JPH08337659A - Container made from copolyester - Google Patents

Abstract

PURPOSE: To obtain a container which is made from a substantially unstretched impact-resistant copolyester and has improved resistances to chemicals and heat, clarity, moldability, and productivity by using a copolyester produced from terephthalic acid, ethylene glycol, and a specific diol. CONSTITUTION: This container is obtd. by molding a substantially unstretched copolyester which is produced by using a dicarboxylic acid component comprising terephthalic acid and a diol component mainly comprising ethylene glycol and contg. 0.5-50mol% 2,2-dialkyl-1,3-propanediol represented by the formula (wherein (m) and (n) are each independently an integer of 0-5) and which has an intrinsic viscosity of 0. 50-2.00dl/g when measured in a phenol/ tetrachloroethane mixed solvent (a wt. ratio of 1/1) at 30 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester container having excellent impact resistance, chemical resistance, heat resistance, transparency, shapeability, productivity and the like.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter referred to as "P
ET)) and other polyester resin packaging materials have excellent mechanical strength, chemical stability, transparency, gas barrier properties, hygiene properties, etc., and are relatively inexpensive and lightweight. Widely used as sheets, containers, etc. In particular, in recent years, from the viewpoint of waste disposal problems and environmental protection, the development of extruded sheets, drawing containers, extrusion blow hollow containers, injection molding containers, etc., which are conventionally made of polyvinyl chloride or polystyrene, has been remarkably expanded. .

In the field of such a container, for example, in an extrusion blow hollow container, a molten plasticized resin is extruded through a die orifice to form a cylindrical parison, which is sandwiched by a mold to blow a gas inside. Is molded in. In such a case, the molded product is in an unstretched or low-stretched state, and the conventional polyester molded product such as PET has a problem that the impact resistance is insufficient.

On the other hand, attempts have been made to produce a packaging material having improved impact resistance by using PET having a high degree of polymerization, but even in this case, the impact resistance is still insufficient. Further, since PET having a high degree of polymerization takes a long time to be polymerized, it is generally low in productivity and expensive, and it is economically problematic when used as a packaging material.

Further, isophthalic acid and 2,2-bis (4-
Various attempts have been made to produce a packaging material with improved impact resistance by using modified PET obtained by copolymerization of ethylene oxide adduct of (hydroxyphenyl) propane, cyclohexanedimethanol, etc. Although it has the effect of improving the shapeability due to the drop and the effect of improving the transparency due to the decrease of the crystallization rate, it has not yet achieved sufficient impact resistance. In addition, since the resin has poor thermal stability, it is severely deteriorated when it stays in the cylinder during molding, resulting in reduced impact resistance, or because it has poor chemical resistance, it cannot be brought into contact with water, alcohol, etc. as a beverage container. In this case, there is a problem that the impact resistance is remarkably deteriorated due to deterioration over time, or the heat resistance is poor, so that the beverage or the like is significantly deformed when heat-filled.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and compared with the conventional polyester container obtained by molding without substantial stretching of the cane.
Excellent impact resistance, chemical resistance, heat resistance, transparency, shapeability,
The present invention relates to a container made of a copolyester which is excellent in productivity and the like and is obtained by molding without being substantially stretched.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above problems, a container obtained by molding a polyester obtained by copolymerizing a specific diol component substantially unstretched Was found to be extremely excellent in various physical properties such as impact resistance, and the present invention was reached. That is, the gist of the present invention is a copolyester having terephthalic acid as a dicarboxylic acid component and ethylene glycol as a main component as a diol component, and a compound represented by the following general formula (1) as a diol component is a total diol. 0.5 to 50 mol% relative to the components, and has an intrinsic viscosity of 0.50 to
The copolymerized polyester of 2.00 dl / g is present in a container made of copolymerized polyester obtained by molding substantially unstretched.

[0008]

Embedded image (However, m and n are each an integer from 0 to 5,
It may be the same or different)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The copolymerized polyester provided in the container of the present invention has a dicarboxylic acid component containing terephthalic acid as a main component as an acid component,
It is a compound consisting of a diol component containing ethylene glycol as a main component as an alcohol component, and a compound represented by the above general formula (1) as a diol component of a copolymerization component 2,2
-Dialkyl-1,3-propanediol in an amount of 0.5 to 50 mol%, preferably 3 to 3 based on the total diol components.
It is characterized in that it is contained in an amount of 0 mol%, more preferably 5 to 20 mol%. 2,2-dialkyl-1,3
-When the copolymerization amount of propanediol is less than 0.5 mol%, sufficient impact resistance when molded into a packaging material cannot be obtained, and when it exceeds 50 mol%, thermal stability is poor and stable. Molding becomes difficult and the impact resistance of the container becomes insufficient.

