JPH08164555A - Saturated polyester bottle and manufacture thereof - Google Patents

Abstract

PURPOSE: To obtain an autonomous bottle which can be reused by a method wherein a bottle is filled with a carbon dioxide-containing beverage having a specified volume at a specified temperature, changes of a bottle height and a barrel diameter at a specified temperature before and after warm bath test in a sealed state are set to below specified percentages and an inversion angle after the test is set to above a specified angle. CONSTITUTION: When a saturated polyester bottle is filled with a carbon dioxide beverage of 2.5 gas volume at 23 deg.C and tested by warm bath test being dipped in a warm bath of 70 deg.C in a sealed state for an hour, the following condition is to be satisfied. That is, a changing rate of dimension of the bottle filled with the carbon dioxide beverage in the direction of height before and after the warm bath test is 5% or below and a changing rate of dimension in the direction of barrel diameter is 5% or below. An inversion angle of the bottle after the warm bath test is 10 deg. or above. The crystallization degree of this saturated polyester bottle is 25-60% at the neck (mouth, mouth cock) and 25-60% at the barrel center, and preferably 25-60% at the central part of the bottom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a saturated polyester bottle and a method for producing the same, and more particularly, to a self-sustaining bottle which is hardly deformed even when heat sterilized in a state where a saturated polyester bottle is filled with a carbonated beverage. TECHNICAL FIELD The present invention relates to a saturated polyester bottle having a property capable of retaining the property (hereinafter, this property is also referred to as “heat resistance property”) 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 juice, natural water, and various types of drinking tea. Among these plastic materials, saturated polyester such as polyethylene terephthalate is transparent. It is widely used because of its excellent properties, gas barrier property, heat resistance and mechanical strength.

The various liquids as described above to be filled in such a saturated polyester bottle may be filled at a high temperature after being sterilized by heating, and in this case, the heat resistance of the bottle to be used is high. If it is not good, problems such as deformation, contraction, and expansion may occur. Further, in the case of a carbonated beverage, the carbonated beverage may be heat-sterilized after filling the bottle with the carbonated beverage, and the bottle used for such an application may not be deformed under heating. It is required to have a small amount of properties (heat resistant pressure property) capable of maintaining independence after heat sterilization.

Conventionally, a bottle with a base cup in which a base cup is attached to the bottom of a round bottom bottle has been used for such an application. However, in such a bottle with a base cup, the manufacturing cost is high, and since the bottle body is made of the saturated polyester as described above and the base cup is made of polyethylene, which is a different material from this, the entire bottle is melted as it is. However, even if it is remolded into a bottle or the like and is reused, only a poor transparency is obtained, and there is a problem that it is difficult to reuse (recycle).

Based on the above findings, the present inventors have diligently studied to obtain a reusable self-supporting bottle which is entirely composed of the same material, and the conventional bottle is filled with the self-supporting bottle. Pay attention to the fact that when the contents are heat-sterilized, large deformation occurs at the mouth, neck, and bottom of the bottle. It is sufficient to use a polyester bottle that meets certain conditions in, the neck and neck of the bottle,
The present invention has been completed by finding out that a polyester bottle in which the crystallinity in the body portion and the bottom portion is in a specific range may be used.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art, and is excellent in that it is possible to perform a heat sterilization treatment after filling a bottle with a carbonated beverage. An object of the present invention is to provide a saturated polyester bottle having a heat and pressure resistant property and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION The saturated polyester bottle according to the present invention is subjected to a hot bath test in which the bottle is filled with 2.5 gas volume of a carbonated beverage at 23 ° C., and the bottle is tightly sealed and immersed in a 70 ° C. hot bath for 1 hour. It is characterized by satisfying the following conditions.

Condition 1: Dimensional change in the height direction of the beverage filled bottle containing carbon dioxide before and after the hot bath test is 5% or less,
The dimensional change rate in the body diameter direction is 5% or less.

Condition 2: The bottle has a falling angle of 10 degrees or more after the hot bath test. The crystallinity of such a saturated polyester bottle is 25 to 60% at the mouth and neck (also referred to as mouth and mouth plug),
The center of the body is 25-60%, and the center of the bottom is 25-
It is preferably 60%. Moreover, the bottle made of saturated polyester according to the present invention satisfies the same conditions as the bottle made of saturated polyester described above, and the crystallinity of the neck and neck of the bottle is 25% to 60%, and the crystallization of the center of the body is performed. 25 degrees
When the distance from the center part of the bottom part to the peripheral part of the bottom part is R, it is (i) the center part of the bottom part to 7R / 10.
The sum of thermal crystallinity and oriented crystallinity in the range of 25 to 60
%, And (ii) 7R / 10 to 9R / 1 from the center of the bottom
The thermal crystallinity in the range of 0 is 1 to 25%, the oriented crystallinity is 20 to 30%, and the sum of the thermal crystallinity and the oriented crystallinity is 30 to 60%, iii) It is preferable that the crystallinity in the range of 9R / 10 to the peripheral portion (10R / 10) of the bottom from the center of the bottom is 25 to 60%.

