JP3403540B2 - Polyester composition bottle and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition bottle and a method for producing the same, and more particularly to a polyester composition capable of maintaining self-sustaining property without being deformed even when filled with a heated beverage or the like. The present invention relates to a bottle and a manufacturing method thereof.

[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, polyester such as polyethylene terephthalate is transparent. It is widely used because of its excellent gas barrier property, heat resistance and mechanical strength.

[0003] By the way, since the above-mentioned drinkable tea or the like is heat-sterilized and filled in a bottle at a high temperature, if the plastic forming the bottle does not have good heat resistance, the bottle will be deformed, contracted, or expanded. May cause problems such as Therefore, even if the bottle is filled with a heated beverage or the like, the bottle is not deformed and the self-sustaining property can be maintained (hereinafter also referred to as “heat-resistant property”).
There is a need for a plastic bottle having.

From the viewpoint of productivity, it is required to shorten the molding cycle, especially the molding cycle at the time of blow molding. Based on the above knowledge, the present inventors have diligently studied to obtain a bottle having a small deformation such as a mouth neck portion and a bottom portion of a bottle filled with a heated beverage, etc., and a specific polyester composition. It has been found that the bottle made of a polyester composition consisting of is excellent in heat resistance. Further, when a bottle is manufactured using the specific polyester composition,
The inventors have found that the molding cycle can be shortened and have completed the present invention.

[0005]

An object of the present invention is to provide a bottle made of a polyester composition and a method for producing the same, which is capable of maintaining the self-supporting property without deforming the bottle even when filled with a heated beverage or the like. There is.

[0006]

SUMMARY OF THE INVENTION A bottle made of a polyester composition according to the present invention comprises a polyester composition formed from 95 to 99.99% by weight of polyester and 0.01 to 5% by weight of rosin or its derivative, Crystallinity of the neck is 2
It is in the range of 5 to 60%, and the crystallinity in the center of the body is 25 to
It is in the range of 60%, and the crystallinity of the bottom is in the range of 0 to 60%.

Such a polyester composition bottle has a crystallization rate of 150 seconds or less when the polyester composition forming the bottle is measured by a t1 / 2 temperature raising method (140 ° C.) by a differential scanning calorimeter, Moreover, the haze value at the center of the bottle body is preferably 5% or less.

The bottle made of the polyester composition is preferably for non-carbonated beverages such as natural water and tea for drinking. 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 a polyester content of 95-99.99% by weight
And a rosin or a derivative thereof in an amount of 0.01 to 5% by weight, a preform made of a polyester composition is stretch-blown at an area stretch ratio of 6 to 15 to obtain a crystallinity in the center of the bottle body. The feature is that the bottle is in the range of 25 to 60%.

In the present invention, it is preferable that the crystallization rate of the polyester composition measured by a differential scanning calorimeter by the t1 / 2 temperature raising method (140 ° C.) is 150 seconds or less.
Further, it is preferable to perform heat setting after the 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 The polyester composition bottle and the method for producing the same according to the present invention will be described below.

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

It is desirable that the haze value at the center of the body of the polyester composition bottle according to the present invention is 5% or less, preferably 3% or less. Such a bottle made of a polyester composition according to the present invention is formed of a polyester composition containing polyester and rosin or its derivative.

The polyester and rosin or its derivative will be specifically described below. Examples of the polyester used in the polyester composition bottle according to the present invention include polyethylene terephthalate, polyethylene naphthalate, and the following copolymerized polyesters (1) to (4).

Polyethylene terephthalate Polyethylene terephthalate is produced by using terephthalic acid and ethylene glycol as raw materials. This polyethylene terephthalate is copolymerized with 20 mol% or less of another dicarboxylic acid and / or another dihydroxy compound. May be.

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, 2,2-
Examples thereof include aromatic diols such as bis (4-β-hydroxyethoxyphenyl) propane.

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

In such polyethylene terephthalate, the intrinsic viscosity [η] (value measured at 25 ° C. in o-chlorophenol) is usually 0.6 to 1.5 dl / g, preferably 0.7 to 1.2 dl. / G is desirable. 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.
-More than 60 mol% of naphthalate units, preferably 80
It is desirable that the content of the structural unit other than ethylene-2,6-naphthalate is less than 40 mol%, although it is desirable that the content is at least mol%, more preferably at least 90 mol%.