Regarding the alkyl group of 2,2-dialkyl-1,3-propanediol, m and n in the general formula (1) are each an integer of 0 to 5, preferably an integer of 0 to 3. , And more preferably an integer of 0 to 2. The numbers m and n may be the same or different. Specifically, neopentyl glycol, 2,
2-diethyl-1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2,2-dipentyl-
1,3-propanediol, 2,2-dihexyl-1,
3-propanediol, 2-ethyl-2-propyl-
1,3-propanediol, 2-butyl-2-ethyl-
1,3-propanediol, 2-ethyl-2-hexyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol and the like can be mentioned, among which 2-butyl-2-ethyl- 1,3-propanediol,
Neopentyl glycol is preferred, 2-butyl-2-
Ethyl-1,3-propanediol is particularly preferred.
When m and n are 6 or more, the polymerizability is poor and the productivity of polyester tends to be low, and there is a problem in the economical efficiency when used as a packaging material.

The copolymerized polyester provided in the container of the present invention is represented by a dicarboxylic acid component other than terephthalic acid, ethylene glycol and the general formula (1) as a copolymerization component within a range not impairing the effects of the present invention. A diol component other than the diol to be used may be contained. These copolymerization components are used in the dicarboxylic acid component or the diol component in an amount of usually 20 mol% or less, preferably 10 mol% or less.

Examples of the dicarboxylic acid component other than terephthalic acid which constitutes the copolyester used in the container of the present invention include isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, dibromoisophthalic acid and sodium sulfoisophthalate. , Biphenyl dicarboxylic acid, biphenyl ether dicarboxylic acid, biphenyl sulfone dicarboxylic acid, biphenyl ketone dicarboxylic acid, biphenoxyethane dicarboxylic acid,
Aromatic dicarboxylic acids such as phenylenedioxydicarboxylic acid, and also aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid, piperic acid, suberic acid, azelaic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. To be

Examples of the diol component other than ethylene glycol and the diol represented by the general formula (1) include trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, Aliphatic glycols such as propylene glycol, diethylene glycol, polyethylene glycol, polyoxytetramethylene glycol, alicyclic glycols such as cyclohexanedimethanol, aromatic glycols such as xylylene glycol, 2,2-bis (4-hydroxyphenyl) propane Ethylene oxide adduct and propylene oxide adduct.

Further, the copolyester provided in the container of the present invention may contain a small amount of a monofunctional component or a polyfunctional component without departing from the effects of the present invention. For example, monofunctional components such as stearic acid and benzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid, gallic acid, trimethylolpropane, triethylolethane, pentaerythritol, glycerin, tetrakis [methylene-3- ( 3 ', 5'-di-t-butyl-
4′-hydroxyphenyl) propionate] methane and other polyfunctional components having three or more functional groups are mentioned.

The copolyester used in the container of the present invention usually has an intrinsic viscosity of {value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1)}. 50 to 2.00 dl / g, preferably 0.60 to 1.50 dl / g, and particularly 0.80 to 1.5 for a hollow container obtained by extrusion blow molding.
The range of 0 dl / g is preferable, and the range of 0.60 to 0.90 dl / g is preferable for a container obtained by drawing a sheet material formed by extrusion molding or for a container obtained by injection molding. If the intrinsic viscosity is less than 0.50 dl / g, the melt viscosity of the resin will be too low, and drawdown of parison etc. will occur during extrusion, blow, etc., and backflow etc. will occur during injection molding etc. for stable molding. Is difficult and
The impact resistance of the container is insufficient and the intrinsic viscosity is 2.00d.
If it exceeds 1 / g, the melt viscosity of the resin becomes too high, making extrusion and blowing difficult. The drawdown is a phenomenon in which a molten resin such as parison cannot withstand its own weight and falls. Further, the backflow is a phenomenon in which molten resin in the cylinder leaks in a direction opposite to the injection direction through a gap between the screw and the cylinder during injection.