The degree of plane orientation (ΔNp) of the saturated polyester bottle as described above is 0.10 at the center of the body.
0.20, and the bottom 7R / 10 to 9R / 10 is 0.
It is preferably from 05 to 0.20.

The saturated polyester bottle according to the present invention may be a self-supporting bottle having legs at the bottom thereof. The method for producing a saturated polyester bottle according to the present invention, by stretch blow molding the preform,
Alternatively, it is characterized in that the crystallinity of the bottom of the bottle is set to 30 to 60% by heat-crystallization of the bottom of the preform and then stretch blow molding. In a preferred embodiment of the present invention, it is preferable that the bottom portion of the preform is heated and crystallized to have a crystallinity (thermal crystallinity) of 30 to 60%, and then stretch blow molding is performed. The crystallized preform is preferably stretch blow molded at an area stretching ratio of 6 to 15 times. Further, after stretch blow molding as described above, the obtained bottle is heat set and then the inside of the bottle is cooled. Is more preferable.

The saturated polyester bottle according to the present invention has a characteristic (heat resistant pressure characteristic) such that it is hardly deformed even if it is sterilized by heating in a state where the bottle is filled with a beverage containing carbon dioxide gas (heat resistance characteristic). are doing.

According to the method for producing a saturated polyester bottle as described above, a bottle having such a heat and pressure resistant property can be obtained.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The saturated polyester bottle and the method for producing the same according to the present invention will be specifically described below. First, the saturated polyester resin used in the bottle of the present invention will be described. Saturated Polyester Bottle The saturated polyester bottle according to the present invention has 2 bottles.
The following conditions were satisfied when a hot bath test was conducted in which a 2.5 gas volume of a carbonated beverage was filled at 3 ° C. and the container was tightly sealed and immersed in a hot bath at 70 ° C. for 1 hour.

Condition 1: the dimensional change in the height direction of the carbonated gas filled bottle before and after the hot bath test is 5% or less,
The dimensional change rate in the body diameter direction is 5% or less.

Condition 2: The bottle has a tipping angle of 10 degrees or more after the hot bath test. In a preferred embodiment of the present invention, the dimensional change rate in the height direction of the saturated polyester bottle filled with the carbonated gas-filled beverage before and after the hot bath test of the condition 1 is:
It is preferably 5% or less, and more preferably the dimensional change rate in the body radial direction is 5% or less. The falling angle of the bottle after the hot bath test of condition 2 is preferably 10 degrees or more. The method of measuring the falling angle of the bottle will be described later.

The dimensional change rate of the bottle is determined by the following equations both in the height direction and the body diameter direction.

[0018]

[Equation 1]

The crystallinity of the saturated polyester bottle of the present invention is determined by, for example, X-ray diffraction, and the mouth has a diameter of 25 to 25.
60%, preferably 15-50%, with 2 in the center of the body
5-60%, preferably 25-50%, and the center of the bottom is 25-60%, preferably 25-50%.

The bottle made of saturated polyester according to the present invention is
The same conditions as those of the saturated polyester bottle are satisfied, and the crystallinity of the mouth and neck is 25% to 60%,
When the crystallinity of the center of the body is 25 to 60% and the distance from the center of the bottom to the peripheral edge of the bottom is R, then (i) the center of the bottom to the temperature of 7R / 10 The sum of crystallinity and oriented crystallinity is 25 to 60%, preferably 25.
-50%, (ii) 7R / 10-9 from the center of the bottom
The thermal crystallinity in the range of R / 10 is 1 to 25%, the oriented crystallinity is 20 to 30%, and the sum of the thermal crystallinity and the oriented crystallinity is 25 to 60%, preferably 25 to 50. %, And (i
ii) 9R / 10 from the center of the bottom to the periphery of the bottom (10
The crystallinity in the range of R / 10) is 25 to 60%, preferably 25 to 50%.

The degree of surface orientation (ΔNp) of the bottle is 0.10 to 0.20 at the center of the body and 7R / 10 to 9R / at the bottom.
10 is preferably 0.05 to 0.20. The plane orientation degree (ΔNp) of the bottle is obtained by the method described later.

As the saturated polyester bottle,
Examples include a self-supporting bottle having legs on its bottom and a five-legged bottle. Next, the saturated polyester resin used in the saturated polyester bottle according to the present invention will be described in detail. Examples of such saturated polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, and the following copolymerized polyester resins (1) to (7).

Hereinafter, each resin will be described more specifically. Polyethylene terephthalate resin The polyethylene terephthalate resin used in the saturated polyester bottle according to the present invention is produced from terephthalic acid and ethylene glycol as raw materials.
The polyethylene terephthalate resin may be copolymerized with 20 mol% or less of another dicarboxylic acid and / or another dihydroxy compound.

