JPH106387A - Bottle made of polyester composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bottle made of a polyester compsn. not deformed even if filled with a heated beverage or the like and capable of holding a self-supporting state. SOLUTION: This bottle is composed of a polyester compsn. consisting of 99.9-99.99999wt.% of polyester and 0.1ppm-0.1wt.% of talc and characterized by that the degree of crystallization of the mouth neck part thereof is 25-60% and that of the central part of the body part thereof is 25-60%. A preform composed of the polyester compsn. is subjected to stretch blowing in area stretching magnificaton of 6-15 times to set the degree of crystallization of the central part of the body part of the bottle to 25-60%. By this constitution, a polyester bottle excellent in heat resistance can be efficiently produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bottle made of a polyester composition and a method for producing the same. The present invention relates to a polyester composition bottle that can be kept and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION In recent years, various plastic materials have been used as materials for beverage bottles such as carbonated beverages, carbonated beverages containing fruit juices, juices, natural waters, and various drinking teas. Of these plastic materials, polyethylene is used. Polyesters such as terephthalate are widely used because of their excellent transparency, gas barrier properties, heat resistance and mechanical strength.

[0003] Since the above-mentioned drinking tea and the like are heat-sterilized and filled into a bottle at a high temperature, if the plastic forming the bottle has poor heat resistance, the bottle may be deformed or shrunk. This may cause problems such as expansion. Therefore, there is a need for a plastic bottle having a property of maintaining its independence without deforming the bottle even when the bottle is filled with a heated beverage or the like (hereinafter, sometimes referred to as “heat-resistant property”). .

[0004] Further, from the viewpoint of productivity, it is required to shorten a molding cycle, particularly a molding cycle during blow molding. The present inventors, based on the above findings, even after filling heated beverages and the like, as a result of intensive study to obtain a bottle with small deformation of the mouth, neck, bottom, etc. of the bottle, a specific polyester composition Was found to be excellent in heat resistance. Also, when manufacturing a bottle using the specific polyester composition,
The inventors have found that the molding cycle can be shortened, and have completed the present invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a bottle made of a polyester composition which can maintain its independence without deforming the bottle even when filled with a heated beverage or the like, and a method for producing the same. I have.

[0006]

SUMMARY OF THE INVENTION The polyester composition bottle according to the present invention comprises 99.9 to 99.9999% by weight of polyester.
And a polyester composition formed from 0.1 ppm to 0.1% by weight of talc, and the crystallinity of the mouth and neck is in the range of 25 to 60%, and the crystallinity of the center of the body is 25.
-60%, and the crystallinity at the bottom is 0-60%.

In such a bottle made of a polyester composition, the crystallization rate of the polyester composition forming the bottle measured by a t1 / 2 heating method (140 ° C.) using a differential scanning calorimeter is 200 seconds or less; In addition, the haze value at the center of the body of the bottle is preferably 5% or less.

The polyester composition bottle is preferably used for non-carbonated beverages such as natural water and drinking tea. The polyester composition bottle according to the present invention,
Excellent heat resistance.

The method for producing a bottle made of a polyester composition according to the present invention comprises the steps of:
And a preform comprising a polyester composition formed from 0.01 to 5% by weight of talc and stretch blown at an area stretch ratio of 6 to 15 times, and the crystallinity at the center of the bottle body is 25 to 60. % Of the bottles.

In the present invention, the crystallization rate of the polyester composition measured by a t1 / 2 heating method (140 ° C.) using a differential scanning calorimeter is preferably 150 seconds or less.
Further, it is preferable to perform heat setting after stretch blow molding.

The method for producing a polyester composition bottle according to the present invention can produce a polyester composition bottle having excellent heat resistance.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a bottle made of a polyester composition according to the present invention and a method for producing the same will be described.

The bottle made of the polyester composition according to the present invention comprises the polyester composition as described below, and has a crystallinity of the mouth and neck of 25 to 60%, preferably 25 to 50%.
The crystallinity at the center of the body is in the range of 25 to 60%, preferably 25 to 50%, and the crystallinity at the center of the bottom is 0 to 60%, preferably 0 to 50%. It is desirable to be within the range. The crystallinity of each part of the bottle is determined by an X-ray diffraction method as described later.