The copolymerized polyester provided in the container of the present invention can be produced by a method conventionally known for PET, such as melt polymerization and, if necessary, subsequent solid phase polymerization. For melt polymerization, for example, terephthalic acid, ethylene glycol, and 2,2-dialkyl-
There is a method in which a direct esterification reaction is carried out using 1,3-propanediol under pressure, and then the temperature is further raised in the presence of a catalyst and the pressure is gradually reduced to carry out a polycondensation reaction. Alternatively, an ester derivative of terephthalic acid, for example, dimethyl terephthalic acid, and ethylene glycol and 2,2-dialkyl-1,3-propanediol are used for transesterification in the presence of a catalyst, and then the resulting reaction product is used. The polycondensation reaction is the same as the above direct esterification reaction. In addition, 2,2-dialkyl-
1,3-Propanediol can be added at any time during the esterification reaction or transesterification reaction, or at the initial stage of the polycondensation reaction.

The copolymerized polyester thus obtained by melt polymerization is usually melt-extruded in a strand shape and then cut into granular chips by a cutter. In the above esterification reaction, transesterification reaction, and polycondensation reaction, it is preferable to use necessary amounts of an esterification catalyst, a transesterification catalyst, a polycondensation catalyst, a stabilizer, and the like.
Since terephthalic acid serves as an autocatalyst for the esterification reaction, it is not necessary to use an esterification catalyst, but it can be carried out in the coexistence of a polycondensation catalyst described later, and a small amount of an inorganic acid or the like is used. You can also As the transesterification catalyst, alkali metal salts such as sodium and lithium, and alkaline earth metal salts such as magnesium and calcium, and metal compounds such as zinc and manganese are preferably used, but manganese compounds are particularly preferable from the viewpoint of transparency. . The use ratio of these catalysts is usually within the range of 5 to 2000 ppm as the amount of metal in the catalyst in all the polymerization raw materials.

As the polycondensation catalyst, a compound soluble in the reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound or a tin compound may be used alone or in combination. Germanium is particularly preferred. Stabilizers include trimethyl phosphate, triethyl phosphate, tri-n
-Butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate and other phosphate esters, triphenyl phosphite, trisdodecyl phosphate, tris nonyldecyl phosphate and other phosphite esters, methyl acid phosphate, Acidic phosphoric acid esters such as isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate, and phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid and polyphosphoric acid are preferable. The use ratio of these catalysts or stabilizers is usually 5 to 200 as the weight of the metal in the catalyst in the case of using the catalyst in all the polymerization raw materials.
Used in the range of 0 ppm. In the case of stabilizers,
The weight of phosphorus atoms in the stabilizer is usually 10 to 1000.
Used in the ppm range. These catalysts and stabilizers can be supplied at the time of preparing the raw material slurry, at any stage of the esterification reaction or transesterification reaction, and further at the initial stage of the polycondensation reaction step.

Further, if necessary, the polymer chips obtained by the melt polymerization can be subjected to a heat treatment to increase the degree of polymerization by solid-phase polymerization, lower acetaldehyde, lower oligomer. The heat treatment is usually performed at 60 to 180 ° C. under an inert gas such as dry nitrogen, argon, carbon dioxide, or under steam or under an inert gas containing steam.
After crystallizing the surface of the polymer chip at the above temperature, directly below the adhesive temperature of the resin to 80 ° C under reduced pressure or under an inert gas.
It is carried out at a low temperature within a range of several tens of hours or less. At this time, in the polyester to be used in the container of the present invention, a polyester having a higher solid phase polymerization rate and a higher degree of polymerization than ordinary homo-PET can be obtained with high productivity. Further, in the solid phase polymerization, it is preferable that the polymer chips are fluidized by an appropriate method such as a tumbling method or a gas fluidized bed method so that the polymer chips do not stick to each other.

