JP3055108B2 - Flexible bottle - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible bottle, and more particularly, to a polyester flexible bottle capable of buckling vertically when not filled and a multilayer flexible bottle capable of buckling vertically when not filled.

[0002]

BACKGROUND OF THE INVENTION Conventionally, metal containers are often used as large containers for filling beer, juice and the like. However, although such a metal container is robust, it is heavy and difficult to carry, and even when an empty container is collected, there are problems such as hygiene of the collection container and collection cost.

[0003] In addition, even if a conventional plastic container is used, it is expensive to collect and reuse it, and when it is discarded, there are problems such as high bulk. further,
When a polyolefin or the like is used as the material of the plastic container, there is a problem that the gas barrier property is not sufficient and the content liquid has an olefin odor and taste is reduced.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve such a problem. After discharging the contents, the contents can be crushed by hand and folded and discarded, and the gas barrier property and the pressure resistance are excellent. Moreover, it aims to provide a flexible one-way bottle that does not detract from the taste of the liquid content.

[0005]

SUMMARY OF THE INVENTION A first flexible bottle according to the present invention is a polyester bottle comprising a plug portion and a body portion, wherein the body portion has a wall thickness of 20 to 150 .mu.m .
Volume stretch ratio (content of bottle / content of preform)
Product) is 100 to 240 times, and the bottle
A force of several kgf or less was applied from the stopper toward the trunk.
Sometimes, the second flexible bottle according to the present invention is characterized by being capable of buckling in the vertical direction, a multilayer flexible bottle comprising a plug portion and a body, wherein the body is made of a polyester resin and Group i) Polyamide resin ii) Resin selected from copolymerized polyester resin (II) formed from dicarboxylic acid structural unit, dihydroxy compound structural unit, and polyfunctional hydroxy compound structural unit having at least three hydroxy groups Are laminated, the thickness of the body is 20 to 150 μm, and the volume expansion ratio of the bottle (internal volume of bottle / pref
The inner volume of the bottle is 100 to 240 times, and several kgf or less from the plug of the bottle toward the body when not filled.
It is characterized in that it can buckle up and down when a force is applied .

[0006] Such a flexible bottle according to the present invention can be crushed and folded by hand after discharging the content liquid, and is excellent in gas barrier property and pressure resistance, and does not deteriorate the taste of the content liquid. .

[0007] In the present specification, the term "capable of buckling in the vertical direction when the bottle is not filled" means that when a force of several kgf or less is applied in the body direction to the plug portion of the bottle, the bottle is not squeezed as shown in FIG.
It means to be transformed like That is, in this specification
That it can buckle vertically when not filling
Apply a force of several kgf or less from the spout toward the trunk.
When the bottle is deformed as shown in FIG.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the flexible bottle according to the present invention will be specifically described. First, each resin constituting the first flexible bottle and the second flexible bottle according to the present invention will be described.

The polyester resin used in the first flexible bottle according to the present invention includes polyethylene terephthalate resin, polyethylene naphthalate resin, and the following copolymerized polyester resins (1) to (7).
And the like.

Hereinafter, each resin will be described more specifically. Polyethylene terephthalate resin Polyethylene terephthalate resin (hereinafter, sometimes referred to as PET) used in the first flexible bottle according to the present invention includes terephthalic acid or an ester-forming derivative thereof, and ethylene glycol or an ester-forming derivative thereof. The polyethylene terephthalate resin may be copolymerized with 20 mol% or less of another dicarboxylic acid and / or another dihydroxy compound.

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, 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, specifically, aliphatic glycols such as trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol; cyclohexane Alicyclic glycols such as dimethanol; bisphenols; hydroquinone, 2,2-bis (4-
and aromatic diols such as (β-hydroxyethoxyphenyl) propane.

[0013] Such a polyethylene terephthalate resin can be used to convert a substantially linear polyester by a single unit of the ethylene terephthalate component unit or a random arrangement of the ethylene terephthalate component unit and the dioxyethylene terephthalate component unit to form an ester bond. Has formed. 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.