Specific examples of the dicarboxylic acid used in the copolymerization other than terephthalic acid include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; adipic acid and sebacine. Examples thereof include aliphatic dicarboxylic acids such as acids, azelaic acid and decanedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

As dihydroxy compounds used for copolymerization other than ethylene glycol, specifically, 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,
Examples thereof include aromatic diols such as 2-bis (4-β-hydroxyethoxyphenyl) propane.

Such a polyethylene terephthalate resin is a substantially linear polyester by forming ethylene ester alone or by randomly arranging the ethylene terephthalate component units and the dioxyethylene terephthalate component units to form an ester bond. Is forming. The fact that the polyethylene terephthalate resin is substantially linear is confirmed by the fact that the polyethylene terephthalate resin is dissolved in o-chlorophenol.

Such polyethylene terephthalate resin has an intrinsic viscosity [η] (25 in o-chlorophenol).
It is desirable that the value (measured at 0 ° C.) is usually 0.6 to 1.5 dl / g, preferably 0.7 to 1.2 dl / g. 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 resin The polyethylene naphthalate resin used in the saturated polyester bottle of the present invention contains 60 mol% of ethylene-2,6-naphthalate units derived from 2,6-naphthalenedicarboxylic acid and ethylene glycol. Or more, preferably 80 mol% or more, more preferably 90 mol% or more.
-A constitutional unit other than naphthalate may be contained in an amount of less than 40 mol%.

As constitutional units other than ethylene-2,6-naphthalate, terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 4 Aromatic dicarboxylic acids such as 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid and dibromoterephthalic acid; adipic acid, azelaic acid, sebacic acid, decane Aliphatic dicarboxylic acids such as dicarboxylic acids; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, and hexahydroterephthalic acid; glycolic acid, p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid, etc. Of hydroxycarboxylic acid, propylene glycol, trimethylene glycol , Diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, p-xylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxy sulfone, 1,4-
Examples include constitutional units derived from bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenol) propane, polyalkylene glycol, p-phenylenebis (dimethylsiloxane), glycerin and the like. it can.

The polyethylene naphthalate resin used in the present invention contains a small amount of structural units derived from a polyfunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane and pentaerythritol, for example, 2 mol% or less. May be included in the amount of.

Further, the polyethylene naphthalate resin used in the present invention contains a small amount of a structural unit derived from a monofunctional compound such as benzoylbenzoic acid, diphenylsulfone monocarboxylic acid, stearic acid, methoxypolyethylene glycol and phenoxypolyethylene glycol, for example, 2 mol. It may be contained in an amount of not more than%.

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

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

The intrinsic viscosity [η] of the polyethylene naphthalate resin is measured by the following method. That is, polyethylene naphthalate resin was dissolved in o-chlorophenol at a concentration of 1 g / 100 ml, the solution viscosity was measured using an Ubbelohde-type capillary viscometer at 25 ° C., and then o-chlorophenol was gradually added, The solution viscosity on the low concentration side is measured, and the limiting viscosity ([η]) is obtained by searching for the 0% concentration.

The temperature rising crystallization temperature (Tc) of the polyethylene naphthalate resin when heated by a differential scanning calorimeter (DSC) at a rate of 10 ° C./min is usually 150 ° C. or higher, preferably. 160-230 ° C, more preferably 1
It is preferably in the range of 70 to 220 ° C.

The temperature rising crystallization temperature (Tc) of the polyethylene naphthalate resin is measured by the following method.
That is, using a Perkin Elmer DSC-2 type differential calorimeter, at about 140 ° C. under a pressure of about 5 mmHg, about 5 mm.
A thin piece of about 10 mg of a sample collected from the central portion of a polyethylene naphthalate resin chip dried for more than an hour is enclosed in a liquid aluminum pan under a nitrogen atmosphere for measurement. The measurement conditions are as follows: the peak temperature of the exothermic peak detected when the temperature is raised rapidly from room temperature, melted and held at 290 ° C. for 10 minutes, rapidly cooled to room temperature, and then raised at a temperature rising rate of 10 ° C./min. Ask for.

Copolymerized Polyester Resin (1) The copolymerized polyester resin (1) used in the saturated polyester bottle of the present invention comprises a dicarboxylic acid constituent unit containing a terephthalic acid component unit and an isophthalic acid component unit, and an ethylene glycol component. And a dihydroxy compound constitutional unit containing a unit.

The terephthalic acid component unit in the dicarboxylic acid constitutional unit constituting the copolyester resin (1) is 85 to 99.5 mol%, preferably 90 to 99.5 mol%.
And the isophthalic acid component unit is present in an amount of 0.5 to 15 mol%, preferably 0.5 to 10 mol%.

In the copolyester resin (1) according to the present invention, in addition to the above-mentioned terephthalic acid and isophthalic acid as the dicarboxylic acid component, a range not impairing the characteristics of the copolyester resin (1) obtained, for example, 1 Other dicarboxylic acids can also be used in amounts up to mol%.