As structural 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'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid and dibromoterephthalic acid; adipic acid,
Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid and decanedicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid and hexahydroterephthalic acid; glycolic acid, p-hydroxybenzoic acid, Hydroxycarboxylic acid 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, 1, 4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxysulfone, 1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenol) propane, polyalkyle And a structural unit derived from p-phenylene bis (dimethylsiloxane), glycerin and the like.

Further, polyethylene naphthalate contains a small amount of structural units derived from a polyfunctional compound such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane and pentaerythritol in an amount of 2 mol% or less. Good.

Further, polyethylene naphthalate includes benzoyl benzoic acid, diphenyl sulfone monocarboxylic acid, stearic acid, methoxy polyethylene glycol,
The constitutional unit 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, which is confirmed by the dissolution of the polyethylene naphthalate in o-chlorophenol.

The intrinsic viscosity [η] of polyethylene naphthalate measured in o-chlorophenol at 25 ° C. is 0.2.
~ 1.1 dl / g, preferably 0.3-0.9 dl /
g, and 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 added to o-chlorophenol at 1 g / 1
Melt at a concentration of 00 ml, measure the solution viscosity using an Ubbelohde-type capillary viscometer at 25 ° C, and then gradually add o-chlorophenol to measure the solution viscosity on the low concentration side to reach 0% concentration. The outside viscosity is searched to find the intrinsic viscosity ([η]).

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

The temperature rising crystallization temperature (Tc) of polyethylene naphthalate is measured by the following method. That is,
Using a Perkin-Elmer DSC-2 type differential scanning calorimeter, a thin piece of about 10 mg of a sample collected from the central portion of a polyethylene naphthalate chip dried at about 140 ° C. under a pressure of about 5 mmHg for about 5 hours or more was used. The measurement is performed in a liquid aluminum pan in a nitrogen atmosphere. 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 (1) The copolyester (1) is composed of a dicarboxylic acid constituent unit containing a terephthalic acid component unit and an isophthalic acid component unit, and a dihydroxy compound constituent unit containing an ethylene glycol component unit. .

The dicarboxylic acid constitutional unit constituting this copolyester (1) contains 85 terephthalic acid component units.
Is present in an amount of ˜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%. Is desirable.

In the copolyester (1), in addition to the above-mentioned terephthalic acid and isophthalic acid as the dicarboxylic acid component, in a range that does not impair the characteristics of the resulting copolyester (1), for example, 1 mol% or less. Other dicarboxylic acids can also be used.

Examples of such dicarboxylic acids include phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolyester (1), in addition to ethylene glycol as the dihydroxy compound, other dihydroxy compounds may be added in a range that does not impair the properties of the resulting copolyester (1), for example, 1 mol% or less. It can also be used.

Examples of such dihydroxy compounds include:
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
The number of carbon atoms of benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone is 3 to 3 There may be mentioned 15 dihydroxy compounds.

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

The dicarboxylic acid constitutional unit constituting this copolyester (2) has 80 terephthalic acid component units.
In an amount of ˜99.5 mol%, preferably 90 to 99.5 mol%, and the 2,6-naphthalenedicarboxylic acid component unit is 0.5 to 20 mol%, preferably 0.5 to 10 mol%. It is desirable to be present in an amount.

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

Examples of such dicarboxylic acid include isophthalic acid, phthalic acid and 2-methylterephthalic acid. Further, in the copolyester (2),
As the dihydroxy compound, other than the ethylene glycol as described above, another dihydroxy compound may be used in a range that does not impair the properties of the resulting copolyester (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)
The number of carbon atoms of benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone is 3 to 3 There may be mentioned 15 dihydroxy compounds.

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

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

In the copolyester (3), in addition to terephthalic acid and adipic acid as the dicarboxylic acid components, the amount of the copolyester (3) is not impaired, for example, 1 mol% or less. Other dicarboxylic acids can also be used.