In such a polyethylene terephthalate resin, the intrinsic viscosity [η] (25 ° C. in o-chlorophenol)
Is usually 0.6 to 1.5 dl / g, preferably 0.7 to 1.2 dl / g. 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 resin The polyethylene naphthalate resin used in the first flexible bottle according to the present invention contains 60 units of ethylene-2,6-naphthalate units derived from 2,6-naphthalenedicarboxylic acid and ethylene glycol. It is desirable that the content is not less than 80 mol%, preferably not less than 80 mol%, more preferably not less than 90 mol%.
-Constituent units other than naphthalate may be contained in an amount of less than 40 mol%.

Structural units other than ethylene-2,6-naphthalate include terephthalic acid, isophthalic acid, 2,7-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, dibromoterephthalic acid; adipic acid, azelaic acid, sebacic acid, decane Aliphatic dicarboxylic acids such as dicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, hexahydroterephthalic acid; glycolic acid, p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid Of hydroxycarboxylic acid and 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-diphenoxysulfone, 2,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-
(β-hydroxyethoxyphenol) propane, polyalkylene glycol, p-phenylenebis (dimethylsiloxane), glycerin and the like.

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.

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, diphenylsulfonemonocarboxylic acid, stearic acid, methoxypolyethyleneglycol, phenoxypolyethyleneglycol, for example, 2 mol. % Or less.

Such a polyethylene naphthalate resin is substantially linear, which is confirmed by the fact that the polyethylene naphthalate resin is dissolved in o-chlorophenol.

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

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

The temperature rise crystallization temperature (Tc) of the polyethylene naphthalate resin is measured by the following method.
That is, using a DSC-2 type differential calorimeter manufactured by Perkin Elmer Co., Ltd. at about 140 ° C. under a pressure of about 5 mmHg for about 5 hours.
A thin section of about 10 mg of a sample collected from the center of the polyethylene naphthalate resin chip dried for more than an hour is sealed in a liquid aluminum pan under a nitrogen atmosphere and measured. 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 Resin (1) The copolyester resin (1) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit and an isophthalic acid component unit, and ethylene And a dihydroxy compound constituent unit containing a glycol component unit.

The dicarboxylic acid constituting unit of the copolymerized polyester resin (1) has a terephthalic acid component unit of 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 copolymerized polyester 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 properties of the obtained copolymerized polyester resin (1), for example, 1 Other dicarboxylic acids can be used in amounts up to mol%.

Examples of such a dicarboxylic acid include phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In addition, in the copolymerized polyester resin (1) according to the present invention, in addition to the above-mentioned ethylene glycol as a dihydroxy compound, the amount of the obtained copolymerized polyester resin (1) is not impaired, for example, an amount of 1 mol% or less. Other dihydroxy compounds 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 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.

Copolyester Resin (2) The copolyester resin (2) used in the first flexible bottle according to the present invention is a dicarboxylic acid containing a terephthalic acid component unit and a 2,6-naphthalenedicarboxylic acid component unit. It is composed of a structural unit and a dihydroxy compound structural unit containing an ethylene glycol component unit.

The dicarboxylic acid constituting unit of the copolymerized polyester resin (2) has a terephthalic acid component unit of 80 to 99.5 mol%, preferably 90 to 99.5 mol%.
It is desirable that 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 copolymerized polyester resin (2) according to the present invention, in addition to the above terephthalic acid and 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component,
Other dicarboxylic acids can be used in a range that does not impair the properties of the obtained copolymerized polyester resin (2), for example, 1 mol% or less.

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

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.

Copolyester Resin (3) The copolyester resin (3) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit and an adipic acid component unit, and ethylene And a dihydroxy compound constituent unit containing a glycol component unit.

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

In the copolymerized polyester resin (3) according to the present invention, in addition to the above-mentioned terephthalic acid and adipic acid as the dicarboxylic acid components, a range in which the properties of the obtained copolymerized polyester resin (3) are not impaired, for example, 1 Other dicarboxylic acids can 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. In the copolyester resin (3) according to the present invention,
In addition to ethylene glycol as a dihydroxy compound,
Other dihydroxy compounds can be used in a range that does not impair the properties of the obtained copolymerized polyester 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.

Copolyester Resin (4) The copolyester resin (4) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit, an ethylene glycol component unit and a diethylene glycol component. And a dihydroxy compound structural unit containing a component unit.