The haze value at the center of the body of the polyester composition bottle according to the present invention is preferably 5% or less, more preferably 3% or less. Such a bottle made of a polyester composition according to the present invention is formed from a polyester composition comprising polyester and talc.

The polyester and talc will be specifically described below. As the polyester used in the polyester composition bottle according to the present invention,
Examples thereof include polyethylene terephthalate, polyethylene naphthalate, and the following copolymerized polyesters (1) to (4).

Polyethylene terephthalate Polyethylene terephthalate is produced using terephthalic acid and ethylene glycol as raw materials, and the polyethylene terephthalate is copolymerized with not more than 20 mol% of another dicarboxylic acid and / or another dihydroxy compound. You may.

In addition to terephthalic acid, specific examples of dicarboxylic acids used for copolymerization include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; adipic acid, sebacine Aliphatic dicarboxylic acids such as acid, azelaic acid and decane dicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid.

Examples of the dihydroxy compound used for copolymerization other than ethylene glycol include aliphatic glycols such as trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol; cyclohexane Alicyclic glycols such as dimethanol; bisphenols; hydroquinone, 2,2-
And aromatic diols such as bis (4-β-hydroxyethoxyphenyl) propane.

Such a polyethylene terephthalate can be used to form a substantially linear polyester by forming an ester bond alone or a random arrangement of the ethylene terephthalate component units and the dioxyethylene terephthalate component units. doing. The fact that the polyethylene terephthalate is substantially linear is confirmed by the fact that the polyethylene terephthalate dissolves in o-chlorophenol.

In such a polyethylene terephthalate, the intrinsic viscosity [η] (measured in o-chlorophenol at 25 ° C.) is usually 0.6 to 1.5 dl / g, preferably 0.7 to 1.2 dl. / G is desirable. Further, the melting point is usually 210 ° C to 265 ° C, preferably 220 ° C.
The glass transition temperature is usually from 50 to 120 ° C, preferably from 60 to 100 ° C.

Polyethylene naphthalate Polyethylene naphthalate is ethylene-2,6 derived from 2,6-naphthalenedicarboxylic acid and ethylene glycol.
-The naphthalate unit is at least 60 mol%, preferably at least 80 mol%.
Although it is desirable to contain it in an amount of at least 90 mol%, more preferably at least 90 mol%, a constitutional unit other than ethylene-2,6-naphthalate may be contained in an amount of less than 40 mol%.

The structural units other than ethylene-2,6-naphthalate include terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, dibromoterephthalic acid; adipic acid,
Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid and decane dicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid and hexahydroterephthalic acid; glycolic acid, p-hydroxybenzoic acid, hydroxycarboxylic acids such as p-hydroxyethoxybenzoic acid and propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, p-xylene glycol, 4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxysulfone, 1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenol) propane, polyalkylene And structural units derived from ethylene glycol, p-phenylenebis (dimethylsiloxane), glycerin and the like.

The polyethylene naphthalate contains a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol, for example, in an amount of 2 mol% or less. Is also good.

Further, polyethylene naphthalate includes benzoyl benzoic acid, diphenyl sulfone monocarboxylic acid, stearic acid, methoxy polyethylene glycol,
Structural units derived from a monofunctional compound such as phenoxy polyethylene glycol may be contained in a small amount, for example, 2 mol% or less.

Such polyethylene naphthalate is
It is substantially linear, as confirmed by the dissolution of the polyethylene naphthalate in o-chlorophenol.

The intrinsic viscosity [η] measured at 25 ° C. in o-chlorophenol of polyethylene naphthalate is 0.2
To 1.1 dl / g, preferably 0.3 to 0.9 dl / g
g, particularly preferably in the range of 0.4 to 0.8 dl / g.

The intrinsic viscosity [η] of polyethylene naphthalate is measured by the following method. That is, polyethylene naphthalate is converted to o-chlorophenol at 1 g / 1
Dissolve at a concentration of 00 ml, measure the solution viscosity using an Ubbelohde capillary viscometer at 25 ° C., then gradually add o-chlorophenol, measure the solution viscosity on the low concentration side, and adjust to 0% concentration. The intrinsic viscosity ([η]) is determined by external search.