Examples of such dicarboxylic acid include phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. Further, in the copolymerized polyester resin (1) according to the present invention, in addition to ethylene glycol as a dihydroxy compound as described above, a range not impairing the characteristics of the obtained copolymerized polyester resin (1), for example, an amount of 1 mol% or less. It is also possible to use other dihydroxy compounds.

Examples of 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 Examples thereof include dihydroxy compounds having 3 to 15 carbon atoms such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone.

Copolymerized Polyester Resin (2) The copolymerized polyester resin (2) used in the saturated polyester bottle of the present invention is a dicarboxylic acid constituent unit containing a terephthalic acid component unit and a 2,6-naphthalenedicarboxylic acid component unit. And a dihydroxy compound constituent unit containing an ethylene glycol component unit.

The dicarboxylic acid constitutional unit constituting this copolymerized polyester resin (2) contains a terephthalic acid component unit in an amount of 80 to 99.5 mol%, preferably 90 to 99.5 mol%.
And the 2,6-naphthalenedicarboxylic acid component unit is present in an amount of 0.5 to 20 mol%, preferably 0.5 to 10 mol%.

In the copolyester resin (2) according to the present invention, in addition to the above-mentioned terephthalic acid and 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component,
Other dicarboxylic acids may be used in a range that does not impair the properties of the resulting copolyester resin (2), for example, 1 mol% or less.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid and 2-methylterephthalic acid. In the copolymerized polyester resin (2) according to the present invention, other than ethylene glycol as described above as the dihydroxy compound, a range not impairing the characteristics of the obtained copolymerized polyester resin (2), for example, 1
Other dihydroxy compounds can also be used in amounts up to mol%.

Examples of 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 Examples thereof include dihydroxy compounds having 3 to 15 carbon atoms such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone.

Copolymerized Polyester Resin (3) The copolymerized polyester resin (3) used in the saturated polyester bottle of the present invention comprises a dicarboxylic acid constituent unit containing a terephthalic acid component unit and an adipic acid component unit, and an ethylene glycol component. And a dihydroxy compound constitutional unit containing a unit.

The terephthalic acid component unit in the dicarboxylic acid constitutional unit constituting the copolyester resin (3) is 85 to 99.5 mol%, preferably 90 to 99.5 mol%.
And the adipic acid component unit is preferably present in an amount of 0.5 to 15 mol%, preferably 0.5 to 10 mol%.

In the copolyester resin (3) according to the present invention, in addition to the above-mentioned terephthalic acid and adipic acid as the dicarboxylic acid component, the range which does not impair the properties of the copolyester resin (3) obtained, for example, 1 Other dicarboxylic acids can also be used in amounts up to mol%.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid and 2,6-naphthalenedicarboxylic acid. Further, in the copolyester resin (3) according to the present invention,
Besides ethylene glycol as a dihydroxy compound,
Other dihydroxy compounds may be used in a range that does not impair the properties of the resulting copolyester resin (3), 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 Examples thereof include dihydroxy compounds having 3 to 15 carbon atoms such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone.

Copolymerized Polyester Resin (4) The copolymerized polyester resin (4) used in the saturated polyester bottle of the present invention comprises a dicarboxylic acid constituent unit containing a terephthalic acid constituent unit, an ethylene glycol constituent unit and a diethylene glycol constituent unit. And a dihydroxy compound structural unit containing

The dihydroxy compound constitutional unit which constitutes the copolymerized polyester resin (4) has an ethylene glycol component unit of 93 to 98 mol%, preferably 95 to 98.
Desirably, the diethylene glycol component units are present in an amount of 2 to 7 mol%, preferably 2 to 5 mol%.

In the copolyester resin (4) according to the present invention, in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, a range not impairing the properties of the copolyester resin (4) obtained, for example, 1 mol% or less. Other dicarboxylic acids can also be used in an amount of

Examples of such dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. Further, in the copolyester resin (4) according to the present invention,
Other than ethylene glycol and diethylene glycol as described above, other dihydroxy compounds may be used as the dihydroxy compound in a range that does not impair the characteristics of the resulting copolyester resin (4), for example, 1 mol% or less.

Examples of 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 Dihydroxy compounds having 3 to 15 carbon atoms such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone are used.

Copolymerized Polyester Resin (5) The copolymerized polyester resin (5) used in the saturated polyester bottle according to the present invention comprises a dicarboxylic acid constituent unit containing a terephthalic acid constituent unit, an ethylene glycol constituent unit and neopentyl glycol. And a dihydroxy compound constitutional unit containing a constituent unit.

The dihydroxy compound constitutional unit constituting the copolyester resin (5) has an ethylene glycol component unit of 85 to 99.5 mol%, preferably 90 to
The amount of the neopentyl glycol component unit is 0.5 to 15 mol%, preferably 0.5 to 10 in an amount of 99.5 mol%.
It is preferably present in an amount of mol%.