Examples of such dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid, and 2,6-naphthalenedicarboxylic acid. In the copolyester (3), other than ethylene glycol as a dihydroxy compound, a range not impairing the properties of the copolyester (3) obtained, for example, 1 mol%
Other dihydroxy compounds can also be used in the following amounts.

Examples of such dihydroxy compounds include:
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
The number of carbon atoms of benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone is 3 to 3 There may be mentioned 15 dihydroxy compounds.

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

The dihydroxy compound constitutional unit constituting the copolyester (4) contains the ethylene glycol component unit in an amount of 93 to 98 mol%, preferably 95 to 98 mol%, and the diethylene glycol component unit is 2 to 2 mol%.
It is desirable to be present in an amount of 7 mol%, preferably 2-5 mol%.

In the copolyester (4), in addition to the above-mentioned terephthalic acid as the dicarboxylic acid component, other dicarboxylic acids can be used within a range that does not impair the characteristics of the resulting copolyester (4), for example, 1 mol% or less. Acids can also be used.

Examples of such dicarboxylic acid include isophthalic acid, phthalic acid, 2-methylterephthalic acid and 2,6-naphthalenedicarboxylic acid. In the copolyester (4), other than diethylene glycol and diethylene glycol as described above as dihydroxy compounds, other dihydroxy compounds can be used in a range that does not impair the properties of the resulting copolyester (4), for example, 1 mol% or less. Compounds can also be used.

Examples of such dihydroxy compounds include:
1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy)
The number of carbon atoms of benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl) sulfone is 3 to 3 15 dihydroxy compounds are used.

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

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

Examples of rosins or derivatives thereof include natural rosins such as gum rosin, tall oil rosin, and wood rosin; disproportionated rosins, hydrogenated rosins, dehydrogenated rosins, polymerized rosins, α, β-ethylenically unsaturated rosins. Examples include various modified rosins such as carboxylic acid modified rosins; purified products of the above natural rosins, and purified products of modified rosins. The unsaturated carboxylic acid used in the preparation of the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid. , Methacrylic acid and the like.

Of these, at least one rosin selected from the group consisting of natural rosin, modified rosin, purified product of natural rosin and purified product of modified rosin is preferable. Here, the rosin is a plurality of resin acids selected from pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, and the like. Contains.

Examples of rosin derivatives include metal salts of rosins, which are reaction products of rosins and metal compounds. Examples of the metal compound which reacts with the rosin to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin. Specific examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of the above metals.

In the present invention, the metal salt of rosin is at least one metal salt of rosin selected from the group consisting of sodium salt of rosin, potassium salt of rosin and magnesium salt of rosin. It is preferable. Further, the metal salt of rosin is preferably at least one metal salt of rosin selected from the group consisting of metal salts of hydrogenated rosin, metal salts of disproportionated rosin and metal salts of dehydrogenated rosin. Among these, at least one metal salt of rosins selected from the group consisting of metal salts of dehydroabietic acid, metal salts of dihydroabietic acid and metal salts of dihydropimaric acid is preferable.

As a method for producing such a metal salt of rosin, a conventionally known method can be adopted. In the present invention, a compound [compound (IA)] represented by the following formula (IA) or a compound [compound (B)] represented by the following formula (IB) can be used as the rosin.

[0057]

[Chemical 1]

In formula (IA) and formula (IB), R ¹ and R
² and R ³ are a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. Specific examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, pentyl, heptyl and octyl. These groups may have a substituent such as hydroxyl group, carboxyl group, alkoxy group and halogen.

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl, and these groups include hydroxyl group, carboxyl group, alkoxy group and halogen. It may have a substituent.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups include a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. May have.

The groups represented by R ¹ , R ² and R ³ may be the same or different. Among such compound (IA) and compound (IB), compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups are preferable, and R ¹ is i-
More preferred is a compound that is a propyl group and R ² and R ³ are methyl groups. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound (IA) include dehydroabietic acid and the like, and specific examples of the compound represented by the compound (IB) include dihydroabietic acid and the like.

Among such compounds (IA) and (IB), for example, dehydroabietic acid represented by the formula (IA) is a disproportionation or dehydration of natural rosin such as gum rosin, tall oil rosin and wood rosin. Obtained by nitration and subsequent purification. In addition, natural rosin is usually a plurality of resin acids such as pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid. Seed included.