The temperature-rising crystallization temperature (Tc) when the polyethylene naphthalate is heated at a rate of 10 ° C./min with a differential scanning calorimeter (DSC) is usually 150 ° C. or higher, preferably 160 ° C. or higher. ~ 230 ° C, more preferably 17
It is desirable to be in the range of 0 to 220 ° C.

The temperature rise crystallization temperature (Tc) of polyethylene naphthalate is measured by the following method. That is,
Using a Perkin Elmer DSC-2 scanning calorimeter, a sample of about 10 mg sliced from the center of a polyethylene naphthalate chip dried at about 140 ° C. under a pressure of about 5 mmHg for about 5 hours or more, The measurement is carried out by enclosing in a liquid aluminum pan under a nitrogen atmosphere. The measurement conditions were as follows: first, the temperature was rapidly raised from room temperature, melted and maintained at 290 ° C. for 10 minutes, then rapidly cooled to room temperature, and then the peak temperature of the exothermic peak detected when the temperature was raised at a rate of 10 ° C./min. Ask for.

Copolyester (1) The copolyester (1) is composed of a dicarboxylic acid structural unit containing a terephthalic acid component unit and an isophthalic acid component unit, and a dihydroxy compound structural unit containing an ethylene glycol component unit. .

The dicarboxylic acid constituting unit constituting the copolymerized polyester (1) has a terephthalic acid component unit of 85 units.
-99.5 mol%, preferably 90-99.5 mol%, and isophthalic acid component units present in an amount of 0.5-15 mol%, preferably 0.5-10 mol%. Is desirable.

In the copolyester (1), in addition to the above-mentioned terephthalic acid and isophthalic acid as the dicarboxylic acid component, the diester is used in an amount not to impair the properties of the obtained copolyester (1), for example, 1 mol% or less. Other dicarboxylic acids can be used.

Examples of such a dicarboxylic acid include phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester (1), other dihydroxy compounds are used as dihydroxy compounds in addition to ethylene glycol as described above in a range that does not impair the properties of the obtained copolymerized polyester (1), for example, 1 mol% or less. It can also be used.

As such a dihydroxy compound,
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
Benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone, etc. 15 dihydroxy compounds.

Copolyester (2) The copolyester (2) comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit and a 2,6-naphthalenedicarboxylic acid component unit, and a dihydroxy compound structural unit containing an ethylene glycol component unit. Is formed from.

The dicarboxylic acid constituting unit constituting the copolymerized polyester (2) has 80 units of terephthalic acid component.
-99.5 mol%, preferably 90-99.5 mol%, and the 2,6-naphthalenedicarboxylic acid component unit is 0.5-20 mol%, preferably 0.5-10 mol%. Desirably it is present in an amount.

In the copolyester (2), in addition to the above-mentioned terephthalic acid and 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component, a range in which the properties of the obtained copolyester (2) is not impaired, for example, 1 mol %
Other dicarboxylic acids can be used in the following amounts.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid and the like. In the copolymerized polyester (2),
As the dihydroxy compound, other than the above-mentioned ethylene glycol, other dihydroxy compounds can be used in a range that does not impair the properties of the obtained copolymerized polyester (2), for example, 1 mol% or less.

As such a dihydroxy compound,
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
Benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone, etc. 15 dihydroxy compounds.

Copolyester (3) The copolyester (3) is composed of a dicarboxylic acid structural unit containing a terephthalic acid component unit and an adipic acid component unit, and a dihydroxy compound structural unit containing an ethylene glycol component unit. .

The dicarboxylic acid constituting unit of the copolymerized polyester (3) is composed of 85 units of terephthalic acid.
-99.5 mol%, preferably 90-99.5 mol%, and the adipic acid component unit is present in an amount of 0.5-15 mol%, preferably 0.5-10 mol%. Is desirable.

In the copolymerized polyester (3), in addition to the above-mentioned terephthalic acid and adipic acid as the dicarboxylic acid component, an amount of the copolymerized polyester (3) in a range not impairing the obtained polyester (3), for example, 1 mol% or less. Other dicarboxylic acids can be used.

