer units and by gas chromatography under normal pressure. It was confirmed that there is. The composition of this copolyester resin is shown in [Table 1] below. In this table, "NDC" is naphthalene dicarboxylic acid, "TPA" is terephthalic acid, and "C".
"HDM" is 1,4-cyclohexanedimethanol,
“EG” represents ethylene glycol, respectively. In addition, "NDC / TPA", "CHMD / EG", "ci
"s / trans (cis isomer / trans isomer ratio)" represents a molar ratio (however, 100 mol% in total). further,
"Blend ratio" is (weight of copolyester resin /
Represents the weight of the polycarbonate resin).

Examples 2-35, Comparative Examples 1-19 The carboxylic acid component ratio A / B, the glycol component ratio C
/ D and the same operation as in Example 1 except that the ratio of the cis isomer to the trans isomer in 1,4-cyclohexanedimethanol was variously changed to prepare a target copolyester resin. The compositions of these copolyester resins are shown in [Table 2], [Table 3] and [Table 4].

[0040]

[Table 2] ─────────────────────────────────── Copolymerized polyester resin alloy Characteristics of compressed air molded products CHDM δ Blend NDC / CHDM / cis / Ratio ABCDEF UV TPA EG trans ─────────────────────────────────── Example 1 5/95 53/47 0/100 11.38 70/30 ○ ○ ○ ○ ○ ○ ○ 2 5/95 53/47 24/76 11.38 70/30 ○ ○ ○ ○ ○ ○ ○ 3 5/95 53/47 40/60 11.38 70/30 ○ ○ ○ ○ ○ ○ ○ 4 5/95 87/13 0/100 10.96 70/30 ○ ○ ○ ○ ○ ◎ ○ 5 5/95 87/13 24/76 10.96 70/30 ○ ○ ○ ○ ○ ◎ ○ 6 5/95 87/13 40/60 10.96 70/30 ○ ○ ○ ○ ○ ◎ ○ 7 5/95 95/5 0/100 10.87 70/30 ○ ○ ○ ○ ○ ◎ ○ 8 5 / 95 95/5 24/76 10.87 70/30 ○ ○ ○ ○ ○ ◎ ○ 9 5/95 95/5 40/60 10.87 70/30 ○ ○ ○ ○ ○ ◎ ○ 10 50/50 53/47 0/100 11.60 70/30 ○ ○ ○ ○ ○ ○ ○ 11 50/50 53/47 24/7 6 11.60 70/30 ○ ○ ○ ○ ○ ○ ○ 12 50/50 53/47 40/60 11.60 70/30 ○ ○ ○ ○ ○ ○ 13 13 50/50 87/13 0/100 11.18 70/30 ○ ○ ○ ○ ○ ◎ ○ 14 50/50 87/13 24/76 11.18 50/50 ○ ○ ○ ○ ○ ◎ ○ 15 50/50 87/13 24/76 11.18 70/30 ○ ○ ○ ○ ○ ◎ ○ 16 50/50 87/13 24/76 11.18 80/20 ○ ○ ○ ○ ○ ◎ ○ 17 50/50 87/13 40/60 11.18 70/30 ○ ○ ○ ○ ○ ◎ ○ 18 50/50 95/5 0/100 11.08 70 / 30 ○ ○ ○ ○ ○ ◎ ○ ───────────────────────────────────

[0041]