In the copolyester resin (5) according to the present invention, other than terephthalic acid as the dicarboxylic acid component, a range not impairing the properties of the copolyester resin (5) obtained, for example, 1 mol% or less. Other dicarboxylic acids can also be used in an amount of

Examples of such dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. Further, in the copolyester resin (5) according to the present invention,
In addition to the above ethylene glycol and neopentyl glycol as the dihydroxy compound, a range that does not impair the properties of the resulting copolyester resin (5),
For example, other dihydroxy compounds can be used in an amount of 1 mol% or less.

As such a dihydroxy compound,
1,3-propanediol, 1,4-butanediol, cyclohexanediol, cyclohexanedimethanol,
1,3-bis (2-hydroxyethoxy) benzene, 1,4
-Dihydroxy compounds having 3 to 15 carbon atoms such as bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone. Can be mentioned.

Copolymerized Polyester Resin (6) The copolymerized polyester resin (6) used in the saturated polyester bottle of the present invention comprises a dicarboxylic acid constituent unit containing a terephthalic acid constituent unit, an ethylene glycol constituent unit and cyclohexanedimethanol. And a dihydroxy compound constitutional unit containing a constituent unit.

The dihydroxy compound constitutional unit constituting the copolyester resin (6) has an ethylene glycol component unit of 85 to 99.5 mol%, preferably 90 to
In an amount of 99.5 mol% and the cyclohexanedimethanol component unit is 0.5 to 15 mol%, preferably 0.5 to
It is preferably present in an amount of 10 mol%.

In the copolyester resin (6) according to the present invention, in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, a range of not deteriorating the characteristics of the copolyester resin (6) obtained, for example, 1 mol% or less. It is also possible to use other dicarboxylic acids in amounts.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid and 2,6-naphthalenedicarboxylic acid. Further, in the copolyester resin (6) according to the present invention,
As the dihydroxy compound, other than the above ethylene glycol and cyclohexanedimethanol, other dihydroxy compounds can be used in a range that does not impair the properties of the resulting copolyester resin (6), for example, 1 mol% or less.

As such a dihydroxy compound,
1,3-propanediol, 1,4-butanediol, cyclohexanediol, cyclohexanedimethanol,
1,3-bis (2-hydroxyethoxy) benzene, 1,4
-Dihydroxy compounds having 3 to 15 carbon atoms such as bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone Used.

Copolymerized Polyester Resin (7) The copolymerized polyester resin (7) used in the saturated polyester bottle of the present invention has a dicarboxylic acid constitutional unit, a dihydroxy compound constitutional unit, and at least three hydroxy groups. And a polyfunctional hydroxy compound constituent unit.

The dicarboxylic acid constitutional unit constituting the copolyester resin (7) contains the isophthalic acid component unit in an amount of 20 to 100 mol%, preferably 50 to 98 mol%, and the terephthalic acid component unit is 0. It is desirable to be present in an amount of -80 mol%, preferably 0.5-50 mol%.

The dihydroxy compound constitutional unit contains the dihydroxyethoxyresole component unit in an amount of 5 to 90 mol%, preferably 10 to 85 mol%, and the ethylene glycol component unit in an amount of 10 to 95 mol%, preferably 15 mol%. It is desirable to be present in an amount of ˜90 mol%.

This copolyester resin (7) contains
There are polyfunctional hydroxy compound building blocks having at least 3 hydroxy groups. The polyfunctional hydroxy compound constituent unit is 0.05 to 1.0 part by mol, preferably 0.1 to 100 parts by mol of the dicarboxylic acid component unit.
It is preferably present in an amount of 0.5 part by mole.

Such a polyfunctional hydroxy compound constitutional unit is derived from a compound such as trimethylolmethane, trimethylolethane or trimethylolpropane, of which trimethylolpropane is preferred.

In the copolyester resin (7) according to the present invention, other than isophthalic acid and terephthalic acid as the dicarboxylic acid component, the range which does not impair the characteristics of the copolyester resin (7) obtained, for example, 1 Other dicarboxylic acids can also be used in amounts up to mol%.

Examples of such dicarboxylic acids include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. Further, in the copolyester resin (7) according to the present invention,
Other than the above-mentioned dihydroxyethoxy resole and ethylene glycol as the dihydroxy compound, other dihydroxy compounds can be used in a range that does not impair the properties of the resulting copolyester resin (7), 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 Dihydroxy compounds having 3 to 15 carbon atoms such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone are used.

The molecular weight of the above-mentioned copolymerized polyester resins (1) to (7) is not particularly limited as long as it can produce various molded products such as bottles from the resulting saturated polyester resin composition. Usually o
-The intrinsic viscosity [η] of the copolyester resin in the chlorophenol solvent is 0.5 dl / g to 1.5 dl / g
Above, it is desirable to be within the range of preferably 0.6 to 1.2 dl / g.