Examples of such dicarboxylic acids include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester (3), in addition to ethylene glycol as the dihydroxy compound, a range that does not impair the properties of the obtained copolymerized polyester (3), for example, 1 mol%
Other dihydroxy compounds can be used in the following amounts.

As such a dihydroxy compound,
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
Benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone, etc. 15 dihydroxy compounds.

Copolyester (4) The copolymer polyester (4) is composed of a dicarboxylic acid constituent unit containing a terephthalic acid component unit and a dihydroxy compound constituent unit containing an ethylene glycol component unit and a diethylene glycol component unit.

The dihydroxy compound constituting unit constituting the copolymerized polyester (4) has an ethylene glycol component unit in an amount of 93 to 98 mol%, preferably 95 to 98 mol%, and a diethylene glycol component unit of 2 to 98 mol%.
Desirably it is present in an amount of 7 mol%, preferably 2 to 5 mol%.

In the copolymerized polyester (4), in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, other dicarboxylic acids may be used in an amount not to impair the properties of the obtained copolymerized polyester (4), for example, 1 mol% or less. Acids can also be used.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester (4), in addition to the above-mentioned ethylene glycol and diethylene glycol as the dihydroxy compound, other dihydroxy compounds may be used in an amount not impairing the properties of the obtained copolymerized polyester (4), for example, 1 mol% or less. Compounds can also be used.

Such dihydroxy compounds include:
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
Benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone, etc. 15 dihydroxy compounds are used.

The above-mentioned copolymerized polyester (1) to
The molecular weight of (4) is not particularly limited as long as various molded articles such as bottles can be produced from the obtained polyester composition, but usually, the intrinsic viscosity [η] of the copolymerized polyester in an o-chlorophenol solvent. Is in the range of 0.5 to 1.5 dl / g, preferably 0.6 to 1.5 dl / g.
It is desirable to be within the range of 1.2 dl / g.

The above-described polyethylene terephthalate, polyethylene naphthalate, and copolymerized polyesters (1) to (4) can be produced by a conventionally known production method.

Talcs Talcs are inorganic compounds represented by a composition formula of 2MgO.4SiO2.H2O. Chemical composition is SiO2, Mg
O, CaO, Al2O3, Fe2O3, etc.
2. MgO is the main component. The composition ratio of SiO2 is 55
７０70% by weight, preferably 60-65% by weight. The composition ratio of MgO is 25 to 40% by weight, preferably 30 to 35% by weight. SiO2 and M
The total ratio of gO is preferably 85% by weight or more, more preferably 90% by weight or more. CaO, Al2O
3. The composition ratio of Fe2O3 is usually 10% by weight or less, preferably 5% by weight or less, and more preferably 3% by weight or less. Talcs are available in China, the United States, Russia, Brazil, India, Finland,
It is produced in countries around the world, including France, Australia and Korea. Talc from China, Korea, Australia and India is preferred.

The particle size of talc is usually 75% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more, with a sieve of 45 μm. The average particle size is preferably talc of 20 μm or less, and more preferably 10 μm or less.

The bottle made of the polyester composition according to the present invention is formed from a polyester composition comprising the above-mentioned polyester and talc. This polyester composition comprises polyester 99.9 to 99.9999.
9 wt% and talc 0.1 ppm to 0.1 wt%, preferably 99.99 to 99.99999 polyester
And talc 0.1 ppm to 0.01% by weight, more preferably polyester 99.999 to 99.99999.
% By weight and 0.1 ppm to 0.001% by weight of talc.

As the method for preparing the polyester composition, any known method can be employed. For example, polyethylene terephthalate (A) and talc (B) are directly mixed by a mixer such as a tumbler blender or a Henschel mixer. A method of melt kneading, a method of melt kneading polyethylene terephthalate (A) and talc (B) to prepare a masterbatch, and appropriately blending the masterbatch with polyethylene terephthalate (A) can be adopted.

The polyester composition as described above may be mixed with various components such as a crosslinking agent, a heat stabilizer, a weather stabilizer, an antistatic agent, a lubricant, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye. An agent may be contained within a range that does not impair the purpose of the present invention.