The copolyester thus obtained is a substantially unstretched melt-molding method conventionally used for PET, polyvinyl chloride, polystyrene, etc., specifically extrusion blow molding. The container of the present invention is molded by drawing, injection molding, or the like. When a hollow container is manufactured by extrusion blow molding, for example, a tube-shaped molten parison is once formed by extrusion molding, and one end is melted in a molten state to form a bottom, and then a mold having a predetermined shape is immediately formed. The method of blowing in is applied. The molding temperature in this case, specifically, the temperature of each part of the cylinder and nozzle of the molding machine is at or above the softening point of the resin, usually 180 to 300 ° C., and can be set to a lower molding temperature than in the case of homo-PET. The melt viscosity can be secured and the shapeability is good, and it is possible to suppress the decrease in the intrinsic viscosity due to heat deterioration, the heating amount is small, and the productivity is high. Although the mold temperature is usually set to 0 to 30 ° C., the copolymerized polyester has a lower crystallization rate than homo-PET, and thus the obtained hollow container has high transparency. In addition, the copolymerized polyester has a glass transition point of 1 to 1 as compared with homo PET
Since the extrusion blow container obtained has a high temperature of about 30 ° C. and a high elastic modulus, it does not deform even when filled with hot water or the like, and has high heat resistance.

In producing a draw-formed container, an extruded sheet is formed from the above-mentioned copolymerized polyester, and the extruded sheet is drawn and formed. Specifically, for example,
A sheet obtained by extruding through a die from a single-screw or twin-screw extruder, winding it with a casting roll in which a refrigerant is circulated, and cooling it is preheated to a predetermined temperature and then contacted with a mold having a predetermined shape. The method of letting is applied. In this case, the molding temperature at the time of forming the sheet, specifically, the temperature of each part of the cylinder of the molding machine and the nozzle is equal to or higher than the softening point of the resin, usually 180 to 300 ° C.
Since the molding temperature can be set lower than in the case of ET, an appropriate melt viscosity can be secured and the shapeability is good, and it is possible to suppress the decrease in the intrinsic viscosity due to heat deterioration, and the heating amount is small, High productivity. The thickness of the sheet in this case is usually 100 to 800 μm, preferably 250.
˜550 μm, particularly preferably 270-500 μm.

Further, the preheating temperature during the drawing process is not less than the glass transition point of the extruded sheet, usually 70 to 150.
C., preferably 80 to 130.degree. C., and the squeezing ratio may be a commonly used setting, but is preferably 0.
It is 1 to 10 times. The above preheated sheet does not cause drawdown and is excellent in shapeability. Further, the mold temperature is usually set to 0 to 30 ° C., but since the extruded sheet has a lower crystallization rate than the extruded sheet made of homo PET,
The obtained draw-formed container has high transparency. The copolymerized polyester has a glass transition point of 1 to 3 as compared with homo-PET.
Since the extrusion blow container obtained has a high temperature of about 0 ° C. and a high elastic modulus, it does not deform even when filled with hot water or the like, and has high heat resistance.

In manufacturing an injection-molded container, for example, a method in which a screw is supplied from a hopper into a cylinder to melt and plasticize it, a certain amount of it is retained for a certain period of time, and then it is injected into a mold having a predetermined shape. Applied. In this case, the molding temperature, specifically, the temperature of each part of the cylinder and nozzle of the molding machine is at or above the softening point of the resin, usually 180 to 30.
The melt viscosity is set in the range of 0 ° C., and a lower melt viscosity than that in the case of homo-PET at the same temperature can be secured, and the shapeability is excellent. Also,
Productivity is high because the amount of heat required for injection and mold clamping is small. Although the mold temperature is usually set to 0 to 30 ° C., the copolymerized polyester has a lower crystallization rate than homo-PET, and thus the obtained hollow container has high transparency. Further, the above-mentioned copolymerized polyester has a glass transition point of 1 to 30 ° C. higher than that of homo-PET and has a high elastic modulus, so that the obtained extrusion blow container is not deformed even when it is filled with hot water, etc. It is highly likely.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Various measuring methods and evaluation methods in Examples are shown below. The method for measuring the intrinsic viscosity is as described above.

(1) Copolymerization amount of 2,2-dialkyl-1,3-propanediol The copolyester is dissolved in deuterated trifluoroacetic acid at room temperature to obtain a 3% solution. JEOL JNM-EX
¹ H-NMR of this solution was measured by a 270-type nuclear magnetic resonance apparatus, each peak was assigned, and it was calculated from the integral ratio.
In addition, in Table-1, Table-2 and Table-3 described later,
As the 2,2-dialkyl-1,3-propanediol component, 2-butyl-2-ethyl-1,3-propanediol (m = 1, n = 3 in the general formula (1)) is “BEP”, Neopentyl glycol (m = 0, n = 0 in the general formula (1) above) is indicated by “NPG”. In addition, 2,2-bis (4
The ethylene oxide adduct of -hydroxyphenyl) propane was designated as "BHPP".