[Table 3] ─────────────────────────────────── Copolymerized polyester resin alloy Characteristics of compressed air molded products CHDM δ Blend NDC / CHDM / cis / Ratio ABCDEF UV TPA EG trans ─────────────────────────────────── Example 19 50/50 95/5 24/76 11.08 70/30 ○ ○ ○ ○ ○ ◎ ○ 20 50/50 95/5 40/60 11.08 70/30 ○ ○ ○ ○ ○ ◎ ○ 21 95/5 53/47 0/100 11.84 70/30 ○ ○ ○ ○ ○ ○ ○ 22 95/5 53/47 24/76 11.84 70/30 ○ ○ ○ ○ ○ ○ ○ 23 95/5 53/47 40/60 11.84 70/30 ○ ○ ○ ○ ○ ○ ○ 24 95/5 87/13 0/100 11.40 70/30 ○ ○ ○ ○ ○ ○ ○ 25 95/5 87/13 24/76 11.40 70/30 ○ ○ ○ ○ ○ ○ ○ ○ 26 95 / 5 87/13 40/60 11.40 70/30 ○ ○ ○ ○ ○ ○ ○ 27 95/5 95/5 0/100 11.30 70/30 ○ ○ ○ ○ ○ ○ ○ 28 95/5 95/5 24/76 11.30 70/30 ○ ○ ○ ○ ○ ○ ○ 29 95/5 95/5 40/60 11.30 70/30 ○ ○ ○ ○ ○ ○ ○ 30 50/50 87/13 24/76 11.18 30/70 ○ ○ ○ × ○ ◎ ○ 31 50/50 87/13 24/76 11.18 90/10 ○ ○ × ○ ○ ◎ ○ 32 50/50 89/11 24/76 11.16 2/98 ○ ○ ○ × × ◎ ○ 33 50/50 89/11 24/76 11.16 95/5 ○ ○ × ○ ○ ◎ ○ 34 50/50 69/31 24/76 11.40 50/50 ○ ○ ○ ○ ○ ○ ○ 35 75/25 85/15 24/76 11.32 50/50 ○ ○ ○ ○ ○ ○ ○

[0042]

[Table 4] ─────────────────────────────────── Copolymerized polyester resin alloy Characteristics of compressed air molded products CHDM δ Blend NDC / CHDM / cis / Ratio ABCDEF UV TPA EG trans ─────────────────────────────────── Comparison Example 1 ─── ─── ─── ─── 0/100 ○ ○ ○ × × ◎ × 2 100/0 50/50 24/76 11.91 50/50 ○ ○ ○ ○ × × ○ 3 100/0 0 / 100 ─── 12.55 50/50 ○ ○ ○ ○ × × ○ 4 0/100 100/0 24/76 10.78 50/50 × × ○ × ○ ◎ × 5 0/100 50/50 24/76 11.40 50 / 50 × × ○ ○ ○ ○ × 6 0/100 0/100 ─── 12.01 50/50 × × ○ ○ ○ × × 7 95/5 40/60 24/76 12.00 50/50 ○ ○ ○ ○ ○ × ○ 8 95/5 50/50 24/76 11.93 70/30 ○ ○ ○ ○ ○ × ○ 9 2/98 87/13 24/76 10.95 70/30 × × ○ ○ ○ ◎ × 10 50/50 98/2 24 / 76 11.04 70/30 ○ ○ ○ × × ◎ ○ 11 98/2 53/4 7 24/76 11.92 70/30 ○ ○ ○ ○ × × ○ 12 5/95 53/47 50/50 11.38 70/30 × ○ ○ ○ ○ ○ ○ 13 5/95 95/5 50/50 10.87 70/30 × ○ ○ ○ ○ ◎ ○ 14 50/50 53/47 50/50 11.60 70/30 × ○ ○ ○ ○ ○ ○ 15 50/50 95/5 50/50 11.08 70/30 × ○ ○ ○ ○ ◎ ○ 16 95/5 95/5 50/50 11.30 70/30 × ○ ○ ○ ○ ○ ○ 17 95/5 95/5 50/50 11.30 70/30 × ○ ○ ○ ○ ○ ○ 18 50/50 87/13 50 / 50 11.18 50/50 × ○ ○ ○ ○ ◎ ○ 19 50/50 87/13 50/50 11.18 80/20 × ○ ○ ○ ○ ◎ ○ ────────────────── ──────────────────

[Copolymerized Polyester Resin of Example 1 and P
Polymer Alloy C] After molding the copolyester resin obtained in Example 1 into pellets of a predetermined shape and size,
After drying, the pellets and PC pellets (trade name “UPILON S2000” manufactured by Mitsubishi Gas Chemical Co., Inc., average molecular weight 23,000 to 25,000) were used in a weight ratio (copolymerized polyester resin / PC) of 70 /. No. 30, and the mixed pellets were extruded at 290 ° C. by the same-direction twin-screw extruder to form a sheet having a thickness of 0.6 mm. Using this sheet, with a pressure molding machine, diameter φ80mm, depth 27m
A cup-shaped molded product having a thickness of m and a thickness of 0.3 mm was manufactured. The conditions for this pneumatic molding are a plug temperature of 140 ° C. and a pneumatic pressure of 6
kg / cm ² , cavity temperature 20 ° C., sheet surface temperature 155 ° C., 1 cycle 2 to 5 seconds. Next, various physical properties were examined by the above test methods.