In the present invention, the derivative of the compound (IA) or the derivative of the compound (IB) can also be used. Examples of such derivatives include the following formula (II
A) a reaction product of the above compound (IA) with a metal compound [compound (IIA)], and a compound of the following formula (II)
The reaction product [compound (IIB)] of the above-mentioned compound (IB) and metal compound as represented by B) can be mentioned.

[0065]

[Chemical 2]

In the formulas (IIA) and (IIB), R ¹ and R ²
And R ³ are the same as those in the formulas (IA) and (IB). M is a monovalent metal ion, specifically, a monovalent metal ion such as lithium, sodium, potassium, rubidium or cesium, or a divalent metal ion such as beryllium, magnesium, calcium, strontium, barium or zinc. And a trivalent metal ion such as aluminum.

Of these, M is preferably a monovalent or divalent metal ion, more preferably a sodium ion, a potassium ion or a magnesium ion.

N is the same integer as the valence of the metal ion M, and is an integer of 1 to 3. Among the compounds (IIA) and (IIB), compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups,
Alternatively, a compound in which M is a monovalent or divalent metal ion is preferable, a compound in which R ¹ is an i-propyl group, R ² and R ³ are methyl groups, or a compound in which M is a sodium ion, a potassium ion or A compound which is a magnesium ion is more preferable, a compound in which R ¹ is an i-propyl group, R ² and R ³ are methyl groups, and M is a sodium ion, a potassium ion or a magnesium ion is particularly preferable. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound (IIA) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, zinc dehydroabietic acid and dehydro. Examples thereof include metal salts of dehydroabietic acid such as aluminum abietic acid, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound (IIB) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, and dihydro. Examples thereof include metal salts of dihydroabietic acid such as aluminum abietic acid, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferably used. Such compound (IIA) and compound (IIB) may be used alone or in combination of two or more kinds.

The polyester composition bottle according to the present invention is formed from a polyester composition comprising the above polyester and a rosin or its derivative. This polyester composition is polyester 95 to 9
0.99% by weight and rosin or its derivative 0.01
-5% by weight, preferably polyester 97-99.95
And 0.05 to 3% by weight of rosin or its derivative.

As a method for preparing the polyester composition, any known method can be adopted, and examples thereof include a method in which the polyester and the rosin or its derivative are melt-kneaded using an extruder, a kneader or the like.

Further, the above-mentioned polyester composition contains various components such as a crosslinking agent, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a lubricant, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye. The agent may be contained within a range that does not impair the object of the present invention.

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

The above-mentioned polyester composition has the excellent characteristics inherent in 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 resistance.

The polyester bottle of the present invention is preferably used for non-carbonated beverages such as natural water and tea for drinking. Examples of the polyester composition bottle include self-supporting bottles. FIG. 1 shows an example of a self-supporting bottle. In the figure, 2 is a mouth / neck portion, 3 is an upper shoulder portion, 4 is a body portion, 5 is a bottom portion, and 6 is a brim portion.

The polyester composition bottle according to the present invention has a small rate of deformation, expansion and contraction even when the bottle is filled with a heated beverage or the like. Therefore, the deformation of the bottle body can be kept small even when the beverage or the like subjected to the heat sterilization treatment is filled into the bottle at a high temperature. Moreover, the bottle made of the polyester composition according to the present invention has excellent transparency. Furthermore, since the entire bottle is made of 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 specifically described. The polyester composition bottle 1 according to the present invention has a mouth / neck portion 2, an upper shoulder portion 3, a body portion 4 and a bottom portion 5 as shown in FIG. 1, for example.

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 such as injection molding or extrusion molding. The heating temperature of the polyester composition for forming the preform is usually preferably 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%. A bottle made of a polyester composition is manufactured.

The stretch ratio in stretch blow molding is preferably 6 to 15 times, and more preferably 7 to 12 times in area stretch ratio. In the present specification, the area draw ratio (hereinafter sometimes simply referred to as “draw ratio”) is a draw ratio defined as a product of a longitudinal draw ratio and a lateral draw ratio.