(2) Evaluation of extrusion blow molding Using an extrusion blow molding machine "electric small blow molding machine JEB-7 / P50 / WS60S" manufactured by Japan Steel Works, a cylinder,
The nozzle was set to a temperature set as shown in each of the following examples, an extrusion rate of about 20 kg / hour, a molding cycle of about 20 seconds, and a hollow container having a capacity of 2000 ml, a round bottom, and a basis weight of 90 g was extrusion blow-molded. The mold temperature was controlled at 15 ° C. The molding temperature in the examples indicates the set temperature of the cylinder and nozzle. All the resins used for molding were sufficiently dried before being used for molding.

As a molding evaluation item, blowable parison length was evaluated for the purpose of evaluating shapeability. This is the length of the longest parison that can be molded into a hollow container without drawdown, and was visually evaluated. The longer the length of the parison that can be blown, the higher the shapeability. Also, the transparency of the obtained hollow container was evaluated by visual observation. In Table 1, Table 2 and Table 3 described below, the evaluation of transparency is shown by “◯” when the material is colorless and transparent and “x” when the haze is observed.

(3) Impact resistance test of hollow container A 2000 ml hollow container obtained by the above extrusion blow molding was filled with 1800 ml of demineralized water, sealed and cooled to 5 ° C. in a refrigerator. After cooling for 1 hour, the hollow container was taken out of the refrigerator, and the outside of the hollow container was dropped vertically from a height of 0.5 m onto an iron plate having a thickness of 5 cm in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, without cracking. For example, the hollow container is then dropped vertically from a height of 0.1 m to 0.6 m onto an iron plate having a thickness of 5 cm. In this way, if there is no crack, raise the drop height by 0.1 m and perform a test until the hollow container breaks.
The breaking height of the hollow container was used. This is performed for 10 hollow containers, and the average value of the breaking heights of the 10 hollow containers is rounded to the nearest unit (average breaking height),
The impact resistance of the hollow container was evaluated. (The higher the average breaking height, the better the impact resistance.)

(4) Chemical resistance test of hollow container A 2000 ml hollow container was filled with 1800 ml of an aqueous ethanol solution (water: ethanol = 1: 1), and the container was tightly closed and placed in a constant temperature bath at a temperature of 40 ° C. and a relative humidity of 5%. It was stored for 30 days. After storage, each hollow container was taken out from the constant temperature bath, allowed to cool at room temperature for 1 hour, and further cooled to 5 ° C. in the refrigerator for 1 hour. After that, the hollow container was taken out from the refrigerator, and the outside of the hollow container was at 0.
Drop vertically from a height of 5 m onto a 5 cm thick iron plate,
If there is no crack, then add 0.1 m higher to this hollow container.
Drop vertically from a height of 6 m onto an iron plate also 5 cm thick. In this way, if there is no crack, the drop height is 0.1
The test was conducted until the hollow container was cracked by raising it by m, and the drop height at the time of breaking was taken as the breaking height of the hollow container. Do this for 10 hollow containers,
The average value of the breaking heights of 10 hollow containers was rounded to the nearest unit (average breaking height) to calculate the value. The chemical resistance of the container is evaluated by the ratio (impact resistance retention rate (unit%)) of the average fracture height in this chemical resistance test to the average fracture height in the impact resistance test in the same container. did. (The higher the impact resistance retention rate, the better the chemical resistance.)

(5) Evaluation of drawing molding First, the cylinder and nozzle were set to the set temperatures as shown in the following examples, the screw rotation speed was 40 rpm, and the extrusion amount was 8
A sheet having a wall thickness of 500 μm was molded with a 40 mmφ uniaxial extruder manufactured by Tanabe Plastic Co., Ltd., which was set to 0 g / min. Next, after preheating the extruded sheet to 110 ° C., the mold temperature was set to 1
Asano Laboratory made KF-0231-5 type pressure-assisted vacuum forming machine with plug assist at 5 ° C., length 7 cm, width 10
cm, and a draw forming container having a depth of 3 cm was formed. All the resins used for molding were sufficiently dried before being used for molding.