In the cup, heat resistance (A), hot water resistance (B), cold drop resistance (C), gas barrier property (D),
It was confirmed that all of the heat sealability (E), the transparency (F), and the ultraviolet ray blocking ability (UV) were sufficient as food containers (marked with a circle). The above results are also shown in [Table 2]. The copolymer polyester resin / PC represents the weight ratio.

[Polymer Alloy of Copolymerized Polyester Resin and PC of Examples 2 to 13, Examples 17 to 35 and Comparative Examples 1 to 19] In the same manner as in the case of the copolymerized polyester resin and PC polymer alloy of Example 1. The physical properties of a molding cup made of these polymer alloys were investigated. The results are summarized in [Table 2], [Table 3], and [Table 4]. In addition,
Copolymerized polyester resin / PC represents a weight ratio.
As is clear from these tables, in the polymer alloys of Examples 2 to 29 and Examples 34 and 35, heat resistance (A), hot water resistance (B), cold drop resistance (C), gas barrier property (D). A food container having sufficient heat sealability (E), transparency (F), and UV blocking property (UV) can be obtained. When the naphthalene dicarboxylic acid (NDC) is 70 mol% or less and the ethylene glycol (EG) is 25 mol% or less in the copolyester resin, the haze value is less than 5%, and a molded article having particularly excellent transparency is obtained. You can see that In addition, Comparative Examples 2, 3,
From 6, 7, 8 and 11, the solubility parameter (δ) was 11.
From Comparative Example 4, it can be seen that the transparency decreases when the number exceeds 9.
If the solubility parameter is less than 10.8, it blocks UV rays,
It can be seen that the gas barrier property is lowered. Furthermore, in the example satisfying the limiting condition of claim 3, all of the heat resistance (A), the hot water resistance (B), the transparency (F), and the ultraviolet blocking property (UV) are sufficient. In the case of satisfying the requirements, a food container excellent in all of heat resistance (A) to ultraviolet ray blocking property (UV) can be obtained.

[Polymer Alloy of Copolymerized Polyester Resin of Examples 14, 15 and 16 and PC] In the same manner as in the case of the copolymerized polyester resin / PC polymer alloy of Example 1, the blend ratio of the copolymerized polyester resin and PC is Was changed variously to form a sheet having a thickness of 0.6 mm, a molding cup was produced using these sheets in the same manner as in Example 1, and the physical properties thereof were examined. The results are shown in [Table 2].

In the cup, heat resistance (A), hot water resistance (B), cold drop strength (C), gas barrier property (D),
It was confirmed that the heat-sealing property (E), the transparency (F), and the ultraviolet blocking property (UV) were all sufficient for a food container. The above results are also shown in [Table 2].

[Polymer Alloy of Copolymerized Polyester Resin of Example 30 and PC] In the same manner as in the case of the copolymerized polyester resin / PC polymer alloy of Example 1, the blending ratio (copolymerization of copolymerized polyester resin and PC) A sheet having a thickness of 0.6 mm and made of a polymer alloy having a polyester resin / PC: weight ratio of 30/70 was formed, and its gas barrier property was examined. As a result, the oxygen transmission rate was 3.4 cm ³ · cm / cm ² · sec · cmHg. On the other hand, the oxygen transmission rate of the conventional PET sheet is 5.8 ×
It was 10 ⁻¹² cm ³ · cm / cm ² · sec · cmHg. As described above, the sheet made of the polymer alloy exceeds 4 times the oxygen transmission rate of the PET sheet, so that it cannot be used even for those with a short shelf life of about 3 months, and the gas barrier property is insufficient. all right. In addition, heat resistance etc.
Other physical properties were sufficient. The above results are also shown in [Table 3].