The temperature of the blowing fluid at the time of stretch blow molding is preferably 10 to 400 ° C, preferably 20 to 300 ° C. Examples of the blowing fluid include air, nitrogen, water vapor, water, etc. Of these, air is preferably used.

In the present invention, it is preferable that the preform mouth-neck portion is heated and crystallized prior to the stretching blow so that the preform mouth-neck portion has a crystallinity of 25 to 60%, preferably 25 to 50%. . To heat and crystallize the preform mouth and neck, the preform mouth and neck is usually heated to 150 to 20.
Heat to 0 ° C, preferably 170-190 ° C.

Stretch blow molding in which the area stretch ratio from the preform to the bottle is increased in this manner is preferable because a bottle excellent in 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. By heat setting the stretch blow-molded bottle in this manner, the density of the body portion of the bottle can be improved.

Heat setting was performed by setting the obtained bottle to 10
It is carried out by holding at a mold temperature of 0 to 200 ° C., preferably 110 to 170 ° C. for 1 second or longer, preferably 3 seconds or longer.

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 part of the stretch blow molded bottle made of the polyester composition before heat setting is 1.355 to 1.370 g / cm ^3.
After heat setting, it is usually about 1.370 to 1.410 g / cm ³ , preferably 1.375 to 1.390 g / cm after heat setting, though it depends on the heat setting temperature.
It is about ³ .

In the present invention, it is preferable that the bottle which has been subjected to the stretch blow molding as described above and, if necessary, heat set, is cooled before being taken out. As a cooling method, it is preferable to use an “internal cooling method” in which a cooled gas is blown into the bottle to cool the bottle from the inside toward the outside (outer surface). 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 −
It is desirable to be 100 ° C. to + 50 ° C., preferably −75 ° C. to + 40 ° C., and the cooling rate of the bottle is usually about 300 to 10 ° C./min, although it depends on the thickness of the bottle, the material, and the like. desirable. When cooling such a bottle, the surface temperature on the outside of the bottle is preferably 100 ° C. or lower. Examples of the cooling gas include air and nitrogen, and air is preferably used.

In the method for producing a polyester composition bottle according to the present invention, a specific polyester composition is used and a stretched bottle is molded by the specific method, so that the heat resistance of the obtained bottle is improved. It is possible to reduce the deformation of the bottle after filling with the heated beverage and maintain the self-supporting property of the bottle. Further, the polyester composition used in the present invention has a high crystallization rate, so that the molding cycle of the bottle can be shortened.

[0091]

The polyester composition bottle according to the present invention has excellent heat resistance and transparency. In addition, it is easy to melt a used bottle and reuse it in a bottle or the like.

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

[0093]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[Crystallization rate] It was measured using a differential scanning calorimeter (DSC) manufactured by Perkin Elmer. 10 mg of the sample was weighed in a sample pan, heated from room temperature to 290 ° C. at a heating rate of 320 ° C./min, and then held for 10 minutes. After that, it is rapidly cooled to 30 ° C, and further to 140 ° C 320
The temperature was raised at ° C / min and kept at this temperature. The relationship between the amount of heat generated by crystallization of the sample at this time 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 generated was defined as the crystallization rate.

[Evaluation of Heat Resistance of Bottle] The heat resistance of the bottle was evaluated by comparing the deformation of the bottle after filling the contents at 90 ° C. with that before filling. Good… The deformation of the bottle body is small. Defective ... The body of the bottle has large deformation.

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

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

[0098] Crystallinity Measurement 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 obtained by the subtraction is defined as I _c . The diffracted intensity of 100% amorphous of the same resin that has been measured is defined as I _a . The crystallinity (X _cr ) of the sample is calculated by the following formula. FIG. 4 shows an example of the X-ray diffraction intensity curve.

[0099]

[Equation 1]

[0100]

[Example 1] Polyethylene terephthalate [J125 manufactured by Mitsui Pet Resin Co., Ltd.] (hereinafter referred to as "PET-1")
A polyester composition comprising 99.8% by weight and 0.2% by weight of sodium dihydroabietate (hereinafter referred to as “RS-1”) was molded by an M-100A injection molding machine manufactured by Meiki Seisakusho Co., Ltd. to form a preform. Obtained. The molding temperature at this time was 290 ° C.