Each resin constituting the above-mentioned saturated polyester bottle can be manufactured by a conventionally known manufacturing method. Further, in each of the resins as described above, various compounding agents 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, It can be added within a range that does not impair the object of the present invention. Production of Saturated Polyester Bottle Next, the method for producing a saturated polyester bottle according to the present invention will be specifically described.

The saturated polyester bottle obtained by the present invention comprises, for example, as shown in FIG. 1, a spout part 200, an upper shoulder part 300, a body part 400 and a bottom part 500. In order to manufacture such a bottle, first, a preform is manufactured from the above resin, and the preform can be manufactured by a conventionally known method such as injection molding or extrusion molding. The heating temperature of the saturated polyester resin for forming the preform is preferably 90 to 110 ° C. when the saturated polyester resin is a polyethylene terephthalate resin, for example.

In the present invention, the bottle bottom is obtained by stretch blow molding such a preform, or by heat crystallization of the bottom portion (particularly preferably only the bottom portion) of the preform and then stretch blow molding. The saturated polyester bottle as described above is manufactured with the crystallinity of 30 to 60%.

In the present invention, the sum of the crystallinity (thermal crystallinity) by heat crystallization of the bottom of the bottle and the crystallinity (oriented crystallinity) by stretch blow molding of the bottom as described above is obtained. It is preferable to set it to 25 to 60%, preferably 25 to 50%.

For example, in the case of a preform made of polyethylene terephthalate resin, the bottom of the preform is usually heated to 50 to 200 ° C., preferably 170 to 190 ° C., and the crystallinity (thermal crystallinity) of the bottom is 25. To 60%, preferably 25 to 50%, and then
By stretching blow-molding the preform crystallized at the bottom in an area stretching ratio of 6 to 15 times, preferably 7 to 12 times in the mold, the crystallinity of the bottom of the bottle is 25 to 60. %, Preferably 25 to 50%. In this way, stretch blow molding with a high area draw ratio from the preform to the bottle is preferable because a bottle excellent in heat and pressure 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 specification, the area stretching ratio (also simply referred to as “stretching ratio”) is a value defined as the product of the longitudinal stretching ratio and the transverse stretching ratio.

Further, for example, the crystallinity (thermal crystallinity + orientation crystallinity) at the bottom of the bottle can be obtained by performing only stretch blow molding of the preform without performing heat crystallization of the preform as described above. ) Is 30-
It may be 60%. Also in this case, stretch blow molding can be performed at the above-described area stretch ratio.

In a preferred embodiment of the present invention, it is preferable that the bottom portion of the preform is crystallized by heating to a crystallinity (thermal crystallinity) of 30 to 60% and then stretch blow molding. It is preferable that the preform having the bottom crystallized is stretch blow molded at an area stretching ratio of 6 to 15 times. The temperature of the blowing fluid during stretch blow molding as described above is preferably 10 to 400 ° C, and more preferably 20 to 300 ° C. Examples of the blowing fluid include air, nitrogen, steam, water and the like, among which air is preferable. In the present invention, it is preferable that the stretch-blow molding bottle thus obtained is heat-set after the stretch-blow molding. By heat setting the stretch blow-molded bottle in this manner, the density of the body portion of the bottle can be improved.

The heat setting conditions vary greatly depending on the type of polyester resin used, but the case of polyethylene terephthalate resin will be described below. That is, a polyethylene terephthalate resin (PET) bottle obtained by stretch blow molding in a mold as described above is used at a mold temperature of 100 to 200 ° C., preferably 110
Heat setting is performed by holding at 170 ° C for 1 second or longer, preferably 3 seconds or longer.

By applying the heat setting treatment to 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 portion of the polyethylene terephthalate resin stretch blow molded bottle before heat setting is 1.355 to 1.37.
Although it is about 0 g / cm ^3, it is usually 1.370 to 1.410 after heat setting, though it depends on the heat setting temperature.
g / cm ³ or so, preferably 1.375 to 1.3
It is preferably about 90 g / cm ³ .

In the present invention, the bottle which has been subjected to the stretch blow molding as described above and, if necessary, heat set, is cooled after being taken out from the mold so as not to be deformed or shrunk. It is preferable to take it out. As a cooling method, for example, an “internal cooling method” in which a cooled gas is blown into the bottle to cool it from the inside to the outside (outer surface) of the bottle is preferable. By cooling the bottle from the inside (hollow portion of the bottle) in this way, the bottle can be taken out from the mold without causing deformation, shrinkage, or the like of the bottle. The cooling temperature inside the bottle is usually −100 ° C. to + 50 ° C., preferably −75.
C. to + 40.degree. C. is desirable, and the bottle cooling rate is usually 300 to 10 though it depends on the thickness of the bottle, material, etc.
It is desirable that the temperature is about ° C / minute. When cooling such a bottle, the surface temperature on the outside of the bottle is 100 ° C.
The following is preferable. Examples of the cooling gas include air, nitrogen, water and the like, and air is preferably used.