(6) Evaluation of injection molding Using an injection molding machine "IS-60B" manufactured by Toshiba Machine Co., Ltd., the resin temperature was set to a set temperature as shown in each of the following examples, and about 5 k
With a back pressure of g / cm ² , an injection pressure / holding pressure of about 20 kg / cm ² , a molding cycle of about 30 seconds, a capacity of 150 ml,
A hollow container having a round bottom and a basis weight of 60 g was injection-molded. The mold temperature was controlled at 15 ° C. All the resins used for molding were sufficiently dried before being used for molding.

(7) Impact resistance test of draw-molded container and injection-molded container The container was filled with demineralized water at 23 ° C., and a metal lid was attached to the opening to prevent the content liquid from leaking out of the container. rear,
Cooled to 5 ° C in a refrigerator. After cooling for 1 hour, the container was taken out of the refrigerator, and the outside of the container was dropped vertically from a height of 0.5 m onto an iron plate having a thickness of 5 cm in an atmosphere with a temperature of 23 ° C. and a relative humidity of 50%. Then add this container to 0.1
It is dropped vertically from a height of 0.6 m to a height of 5 cm on an iron plate having a thickness of 5 cm. In this way, if there is no crack, the drop height is increased by 0.1 m, and a test is conducted until the container breaks. The drop height at the time of cracking is taken as the breaking height of the container. Do this for 10 containers, 1
The impact resistance of the container was evaluated using the value (average breaking height) obtained by rounding off the ones place of the average value of the breaking height of 0 containers (average breaking height). (The higher the average breaking height, the better the impact resistance.)

(8) Chemical resistance test of draw-molded container and injection-molded container Aqueous ethanol solution (water: ethanol = 1: 1) in the container.
And a metallic lid attached to the opening to prevent the contents liquid from leaking out of the container. The temperature was 40 ° C and the relative humidity was 5
% In a constant temperature bath for 30 days. After storage, each container was taken out from the constant temperature bath, allowed to cool at room temperature for 1 hour, and further cooled to 5 ° C. in the refrigerator for 1 hour. After that, the container was taken out from the refrigerator and the temperature outside the container was 23 ° C and the relative humidity was 5
In a 0% atmosphere, it is dropped vertically from a height of 0.5 m onto an iron plate with a thickness of 5 cm, and if there is no crack, then this container is increased by 0.1 m from a height of 0.6 m to a thickness of 5 cm. Drop vertically on the iron plate. In this way, if there is no crack, the drop height is increased by 0.1 m, and a test is conducted until the container breaks. The drop height at the time of cracking is taken as the breaking height of the container. This was carried out for 10 containers, and the average value of the breaking heights of the 10 containers was rounded to the nearest digit (average breaking height) to calculate. The chemical resistance of the container is evaluated by the ratio (impact resistance retention rate (unit%)) of the average fracture height in this chemical resistance test to the average fracture height in the impact resistance test in the same container. did. (The higher the impact resistance retention rate, the better the chemical resistance.)

(9) Heat resistance test Temperature 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C
Each container was filled with 10 parts of water at each temperature, capped, and then left to cool at room temperature. The deformation of the container after cooling was evaluated by visual observation. Tables 1 and 2 described later
In Table 3, as the evaluation of heat resistance, "○" means no deformation, "△" means that the body / bottom part is slightly deformed (including the case where deformation does not occur after plugging), and immediately after filling with water. It is indicated by "x" that it is already deformed so that capping is impossible. In addition, the temperature of the filling water such that all 10 containers were “◯” was taken as the heat resistant temperature of the container.

Example 1 65.74 kg (490.1) of terephthalic acid was previously prepared.
3 mol), 2-butyl-2-ethyl-1,3-propanediol 9.33 kg (58.24 mol), ethylene glycol 33.19 kg (534.69 mol) slurry was prepared, to which 1.26 kg (4.95 mol) bis (2-hydroxyethyl) terephthalate was added,
It was sequentially supplied to the esterification tank kept at 250 ° C. over 4 hours.

After the completion of the feeding, the esterification reaction was allowed to proceed for an additional 1 hour, then, half of the amount was transferred to a polycondensation tank, phosphoric acid (to polymer: 150 ppm) and germanium dioxide (to polymer: 120 ppm) were charged, and the temperature was from 250 ° C to 280 ° C.
The temperature is gradually raised from normal pressure to 0.
It was kept at 5 mmHg. After the reaction was carried out for 4 hours, the produced polymer was withdrawn in a strand form from an outlet provided at the bottom of the polycondensation tank, cooled with water, and then cut into chips. This melt-polymerized polymer chip had an intrinsic viscosity of 0.7 dl / g. The esterification reaction and polycondensation reaction proceeded smoothly.