[Polymer Alloy of Copolymerized Polyester Resin of Example 31 and PC] In the same manner as in the case of the copolymerized polyester resin / PC polymer alloy of Example 14, the blending ratio of the copolymerized polyester resin and PC (copolymerized polyester) A resin alloy / PC: weight ratio) of 90/10 is used to form a sheet having a thickness of 0.6 mm, which is made of a polymer alloy, and this sheet is used to obtain a diameter of 80 mm and a depth of 27 m.
A cup-shaped molded product of m was produced, and various physical properties of this cup were examined in the same manner as in the case of the copolyester resin / PC polymer alloy of Example 14. As a result, it was found that the cold drop strength was insufficient. The other heat resistance and hot water resistance were sufficient.

The results of [Table 2], [Table 3] and [Table 4] will be supplementarily described below. The polymer alloy of Example 30 had a blend ratio: copolyester resin / PC of 3
0/70, which is within the limited range of claim 3, but outside the limited range of claim 4. Therefore, it is inferior in gas barrier property. The polymer alloy of Example 31 is
Blend ratio: Copolymerized polyester resin / PC 90/1
0, which is also outside the range defined by claim 4, is inferior in cold shock resistance. In the polymer alloy of Example 32, the blend ratio: copolyester resin / PC was 2/98, which was also outside the limited range of claim 4, and therefore was inferior in gas barrier property and heat seal property. The polymer alloy of Example 33 had a blend ratio of: copolyester resin /
The PC content is 95/5, which is also outside the limited range of claim 4, so that the cold shock resistance is poor. Further, in the polymer alloys of Comparative Example 8 and Comparative Example 10, since the CHDM / EG ratio is outside the range defined by claim 2, the former is inferior in transparency and the latter is inferior in gas barrier property and heat sealability. Furthermore, in the polymer alloys of Comparative Example 9 and Comparative Example 11, the NDC / TPA ratio is out of the range defined by claim 2, so that the former is inferior in heat resistance and hot water resistance, and the latter is inferior in heat sealability and transparency. There is. Further, in the polymer alloys of Comparative Examples 12 to 19, the molar ratio of the cis isomer of CHDM to the trans isomer (cis isomer / trans isomer) is claimed.
The heat resistance is inferior because it is out of the limited range.

Comparative Examples 20 to 23 and Examples 36 to 38 Next, using the copolyester resin of Example 14 and the same PC as used in Example 1, a copolyester resin and PC were prepared. The heat resistance of the molding cup made of the polymer alloy was investigated in detail when the blending ratio (copolymerized polyester resin / PC weight ratio) was variously changed. In this case, the molded cup of the above 100 cc capacity was
The time of immersion in the constant temperature bath for 30 minutes was set to 30 minutes, and the capacity change of the cup was examined. For comparison, heat resistance was also tested on a cup made of PC alone. The test conditions and results are shown in [Table 5] below.

[0052]

[Table 5] ────────────────────────────────── Blending ratio Hot water bath by dipping time Heat resistance (weight ratio) Temperature (℃) 30 minutes ────────────────────────────────── Comparative Example 20 95/5 87 × 21 90/10 87 △ 22 30/70 87 ○ 23 0/100 87 ○ Example 36 80/20 87 ○ 37 70/30 87 ○ 38 50/50 87 ○ ──────── ────────────────────────────

As is clear from [Table 5], by setting the copolymerized polyester resin / PC ratio within the range of 50/50 to 80/20, a food packaging container having sufficient heat resistance is produced. be able to.