The crystallization rate of such a polyester composition measured by a t1 / 2 heating method (140 ° C.) using a differential scanning calorimeter is usually 200 seconds or less, preferably 150 seconds or less, more preferably 130 seconds or less. It is as follows. The crystallization rate of a conventionally known polyester, for example, polyethylene terephthalate is about 200 to 300 seconds, and the crystallization rate of polyethylene naphthalate is about 500 to 1000 seconds. The method for measuring the crystallization rate will be described later.

The above polyester composition has excellent properties inherent to polyester and has a high crystallization rate. Such a polyester composition can produce a molded article having excellent mechanical properties such as rigidity and heat-resistant rigidity.

The polyester bottle of the present invention is suitably used particularly for non-carbonated beverages such as natural water and drinking tea. As the bottle made of the polyester composition, a free-standing bottle is mentioned. FIG. 1 shows an example of a free-standing bottle. In the figure, 2 is the mouth and neck, 3 is the upper shoulder, 4 is the torso, 5 is the bottom, and 6 is the collar.

In the bottle made of the polyester composition according to the present invention, the rate of deformation, expansion and contraction of the bottle is small even when the bottle is filled with a heated beverage or the like. Therefore, even if a beverage or the like that has been heat-sterilized is filled into a bottle at a high temperature, the deformation of the bottle body can be kept small. Further, the bottle made of the polyester composition according to the present invention is excellent in transparency. Furthermore, since the entire bottle is formed from a single resin, it can be melted as it is, molded again into a bottle or the like, and reused.

Next, the method for producing the polyester composition bottle according to the present invention will be described in detail. The bottle 1 made of the polyester composition according to the present invention has, for example, a mouth and neck part 2, an upper shoulder part 3, a trunk part 4, and a bottom part 5, as shown in FIG.

To manufacture such a bottle, first,
A preform is produced from the polyester composition as described above, and the preform can be produced by a conventionally known method, for example, injection molding, extrusion molding and the like. The heating temperature of the polyester composition for forming a preform is usually preferably from 90 to 110 ° C.

In the present invention, such a preform is stretch blow-molded in a mold so that the crystallinity at the center of the bottle body is 25 to 60%, preferably 25 to 50%. Manufactures bottles made of polyester composition.

The stretch ratio at the time of stretch blow molding is desirably 6 to 15 times, preferably 7 to 12 times as the area stretch ratio. In this specification, the area stretching ratio (hereinafter, may be simply referred to as “stretching ratio”) is a stretching ratio defined as a product of a longitudinal stretching ratio and a transverse stretching ratio.

The temperature of the blowing fluid at the time of stretch blow molding is desirably 10 to 400 ° C., preferably 20 to 300 ° C. Examples of the blowing fluid include air, nitrogen, steam, and water, and among them, air is preferably used.

In the present invention, prior to stretching blow, the mouth and neck of the preform is heated and crystallized to make the crystallinity of the mouth and neck of the preform 25 to 60%, preferably 25 to 50%. . In order to heat and crystallize the preform neck and neck, the preform neck and neck are usually 120 to 20 mm.
Heat to 0 ° C, preferably 150-200 ° C, more preferably 170-190 ° C.

It is preferable to carry out stretch blow molding in which the area stretch ratio from the preform to the bottle is increased, since a bottle having particularly excellent heat resistance can be obtained. In addition,
In a conventional stretched bottle, the area stretch ratio from the preform to the bottle is usually about 6 to 10 times.

In the present invention, it is preferable to heat set the obtained stretch blow molded bottle after the stretch blow molding as described above. When the stretch blow-molded bottle is heat-set in this manner, the density of the body of the bottle can be improved.

In the heat setting, the obtained bottle was
This is performed by holding at a mold temperature of 0 to 200 ° C, preferably 110 to 170 ° C for 1 second or more, preferably 3 seconds or more.

By heat setting the bottle in this way, it is possible to obtain a bottle in which the density of the bottle body is improved and the body strength is increased. For example, the density of the body of a stretch blow-molded bottle made of a polyester composition before heat setting is 1.355 to 1.370 g / cm3.
After heat setting, although it depends on the heat setting temperature, it is usually 1.370 to 1.410 g / cm 3.
Degree, preferably 1.375 to 1.390 g /
cm3.