The dihydroxy compound constituting units of the copolymerized polyester resin (4) has an ethylene glycol component unit of 93 to 98 mol%, preferably 95 to 98 mol%.
It is desirable that the diethylene glycol component units be present in an amount of 2 to 7 mol%, preferably 2 to 5 mol%.

In the copolymerized polyester resin (4) according to the present invention, in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, a range in which the properties of the obtained copolymerized polyester resin (4) is not impaired, for example, 1 mol% or less. Other dicarboxylic acids can be used in amounts of.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester resin (4) according to the present invention,
As the dihydroxy compound, other than the above-mentioned ethylene glycol and diethylene glycol, other dihydroxy compounds can be used in a range that does not impair the properties of the obtained copolymerized polyester resin (4), 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 2,2,2-bis (4-β-hydroxyethoxyphenyl) propane and bis (4-β-hydroxyethoxyphenyl) sulfone are used.

Copolyester Resin (5) The copolyester resin (5) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit, an ethylene glycol component unit and a And a dihydroxy compound constituent unit containing a pentyl glycol component unit.

The structural units of the dihydroxy compound constituting the copolymerized polyester resin (5) have an ethylene glycol component unit of 85 to 99.5 mol%, preferably 90 to 99.5 mol%.
In an amount of 99.5 mol%, and 0.5 to 15 mol%, preferably 0.5 to 10 mol% of neopentyl glycol component unit.
Desirably it is present in an amount of mole%.

In the copolymerized polyester resin (5) according to the present invention, in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, a range that does not impair the properties of the obtained copolymerized polyester resin (5), for example, 1 mol% or less Other dicarboxylic acids can be used in amounts of.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester resin (5) according to the present invention,
Other than ethylene glycol and neopentyl glycol as described above as the dihydroxy compound, a range that does not impair the properties of the obtained copolymerized polyester 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.

Copolyester Resin (6) The copolyester resin (6) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit containing a terephthalic acid component unit, an ethylene glycol component unit and cyclohexane. And a dihydroxy compound constituent unit containing a dimethanol component unit.

The structural units of the dihydroxy compound constituting the copolymerized polyester resin (6) have an ethylene glycol component unit of 85 to 99.5 mol%, preferably 90 to 90 mol%.
99.5 mol%, and the cyclohexanedimethanol component unit is 0.5 to 15 mol%, preferably 0.5 to 15 mol%.
Desirably, it is present in an amount of 10 mol%.

In the copolymerized polyester resin (6) according to the present invention, in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, a range of not impairing the properties of the obtained copolymerized polyester resin (6), for example, 1 mol% or less. Other dicarboxylic acids can be used in amounts.

Examples of such a dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolymerized polyester resin (6) according to the present invention,
As the dihydroxy compound, other than the above-mentioned ethylene glycol and cyclohexanedimethanol, other dihydroxy compounds can be used in a range that does not impair the properties of the obtained copolymerized polyester 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 2-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone, Used.

Copolyester Resin (7) The copolyester resin (7) used in the first flexible bottle according to the present invention comprises a dicarboxylic acid structural unit, a dihydroxy compound structural unit and at least 3
And a polyfunctional hydroxy compound structural unit having two hydroxyl groups.

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

The dihydroxy compound constituent unit has a dihydroxyethoxy resole component unit in an amount of 5 to 90 mol%, preferably 10 to 85 mol%, and an ethylene glycol component unit in an amount of 10 to 95 mol%, preferably 15 to 95 mol%. Desirably, it is present in an amount of ~ 90 mol%.

The copolymerized polyester resin (7) includes:
A polyfunctional hydroxy compound structural unit having at least three hydroxy groups is present. This polyfunctional hydroxy compound structural unit is used in an amount of 0.05 to 1.0 mole part, preferably 0.1 to 1.0 mole part, per 100 mole parts of the dicarboxylic acid component unit.
Desirably it is present in an amount of 0.5 mole part.

Such a polyfunctional hydroxy compound structural unit is derived from, for example, compounds such as trimethylolmethane, trimethylolethane, and trimethylolpropane. Of these, trimethylolpropane is preferable.