In the method for producing a saturated polyester bottle according to the present invention, the heat and pressure resistance of the bottle is improved to reduce the deformation of the bottle during the heat sterilization process after filling the beverage containing carbon dioxide gas. Independence can be maintained.

[0087]

EFFECTS OF THE INVENTION The saturated polyester bottle according to the present invention has a characteristic (heat resistant pressure characteristic) such that it is hardly deformed even if it is heated and sterilized in a state where the bottle is filled with a carbonated gas-containing beverage (heat resistant pressure characteristic). Have

According to the method for producing a saturated polyester bottle as described above, a bottle having such a heat and pressure resistant property can be obtained. In a preferred embodiment of the present invention, when forming a bottle by stretch blow molding a saturated polyester preform, the draw ratio from the preform to the bottle is made larger than before, and the bottle is heat set. Since the bottle is taken out from the mold after being cooled and the inside of the bottle is cooled, the portion of the bottle that is easily deformed is reduced, and a bottle having excellent heat and pressure resistance is obtained.

[0089]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Evaluation of heat-resistant and pressure-resistant properties of bottles The heat-resistant and pressure-resistant properties of bottles were evaluated by filling the bottles with 2.5 gas volume (GV) contents, immersing them in a hot bath at 70 ° C. for 1 hour, and then removing the bottles. And the self-supporting property was determined by comparison with that before immersion in a warm bath. A bottle was evaluated as having excellent heat and pressure resistance when the deformability of the bottle was small and the bottle retained its self-supporting property.

[Tipping Angle] The tipping angle of the bottle is
It was determined as follows using the dedicated measuring jig shown in FIG.

That is, as shown in FIG. 3A, the measuring bottle 10 is placed on the upper plate 1 of the tipping angle measuring jig 20. Then, by rotating the handle 4 attached to the lower fixing plate 2, the upper plate 1 is gradually inclined as shown in FIG. 3B, and the measuring bottle 10 on the upper plate 1 falls over. At this time, the angle X formed by the lower fixing plate 2 and the upper plate 1 is measured by the angle measuring device (protractor) 3 attached to the end of the upper plate 1 to obtain the falling angle of the bottle. [Measurement of Crystallinity] In the present invention, the crystallinity is the average value of the crystallinity measured for the sample of n = 3 prepared 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 to have a thickness of 1 mm to obtain a measurement sample. Device X-ray diffractometer: RU-300 (manufactured by Rigaku Denki Co., Ltd.) X-ray source: CuKα point focus output: 60 kV, 300 mA Attached device: Wide-angle goniometer, rotating sample stand Optical system: Transmission method (2θscan) Collimator 1 mmφ detection Instrument: Measurement of scintillation counter 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 to 35 °. Subtract the background diffraction intensity from the diffraction intensity measured in. The diffraction intensity curve obtained by subtraction is designated as C. The measured diffraction intensity curve of the same resin in 100% amorphous is designated as A. The crystallinity (X _cr ) of the sample is calculated by the following formula. FIG. 2 shows an example of the X-ray diffraction intensity curve.

[0093]

[Equation 2]

Measurement of degree of plane orientation and secondary refraction Sample from measurement point (length × width = 10 mm × 10 mm)
Then, the refractive index is determined with a polarizing microscope, and the plane orientation degree [ΔNp] and the birefringence [ΔNxy] in the machine direction (MD direction) and the transverse direction (TD direction) of the bottle are calculated as follows. I asked.

The bottle height direction (MD direction) is X.
Let Y be the circumferential direction (TD direction) of the bottle and Z be the thickness direction of the bottle. The relationship among these X, Y, and Z is shown in FIG.

ΔNp = (Nx + Ny) / 2−Nz ΔNxy = Nx−Ny ΔNp; degree of plane orientation ΔNxy; refractive index in x and y directions Nx; refractive index in x direction Ny; refractive index in y direction Nz; refractive index in z direction

[0097]

Example 1 Polyethylene terephthalate [J135 manufactured by Mitsui Pet Resin Co., Ltd., [η]: 0.8 dl / g, melting point: 260 ° C., Tg: 74 ° C.] was manufactured by Meiki Seisakusho Co., Ltd.
A preform was obtained by molding with a -100A injection molding machine. The molding temperature at this time was 290 ° C. At this time, a preform was used so that the stretch ratio during stretch blow molding described below would be 7 times.

Then, after heating and crystallizing the mouth of the preform (plug portion) and the bottom at 200 ° C., the surface temperature of the center of the body of the preform is 90 to 90 ° C. by an infrared heater attached to the molding machine.
Heat to 100 ° C, then CORPOPLAST
Stretch blow molding was carried out using a LB-01 molding machine manufactured by the company so that the area stretch ratio was 7 times, and a heat resistant bottle as shown in FIG. 1 was molded.