In the present invention, it is preferred that the bottle subjected to the stretch blow molding as described above and further subjected to heat setting if necessary be taken out after cooling. As a cooling method, it is preferable to use an “internal cooling method” in which, for example, a cooled gas is blown into the inside of the bottle to cool from the inside to the outside (outer surface) of the bottle. When the bottle is cooled from the inside (the hollow portion of the bottle) in this way, the bottle can be removed from the mold without causing deformation, shrinkage, and the like of the bottle.

The cooling temperature inside the bottle is usually-
It is desirable that the temperature is 100 ° C to + 50 ° C, preferably -75 ° C to + 40 ° C. The cooling rate of the bottle depends on the thickness and material of the bottle, but is usually about 300 to 10 ° C / min. desirable. When the bottle is cooled, it is preferable that the outer surface temperature of the bottle be 100 ° C. or lower. Examples of the cooling gas include air and nitrogen, and air is preferably used.

In the method for producing a bottle made of a polyester composition according to the present invention, the heat resistance of the obtained bottle is improved by forming a stretched bottle by a specific method using a specific polyester composition. The bottle deformation after filling the heated beverage can be reduced, and the bottle can maintain its independence. In addition, the polyester composition used in the present invention has a high crystallization rate, so that the bottle molding cycle can be shortened.

[0074]

The bottle made of the polyester composition according to the present invention is excellent in heat resistance and transparency. Further, it is easy to melt a used bottle and reuse it again for a bottle or the like.

The method for producing a bottle made of a polyester composition according to the present invention can produce a bottle having excellent heat resistance and transparency. Also, the bottle molding cycle can be shortened.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[Crystallization rate] The crystallization rate was measured using a differential scanning calorimeter (DSC) manufactured by PerkinElmer. 10 mg of the sample was weighed into a sample pan, heated from room temperature to 290 ° C. at a rate of 320 ° C./min, and held for 10 minutes. Thereafter, it is rapidly cooled to 30 ° C. and further cooled to 140 ° C.
The temperature was raised at a rate of ° C./min and maintained at this temperature. At this time, the relationship between the amount of heat generated by crystallization of the sample and time was measured, and the time (second) required for the amount of heat generated to reach 1/2 of the total amount of heat generation was defined as the crystallization rate.

[Evaluation of the heat resistance of the bottle] The evaluation of the heat resistance of the bottle was determined by filling the bottle with the contents at 90 ° C and comparing the deformation of the bottle with that before filling. Good: The bottle body has small deformation. Inferior… The bottle body is greatly deformed.

[Measurement of Crystallinity] The crystallinity is an average value of the crystallinity measured by preparing three samples as described below.

A sample having a size of 10 × 10 mm was cut out from the sample bottle, and the cut sample was attached so as to have a thickness of 1 mm to obtain a sample for measurement.

[0081] Measurement of Crystallinity The angle between the diffracted beam and the transmitted beam is constant at 2θ, and the diffraction intensity of the sample is measured in the range of 2θ = 5-35 °. Subtract the background diffraction intensity from the diffraction intensity measured in step 2. The diffraction intensity obtained by subtraction is defined as Ic. Let Ia be the diffraction intensity of the same resin that has been measured and which is 100% amorphous. The crystallinity (Xcr) of the sample is calculated by the following equation. FIG. 4 shows an example of the X-ray diffraction intensity curve.

[0082]

[Formula 1]

[0083]

Example 1 Polyethylene terephthalate [J125 manufactured by Mitsui Petrochemical Co., Ltd.] (hereinafter referred to as “PET-1”) 9
A polyester composition consisting of 9.9999% by weight and 1 ppm of talc (HK-9 manufactured by Hayashi Kasei Co., Ltd. (hereinafter referred to as “HK-9”)) was M-10 manufactured by Meiki Seisakusho Co., Ltd.
A preform was obtained by molding with a 0A injection molding machine. The molding temperature at this time was 290 ° C.