Then, after heating and crystallizing the mouth and neck of the preform at 200 ° C., the surface temperature of the center of the preform body was 90 to 10 by an infrared heater attached to the molding machine.
The mixture was heated to 0 ° C. and stretch-blown with a LB-01 molding machine manufactured by CORPOPLAST to mold a heat resistant bottle as shown in FIG. During stretching, blow mold is 150 ℃
Then, 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 taken out from the mold. The molding cycle at this time was 60 seconds, and the area stretching ratio was 7 times.

Regarding the bottle thus created,
The heat and pressure resistance defined in the specification was evaluated. The results are shown in Table 1.
Shown in.

[0103]

Example 2 A bottle was prepared in the same manner as in Example 1 except that the polyester composition consisting of 98.0% by weight of PET-1 and 2.0% by weight of RS-1 was used.

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0105]

Example 3 PET-1 99.97 in Example 1
A bottle was prepared in the same manner as in Example 1 except that a polyester composition composed of 10% by weight of RS-1 and 0.03% by weight of RS-1 was used.

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0107]

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

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0109]

Example 5 Polyethylene terephthalate [J manufactured by Mitsui Pet Resin Co., Ltd. was used in place of PET-1 in Example 1.
135] (hereinafter referred to as “PET-2”) was used to prepare a bottle in the same manner as in Example 1.

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0111]

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

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0113]

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

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0115]

Comparative Example 3 A bottle was prepared in the same manner as in Example 1 except that the polyester composition consisting of 90.0 wt% PET-1 and 10.0 wt% RS-1 was used in Example 1.

With respect to this bottle, the heat resistance property defined in the specification was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0117]

[Table 1]

[Brief description of drawings]

FIG. 1 is a schematic front view showing an example of a bottle made of a polyester composition according to the present invention, partially broken away.

[Explanation of symbols]

1 ... Bottle 2 ... Mouth and neck 3… Upper shoulder 4 ... torso 5 ... bottom 6 ... Collar

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B29L 22:00 B65D 1/00 C (72) Inventor Michio Tsugawa Man 6-6 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Ayumu Hata 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Kimachi Kazuki 6-1-2 Mitsui Petrochemical Co., Ltd. (56) Reference JP-A-2-98536 (JP, A) JP-A-62-131055 (JP, A) JP-A-58-160343 ( JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) F-term 4F208 3E033 4J002 (AF02. * CF00.)

Claims (6)

(57) [Claims] 1. A polyester containing 95 to 99.99% by weight,
Compound 0.01 represented by the following formula (IIA) or (IIB)
% To 5% by weight, the mouth and neck have a crystallinity in the range of 25 to 60%, the center of the body has a crystallinity in the range of 25 to 60%, and a bottom portion. A polyester composition bottle characterized by having a crystallinity of 0 to 60%; (In the formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, M represents a monovalent metal ion, n Is the same integer as the valence of the metal ion M). 2. The crystallization rate of the polyester composition measured by a differential scanning calorimeter by t1 / 2 temperature raising method (140 ° C.) is 150 seconds or less, and the haze value in the center of the bottle body is 5% or less. The bottle made of the polyester composition according to claim 1. 3. The bottle made of the polyester composition according to claim 1, wherein the bottle is a non-carbonated beverage bottle. 4. A polyester of 95 to 99.99% by weight,
Compound 0.01 represented by the following formula (IIA) or (IIB)
A preform made of a polyester composition formed from 5 to 5% by weight is stretch-blown at an area stretching ratio of 6 to 15 to obtain a bottle having a crystallinity in the center of the bottle body in the range of 25 to 60%. A method for producing a bottle made of a polyester composition, characterized by comprising: (In the formula, R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, M represents a monovalent metal ion, n Is the same integer as the valence of the metal ion M). 5. A polyester composition bottle according to claim 4, wherein the polyester composition has a crystallization rate of 150 seconds or less as measured by a t1 / 2 heating method (140 ° C.) by a differential scanning calorimeter. Method. 6. The method for producing a polyester composition bottle according to claim 4, wherein heat setting is performed after stretch blow molding.