Next, the blow mold at the time of stretching was heated to 150 ° C., the bottle was brought into contact with the mold for 5 seconds for heat setting treatment, and then the bottle was cooled to 100 ° C. or lower and then taken out from the mold.

Regarding the bottle thus created,
The heat resistance and pressure characteristics were evaluated. The results are shown in Table 1.

[0101]

Example 2 A bottle was molded in the same manner as in Example 1 except that the bottom of the preform was also crystallized by stretch blow molding of the entire preform without heat crystallization of the preform. .

Regarding the bottle thus created,
The heat resistance and pressure characteristics were evaluated. The results are shown in Table 1.

[0103]

Example 3 A bottle was molded in the same manner as in Example 1 except that the preform having an area draw ratio of 9 was used.

Regarding the bottle thus created,
The heat resistance and pressure characteristics were evaluated. The results are shown in Table 1.

[0105]

Comparative Example 1 A bottle was prepared in the same manner as in Example 1 except that the mouth and bottom of the preform were not heated and crystallized.

With respect to this bottle, the heat resistance and the like were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0107]

Comparative Example 2 A bottle was prepared in the same manner as in Example 1 except that the bottom of Example 1 was not heated and crystallized.

With respect to this bottle, heat resistance and the like were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0109]

[Table 1]

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of a saturated polyester bottle having heat and pressure resistance.

FIG. 2 is an X-ray diffraction intensity curve showing the relationship between the diffraction angle (2θ) and the X-ray diffraction intensity for explaining the method of calculating the crystallinity of a bottle. In FIG. 2, (A) is 1
It is an X-ray-diffraction-intensity curve in a 00% amorphous, (C) is an X-ray-diffraction-intensity curve of a bottle.

FIG. 3 is a schematic explanatory diagram of a bottle falling angle measuring device.

FIG. 4 is a diagram showing a relationship among a bottle height direction X, a circumferential direction Y, and a thickness direction Z.

[Explanation of symbols]

 100 ... ・ Bottle 200 ・ ・ ・ ・ Port stopper 300 ・ ・ ・ ・ ・ ・ Upper shoulder 400 ・ ・ ・ ・ Body 500 ・ ・ ・ ・ Bottom

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location // B29K 67:00 B29L 22:00 (72) Inventor Ayumi Hata Kazumi Waki, Kuga-gun, Yamaguchi Prefecture Mori Petrochemical Industry Co., Ltd. Mt. 1-2, Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Michio Tsugawa Manipulation No. 1-2-2 Waki, Waki-machi, Kuga-gun, Yamaguchi

Claims (9)

[Claims] 1. When the bottle is filled with 2.5 gas volume of a carbonated gas beverage at 23 ° C. and the bottle is tightly stoppered and immersed in a 70 ° C. hot bath for 1 hour, a hot bath test is performed, and the following conditions are satisfied. Bottle made of saturated polyester. Condition 1: The dimensional change rate in the height direction of the carbonated gas filled bottle before and after the hot bath test is 5% or less, and the dimensional change rate in the body diameter direction is 5% or less. Condition 2: The falling angle of the bottle after the hot bath test is 10 degrees or more. 2. The crystallinity of the neck of the bottle, the crystallinity of the center of the body, and the crystallinity of the center of the bottom are all 25 to 6.
It is 0%, The bottle made from saturated polyester of Claim 1 characterized by the above-mentioned. 3. When the distance from the central portion of the bottom of the bottle to the peripheral portion is R, (i) the sum of the thermal crystallinity and the oriented crystallinity in the range of the central portion of the bottom to 7R / 10 is obtained. 25-60%, (ii) the thermal crystallinity in the range of 7R / 10-9R / 10 from the center of the bottom is 1-25%, and the oriented crystallinity is 20-
30%, and the sum of thermal crystallinity and oriented crystallinity is 25 to 60%. (Iii) 9R / 10 from the center of the bottom to the peripheral edge (1
The saturated polyester bottle according to claim 2, wherein the crystallinity in the range of 0R / 10) is 25 to 60%. 4. A degree of surface orientation (ΔNp) at the center of the body of the bottle.
Is 0.1 to 0.2, and the bottom 7R / 10 to 9R / 1
The saturated polyester bottle according to any one of claims 2 to 3, wherein the degree of plane orientation in the range of 0 is 0.05 to 0.2. 5. The saturated polyester bottle according to any one of claims 1 to 4, wherein the bottle is a self-supporting bottle having legs at its bottom. 6. The crystallinity of the bottom of the bottle is adjusted to 25 to 60% by stretch blow molding the preform, or by heat crystallization of the bottom of the preform and then stretch blow molding. A method for producing a bottle made of a saturated polystel. 7. The method according to claim 6, wherein the bottom portion of the preform is crystallized by heating so that the crystallinity by heating is 25 to 60%. 8. The stretch blow molding ratio is 6 in terms of area draw ratio.
~ 15 times, the method according to any one of claims 6 to 7. 9. The method according to claim 6, wherein heat setting is performed after the stretch blow molding.