Subsequently, the surface of the melt-polymerized polymer chips was crystallized at 150 ° C. with a stirring crystallization machine (Bepex Co.), and then transferred to a stationary solid-phase polymerization tower, 20 L / kg · h.
Under nitrogen flow of r, after drying at about 150 ° C for 3 hours, 205 ° C
Solid-state polymerization was carried out for 28 hours to obtain a solid-state polymerization chip. Table 1 shows the analysis results of this solid-state polymerization chip.

Using the above solid-state polymerized chips, extrusion blow molding was performed by the above method to obtain a 700 ml extrusion blow hollow container. Molding can be suitably performed without any particular problems such as drawdown property, and the results of observation of the transparency of the obtained hollow container were colorless and transparent, which was good. The evaluation results are shown in Table-1.

Examples 2 to 8 and Comparative Examples 1 to 3 In the same manner as in Example 1, the copolymerization components shown in Table 1 are
A copolymerized PET having an intrinsic viscosity was produced, and then each molded product was produced in the same manner as in Example 1. The copolymerized PET used in Example 7 and Comparative Example 3 was difficult to solid-state polymerize, and thus was manufactured by extending the melt polymerization time. Table 1 shows the evaluation results.

[0040]

[Table 1]

Example 9 By following the same procedure as in Example 1, the copolymerization components shown in Table 2 were obtained.
A copolymerized PET having an intrinsic viscosity was produced, and then extrusion-molded by the method (5) described above, and a drawn-molded container was obtained using the obtained extruded sheet. There is no particular problem with molding,
It was able to be performed suitably. The evaluation results are shown in Table-2.

Examples 10 to 13 and Comparative Examples 4 and 5 Molded articles were produced in the same manner as in Example 9 except that the compositions and the intrinsic viscosities shown in Table 2 were used. Since the solid-state polymerization of the copolymerized PET used in Example 11 was difficult, it was obtained by extending the melt polymerization time. Table 2 shows the evaluation results.

[0043]

[Table 2]

Example 14 By following the same procedure as in Example 1, the copolymerization components shown in Table 3 were obtained.
A copolymerized PET having an intrinsic viscosity was produced, and then an injection-molded container was obtained by the method (6). The molding could be preferably performed without any particular problem. The evaluation results are shown in Table-3.

Examples 15 to 18, Comparative Examples 6 and 7 Each molded product was manufactured in the same manner as in Example 9 except that the composition and the intrinsic viscosity shown in Table 3 were used. Since the solid-state polymerization of the copolymerized PET used in Example 11 was difficult, it was obtained by extending the melt polymerization time. Table 3 shows the evaluation results.

[0046]

[Table 3]

[0047]

The copolymer polyester container of the present invention is
It has excellent impact resistance, chemical resistance, heat resistance, transparency, shapeability, and productivity. Therefore, it is suitable as a large container, a container used at a low temperature, or a container that is stored for a long period of time after being filled with contents.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08J 5/18 CFD B65D 1/00 A B29K 67:00 B29L 31:00 (72) Inventor Masahiro Nukii 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Sanryo Chemical Co., Ltd. Yokohama Research Institute

Claims (6)

[Claims] 1. A terephthalic acid as a dicarboxylic acid component,
A copolymerized polyester containing ethylene glycol as a main component as a diol component, containing 0.5 to 50 mol% of a compound represented by the following general formula (1) as a diol component with respect to all diol components, and Intrinsic viscosity is 0.5
A container made of a copolyester obtained by molding a copolyester having a weight ratio of 0 to 2.00 dl / g substantially unstretched. Embedded image (However, m and n are each an integer from 0 to 5,
It may be the same or different) 2. A container made of a copolyester according to claim 1, wherein m = 1 and n = 3 in the general formula (1). 3. The container made of the copolymerized polyester according to claim 1, wherein m = n = 0 in the general formula (1). 4. A copolyester container according to claim 1, wherein the copolyester container is a hollow container obtained by extrusion blow molding. 5. The copolyester container according to claim 1, which is a container obtained by drawing a sheet formed by extrusion blow molding and extrusion molding. Polymerized polyester container. 6. A copolymer polyester container according to claim 1, wherein the copolymer polyester container is a container obtained by injection molding.