Example 39 The copolymerized polyester resin of Example 14 above and Example 1
Gas barrier properties (oxygen permeability) of the molded sheet made of the polymer alloy in the case where the blending ratio of the copolyester resin and the PC was variously changed were tested using the same PC as used in 1. For comparison, PC
A single sheet and a commercially available PET sheet were also examined. The results are shown in Fig. 1. As is apparent from FIG. 1, as the content (% by weight) of the copolymerized polyester resin in the polymer alloy was increased, the oxygen permeability was linearly decreased, and the content of the copolymerized polyester resin was 50 to 8%.
Oxygen permeability of 2.0 × 10 by adjusting to 0% by weight
It can be suppressed within the range of ^{-11 to} 7.2 × 10 ^-12 cm ³ · cm / cm ² · sec · cmHg (hereinafter, the unit of oxygen permeability is the same as this). The oxygen permeability of the PET sheet is 5.8 × 10 ⁻¹² , and the oxygen permeability of the polymer alloy sheet having a copolymerized polyester resin content of 50 to 80% by weight is compared with the latter. It can be seen that the oxygen transmission rate of is less than 4 times that of the PET sheet. Also, P
The oxygen permeability of the sheet made of C alone is 7.7 × 10 ^-11
Met.

[0055]

As is clear from the above description, according to the present invention, heat resistance, hot water resistance (whitening resistance), cold shock resistance (cold drop strength), sufficient gas barrier property, and aluminum closure are obtained. It is possible to provide a polymer alloy that has a heat-sealing property with, and is also excellent in transparency and UV blocking property, and by molding this polymer alloy by an appropriate method, it is possible to provide packaging materials and foods having extremely excellent properties. A packaging container can be manufactured.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the mixing ratio of a copolyester resin and PC and the oxygen transmission rate of a sheet obtained by molding the mixed resin.

Front page continuation (72) Inventor Mr. Hamahiro 4-14-12 Koishikawa, Bunkyo-ku, Tokyo Co-printing Co., Ltd. (72) Inventor Sekine Shin-shi 4-14-12 Koishikawa, Bunkyo-ku, Tokyo Joint printing stock In-company (72) Inventor Takashi Shirane 4-14-12 Koishikawa, Bunkyo-ku, Tokyo Within Kyodo Printing Co., Ltd. (72) Inventor Yuzo Fukawa 4-14-12 Koishikawa, Bunkyo-ku, Tokyo Inside Kyodo Printing (72) ) Inventor Shinichiro Mori 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd. (72) Inventor Yasuhiro Harada 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan KK (72) Invention Junichi Kitagawa 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd.

Claims (7)

[Claims] 1. A polymer alloy of a copolyester resin and a polycarbonate resin having a solubility parameter in the range of 10.8 to 11.9, wherein the copolyester resin has 2,6-naphthalenedicarboxylic acid as an acid component. A polymer alloy comprising an acid and terephthalic acid or a lower alkyl ester thereof, and a glycol component of 1,4-cyclohexanedimethanol and ethylene glycol. 2. The copolymerized polyester resin has a molar ratio (2,6-) of 2,6-naphthalenedicarboxylic acid and terephthalic acid or their lower alkyl esters.
Naphthalenedicarboxylic acid or its lower alkyl ester / terephthalic acid or its lower alkyl ester) is 5/95 to 95/5, and the ratio of the number of moles of 1,4-cyclohexanedimethanol and ethylene glycol (1,4-cyclohexanedimethanol / Ethylene glycol) is 53
/ 47 to 95/5, and 1,4-cyclohexanedimethanol has a molar ratio of cis isomer to trans isomer (cis isomer / trans isomer) of 0/100 to 40/60. Item 1. The polymer alloy according to Item 1. 3. The blend ratio of the copolymerized polyester resin and the polycarbonate resin (weight of copolymerized polyester resin / weight of polycarbonate resin) is 2/98 to 9
It is 5/5, The polymer alloy of Claim 2 characterized by the above-mentioned. 4. The blending ratio of the copolyester resin and the polycarbonate resin (weight of copolyester resin / weight of polycarbonate resin) is 50/50 to.
The polymer alloy according to claim 2, wherein the polymer alloy is 80/20. 5. A packaging material such as a sheet and a film, which is obtained by molding the resin containing the polymer alloy according to claim 1, 2, 3 or 4 as a main component. 6. A packaging container obtained by vacuum forming or pressure forming the packaging material according to claim 5. 7. A resin obtained by direct blow molding, injection molding, injection blow molding or injection biaxial stretch blow molding of the resin containing a polymer alloy as a main component according to claim 1, 2, 3 or 4. Characteristic packaging container.