In the copolymerized polyester resin (7) according to the present invention, in addition to the above-mentioned isophthalic acid and terephthalic acid as the dicarboxylic acid component, a range that does not impair the properties of the obtained copolymerized polyester resin (7), for example, 1 Other dicarboxylic acids can 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. In the copolymerized polyester resin (7) according to the present invention,
As the dihydroxy compound, other than the above-mentioned dihydroxyethoxyresole and ethylene glycol, other dihydroxy compounds can be used in a range that does not impair the properties of the obtained copolymerized polyester 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 2,2,2-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 articles such as bottles from the obtained polyester resin composition. The intrinsic viscosity [η] of the copolymerized polyester resin in an o-chlorophenol solvent is 0.5 dl / g to 1.5 dl / g or more;
Preferably, it is in the range of 0.6 to 1.2 dl / g.

The resin used in the second flexible bottle according to the present invention includes a polyester resin, a polyamide resin, a dicarboxylic acid structural unit, a dihydroxy compound structural unit, and a polyfunctional hydroxy compound structural unit having at least three hydroxy groups. And a copolymerized polyester resin (II) formed from

Hereinafter, each resin will be described more specifically. Polyester resin As the polyester resin used in the second flexible bottle according to the present invention, the polyethylene terephthalate resin, the polyethylene naphthalate resin,
And the above-mentioned copolymerized polyester resins (1) to (7).

Polyamide Resin The polyamide resin used in the second flexible bottle according to the present invention is formed from a metaxylylenediamine constituent unit and an adipic acid constituent unit.

This polyamide resin may be copolymerized with 3 mol% or less of other diamine constituent units and / or other dicarboxylic acid constituent units. Specific examples of the diamine used for copolymerization other than meta-xylylenediamine include 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane,
Linear alkylenediamines such as 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane;

1,4-diamino-1,1-dimethylbutane,
1,4-diamino-1-ethylbutane, 1,4-diamino-1,
2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-
Diamino-2,3-dimethylbutane, 1,2-diamino-1-
Butylethane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane, 1,6-
Diamino-3,3-dimethylhexane, 1,6-diamino-
2,2-dimethylhexane, 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3-dimethylheptane, 1,7-diamino-2,4-dimethylheptane, 1,7-
Diamino-2,5-dimethylheptane, 1,7-diamino-
2,2-dimethylheptane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, 1,8-
Diamino-3,4-dimethyloctane, 1,8-diamino-
4,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-
Diamino-2,4-diethylhexane, 1,9-diamino-5
Branched alkylenediamines such as -methylnonane;

1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine , Bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4 '
-Diamino-3,3'-dimethyldicyclohexylpropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-
Dimethyldicyclohexylmethane, 4,4'-diamino-
3,3'-dimethyl-5,5'-dimethyldicyclohexylpropane, α-α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α-α'-bis (4-aminocyclohexyl) -m-diisopropyl Benzene, α-α'-bis (4
-Aminocyclohexyl) -1,4-cyclohexane, α-
Component units derived from alicyclic diamines such as α'-bis (4-aminocyclohexyl) -1,3-cyclohexane can be mentioned.

Specific examples of the dicarboxylic acids used for copolymerization other than adipic acid include terephthalic acid, phthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid and 2-methylterephthalic acid; aliphatic dicarboxylic acids such as succinic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid; cyclohexanedicarboxylic acid and the like And alicyclic dicarboxylic acids.

As such a polyamide resin, it is possible to use a mixture of low molecular weight substances such as monomers and oligomers remaining when the polyamide resin is polymerized.

The degree of polymerization of the polyamide resin used is not limited, but it is preferable that the limiting viscosity of concentrated sulfuric acid is 0.5 or more.

Copolyester Resin (II) The copolyester resin (II) used in the second flexible bottle according to the present invention is the same as the above-mentioned copolyester resin (7).

The resins constituting the first flexible bottle and the second flexible bottle as described above can be manufactured by a conventionally known manufacturing method. In addition, in each of the above resins, various compounding agents such as heat stabilizers, weather stabilizers, antistatic agents, lubricants, release agents, inorganic fillers, pigment dispersants, pigments or dyes of the present invention. It can be added in a range that does not impair the purpose.