Next, the neck portion of the preform was heated and crystallized at 180 ° C., and then heated by an infrared heater attached to the molding machine so that the surface temperature of the central portion of the preform body became 90 to 100 ° C. LB-01 manufactured by CORPOPLAST
A heat-resistant bottle as shown in FIG. 1 was formed by stretch blowing with a forming machine. During stretching, heat the blow mold to 150 ° C,
The bottle was brought into contact with the mold for 5 seconds to perform a heat setting treatment, and then the bottle was cooled to 100 ° C. or lower and then taken out of the mold. The molding cycle at this time was 60 seconds, and the plane stretching ratio was 7 times.

The bottle thus created is
The heat resistance properties defined in the specification were evaluated. Table 1 shows the results
Shown in

[0086]

Example 2 In Example 1, PET-1 99.99 was used.
A bottle was prepared in the same manner as in Example 1 except that a polyester composition consisting of 95% by weight and HK-95 ppm was used.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0088]

Example 3 PET-1 99.99 in Example 1
A bottle was prepared in the same manner as in Example 1 except that a polyester composition comprising 8% by weight and 20 ppm by weight of HK-9 was used.

This bottle was evaluated for heat resistance as defined in the specification in the same manner as in Example 1. Table 1 shows the results.

[0090]

Example 4 A bottle was prepared in the same manner as in Example 1 except that the molding cycle was changed to 90 seconds.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0092]

Example 5 In Example 1, instead of PET-1, polyethylene terephthalate [J13 manufactured by Mitsui Petrochemical Co., Ltd.
5] (hereinafter referred to as “PET-2”), and a bottle was prepared in the same manner as in Example 1.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0094]

Comparative Example 1 A bottle was prepared in the same manner as in Example 1 except that PET-1 was used in place of the polyester composition and the temperature of the blow mold was set at 30 ° C.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0096]

Comparative Example 2 A bottle was prepared in the same manner as in Comparative Example 1 except that PET-2 was used in place of the polyester composition.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0098]

Comparative Example 3 A bottle was prepared in the same manner as in Example 1 except that a polyester composition comprising 99.5% by weight of PET-1 and 0.5% by weight of HK-9 was used.

This bottle was evaluated for heat resistance as defined in the specification as in Example 1. Table 1 shows the results.

[0100]

[Table 1]

[0101]

[Brief description of the drawings]

FIG. 1 is a partially cutaway front view showing an example of a polyester composition bottle according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Bottle 2 ... Mouth and neck part 3 ... Upper shoulder part 4 ... Trunk part 5 ... Bottom part 6 ... Collar part

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08J 5/00 CFD B65D 1/00 A B29K 67:00 B29L 22:00 31:56

Claims (8)

[Claims] 1. Polyester 99.9 to 99.9999
9% by weight and a polyester composition formed from 0.1 ppm to 0.1% by weight of talcs, the degree of crystallinity at the mouth and neck is in the range of 25% to 60%, and the crystallization at the center of the body is achieved. A polyester composition bottle having a degree in the range of 25 to 60%. 2. The crystallization rate of the polyester composition measured by a t1 / 2 heating method (140 ° C.) using a differential scanning calorimeter is 200 seconds or less, and the haze value at the center of the bottle body is 5% or less. The bottle made of the polyester composition according to claim 1, which is: 3. The bottle made of the polyester composition according to claim 1, wherein the bottle is a bottle for non-carbonated beverages. 4. Polyester 99.9 to 99.9999
A preform made of a polyester composition formed from 9% by weight and 0.1 ppm to 0.1% by weight of talc is stretch-blown at an area stretch ratio of 6 to 15 times to crystallize the center of the bottle body. A method for producing a bottle made of a polyester composition, wherein the bottle has a degree of 25 to 60%. 5. The production of the polyester composition bottle according to claim 4, wherein the crystallization rate of the polyester composition measured by a t1 / 2 heating method (140 ° C.) with a differential scanning calorimeter is 200 seconds or less. Method. 6. The method for producing a polyester composition bottle according to claim 4, wherein heat setting is performed after stretch blow molding. 7. The method for producing a polyester biaxially stretched bottle according to claim 7, wherein the neck portion of the preform is heated and crystallized before performing the biaxial stretch blow molding. 8. The method for producing a polyester biaxially stretched bottle according to claim 7, wherein the neck portion of the bottle is heated and crystallized after the biaxially stretch blow molding.