The first flexible bottle and the second flexible bottle according to the present invention have a body 4 having an upper shoulder 3, a lower shoulder 5, and a bottom 6, as shown in FIG. Alternatively, as shown in FIG. 2B, various shapes can be adopted, such as a shape having a body 4 with no distinct upper and lower shoulders and a bottom.

Here, the body of the flexible bottle according to the present invention is a portion below the support ring 7. In order to produce the first flexible bottle according to the present invention, first, a preform is produced from the polyester resin.
The preform can be manufactured by a conventionally known method, for example, injection molding.

Next, the preform is heated and stretch blow-molded to produce a flexible bottle. In this case, a frame for simply adjusting the shape may be used without using a conventional mold, or stretch blow molding may be performed without using a mold or a frame.

The thickness of the body of the flexible bottle thus produced is 20 to 150 μm, preferably 50 to 150 μm.
It is desirably in the range of about 130 μm. The body of the second flexible bottle according to the present invention has a two-layer structure in which a polyester resin and a polyamide resin are laminated, a two-layer structure in which a polyester resin and a copolymerized polyester resin (II) are laminated, and a polyester. The resin (a), the polyamide resin, and the polyester resin (b) are laminated in this order in a three-layer structure. The polyester resin (a), the copolymerized polyester resin (II), and the polyester resin (b) are A configuration such as a three-layer structure laminated in this order can be adopted.

In such a multilayer flexible bottle, the polyester resin (a) and the polyester resin (b) may be the same or different, but the copolymerized polyester resin (II) and the polyester resin (a) Preferably, the copolymerized polyester resin (II) and the polyester resin (b) are different.

In such a multilayer flexible bottle, when the body has two layers, the polyester resin layer is preferably the inner layer. In order to prepare the second flexible bottle according to the present invention, first, a multilayer preform is prepared from the polyester resin and a copolymerized polyester resin (II) or a polyamide resin. The multilayer preform can be manufactured by a conventionally known method, for example, by coextrusion.

Next, the above multilayer preform is heated and stretch blow molded to produce a multilayer flexible bottle.
In this case, a frame for simply adjusting the shape may be used without using a conventional mold, or stretch blow molding may be performed without using a mold or a frame.

The thickness of the body portion of the multilayer flexible bottle thus produced is desirably in the range of 20 to 150 μm, preferably 50 to 130 μm. When the body has two layers, the polyester resin layer has a thickness of 85 to 97%, preferably 90 to 95% with respect to the total thickness, and comprises a polyamide resin layer or a copolymerized polyester resin (II) layer. Has a thickness of 3 to 15%, preferably 5 to 10%. Also, if the trunk has three layers,
The polyester resin (a) layer has a thickness of 45 to 5 with respect to the total thickness.
0%, preferably 50 to 53%, and the polyamide resin layer or the copolyester resin (II) layer has a thickness of 3%.
15%, preferably 5 to 10%, and the polyester resin (b) layer has a thickness of 40 to 47%, preferably 40 to 4%.
Desirably, the thickness is 2%.

The first and second flexible bottles preferably have a volume expansion ratio of 100 to 240 times, preferably 120 to 200 times. In addition, volume expansion ratio is measured as follows.

[0083]

(Equation 1)

Here, the internal volume is an internal volume below the support ring 7.

[0085]

According to the flexible bottle of the present invention, since the thickness of the body portion is within a certain range, after discharging the content liquid, it can be crushed and folded by hand as shown in FIG. No bulk when discarded. Further, since it has excellent gas barrier properties and pressure resistance and does not impart a taste or odor to the liquid content, it is suitable as a container for beverages such as beer, carbonated beverages and juices.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. In this specification, the carbon dioxide permeability coefficient, the oxygen permeability coefficient, and the pressure resistance of the flexible bottle are measured as follows.

[CO2 Permeation Coefficient] MODERN CO
NTROL CO., LTD. (USA) Carbon dioxide permeation tester PERMA
Using a TRAN C-IV model, the carbon dioxide gas transmission coefficient of a sample consisting of a section at the center of the bottle body was measured by the PERMATRAN method at a temperature of 23 ° C. and a relative humidity of 0%.

[Oxygen Permeability Coefficient] MODERN CONT
ROL company (USA) OXTRAN100 type
The XTRAN method was used to measure the oxygen gas permeability coefficient of a sample consisting of a section at the center of the body of the bottle at a temperature of 23 ° C. and a relative humidity of 0%.

[Pressure Strength] The pressure strength was determined by placing a bottle in a constant temperature water bath at 30 ° C.
Water pressure was applied at a water flow rate of 500 cc / min to measure the pressure at the time of destruction, and this value was used as the pressure resistance.

The measurement was performed three times (n = 3) in each case, and the average value was adopted.

[0091]

Example 1 Polyethylene terephthalate resin [J125 (IV = 0.79dl /
g)] was heated to 270 to 290 ° C. by an injection molding machine and injected into a mold to prepare a preform.

[0092] This preform was subjected to 100
After heating to ° C., the bottle was stretched freely in a simple mold to obtain a bottle having a body thickness of 100 μm, a volume stretch ratio of 159 times, and a volume of 5 liters.

For this bottle, the carbon dioxide permeability coefficient, the oxygen permeability coefficient and the pressure resistance defined in the specification were measured. Table 1 shows the results.

[0094]

Example 2 A three-layer preform of PET / polyamide resin / PET was prepared using an ASB50HT molding machine manufactured by Nissei ASB Co., Ltd. PET is Mitsui Pet Resin Co., Ltd. J12
5 (IV = 0.79 dl / g), and MX nylon 6007 manufactured by Mitsubishi Gas Chemical Company, Ltd. was used as the polyamide resin.

This preform was heated with an infrared heater for 10 hours.
After heating to 0 ° C., the film was stretched freely in a simple mold, the body thickness was 95 μm, the volume stretching ratio was 165 times, and the volume was 5.4.
Created a liter bottle. The thickness of the polyamide resin layer as the intermediate layer was 11 μm.

For this bottle, the carbon dioxide permeability coefficient, oxygen permeability coefficient and pressure resistance defined in the specification were measured. Table 1 shows the results.

[0097]

Comparative Example 1 A parison was formed by melting a polyethylene resin in a cylinder heated to 220 ° C. to form a parison, and blow molding was performed using a stretch blow molding machine to obtain a bottle having a volume of 5 liters.

The bottle was measured for carbon dioxide permeability coefficient, oxygen permeability coefficient and pressure resistance as defined in the specification. Table 1 shows the results.

[0099]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a schematic view showing a state in which a body of a flexible bottle according to the present invention is folded.

FIG. 2 is a schematic view showing a flexible bottle according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Flexible bottle 2 Plug part 3 Upper shoulder part 4 Body part 5 Lower shoulder part 6 Bottom part 7 Support ring

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FIB29L 9:00 22:00 (72) Inventor Ayu Susumu 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Examiner in Industrial Co., Ltd. Akihiro Watani (56) References JP-A-60-240452 (JP, A) JP-A-60-232952 (JP, A) JP-A-56-105936 (JP, A) JP 56-64839 (JP, A) JP-A-58-197050 (JP, A) JP-A-2-233341 (JP, A) JP-A-61-197220 (JP, A) JP-A-63-191737 (JP, A) A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B29C 49/00-49/80 B65D 1/00-1/48 B65D 37/00

Claims (2)

(57) [Claims] 1. A polyester bottle comprising a plug portion and a body portion, wherein the body portion has a thickness of 20 to 150 μm, and the volume of the bottle increases.
Elongation ratio (internal volume of bottle / internal volume of preform) is 1
It is 00 to 240 times, and from the mouth of the bottle when not filling
When a force of several kgf or less is applied toward the trunk,
A flexible bottle made of polyester, which can be buckled vertically . 2. A multilayer bottle comprising a plug portion and a body portion, wherein the body portion comprises a polyester resin and the following group: i) a polyamide resin; ii) a dicarboxylic acid structural unit, a dihydroxy compound structural unit, and at least three hydroxy groups. Bottle having a multilayer structure in which a resin selected from a copolymerized polyester resin (II) formed from a polyfunctional hydroxy compound structural unit having a group is laminated, and a body thickness is 20 to 150 μm; of
Volume stretch ratio (content of bottle / content of preform)
Product) is 100 to 240 times, and the bottle
A force of several kgf or less was applied from the stopper toward the trunk.
When the multilayer flexible bottle, which is a possible buckling in the vertical direction.