JPH10211684A - Polyester laminate and manufacture of polyester multi-layer bottle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a polyester laminate suitable for a polyester multi- layer bottle of superior gas barrier properties, transparency and heat resistance, which is provided with the fast crystallization speed by laminating together first and second resin layers composed of dicarboxylic acid units and diol units. SOLUTION: A first resin layer A to be formed is constituted of first polyester composed of dicarboxylic acid units (a) derived from dicarboxylic acid and diol units (b) derived from diol composed of polyalkylene glycol having ethylene glycol and 2-10C alkylene chains, and the ratio of units (b) is in the range of 0.001-10wt.% including diol units in the first polyester. Also a second resin layer B to be laminated with the first resin layer is constituted of second polyester composed of dicarboxylic acid units (a) and diol units (c) derived from dial containing ethylene glycol, and the ratio of units (b) is less than 0.001wt.% to diol units (a) in the second polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester laminate and a polyester multilayer bottle having a high crystallization rate and excellent gas barrier properties, transparency and heat resistance.

[0002]

BACKGROUND OF THE INVENTION Saturated polyesters such as polyethylene terephthalate are widely used as containers such as bottles because of their excellent gas barrier properties, transparency and mechanical strength. In particular, the bottle obtained by biaxially stretch blow molding polyethylene terephthalate has excellent transparency, mechanical strength, heat resistance, and gas barrier properties,
It is widely used as a container (PET bottle) for filling beverages such as juice, soft drinks, and carbonated drinks. In general, such a bottle is injection-molded with saturated polyester to form a preform having a plug portion and a body portion, and then the preform is inserted into a mold having a predetermined shape and stretch blow-molded. It is manufactured by extending the body portion to form a bottle having a plug portion and an extended body portion.

[0003] Such polyester bottles, particularly polyester bottles used for beverages such as juices, are required to have heat resistance that can cope with heat sterilization of the contents. (Heat setting) to improve heat resistance.

In recent years, bottles manufactured from polyester resins (particularly, polyethylene terephthalate) tend to be miniaturized.
Because the area in contact with the bottle body per unit capacity is large,
The effect on the contents due to gas loss or permeation of oxygen from the outside becomes remarkable, and the storage period of the contents may decrease. For this reason, the appearance of a polyester bottle having better gas barrier properties than before has been desired.

In recent years, it has been required to shorten the production time of bottles produced from polyester resins (particularly polyethylene terephthalate) and to improve productivity.
As a method of shortening the bottle manufacturing time, a method of shortening the crystallization time of the plug portion and the heat setting time of the bottle is effective. In order to shorten the crystallization time of the plug and the heat setting time of the bottle body, it is necessary to use a polyester having a high crystallization rate.

[0006] However, some of the conventional polyesters have a high crystallization rate and can be heated and crystallized in a short time, but there is a problem that the transparency of the obtained bottle is reduced. .

For this reason, if a bottle or the like having a high heating crystallization rate and excellent transparency and gas barrier properties can be manufactured, its industrial value is extremely large. The present inventors have studied polyester bottles having a high crystallization rate and excellent transparency and gas barrier properties, and have found that the above-mentioned properties can be obtained by forming the bottle into a laminate of a specific polyester and another resin. The present inventors have found that a polyester bottle excellent in the present invention can be obtained, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a polyester laminate having a high crystallization rate and excellent gas barrier properties, transparency and heat resistance. It is intended to be.

Another object of the present invention is to provide a method for producing a multilayer polyester bottle having excellent gas barrier properties, transparency and heat resistance.

[0010]

The polyester laminate according to the present invention comprises: [A] a dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid;
A diol structural unit derived from a diol comprising ethylene glycol and a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms, wherein the ratio of the structural unit derived from the polyalkylene glycol is based on the diol structural unit. (B) (i) at least one selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid, and a diol structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0. A second polyester that is less than 001% by weight,
It has a multilayer structure in which a second resin layer made of at least one resin selected from the group consisting of (ii) polyamide and (iii) polyolefin is laminated.

The dicarboxylic acid in the first polyester is preferably terephthalic acid. The dicarboxylic acid in the first polyester is composed of terephthalic acid and isophthalic acid, and the proportion of the structural unit derived from isophthalic acid is preferably in the range of 1 to 15% by weight based on the dicarboxylic acid structural unit.

Further, the dicarboxylic acid in the first polyester comprises naphthalenedicarboxylic acid and, if necessary, isophthalic acid, and the ratio of the structural unit derived from naphthalenedicarboxylic acid is 100 to 55 relative to the dicarboxylic acid structural unit. Preferably it is in the range of weight%.

The degree of polymerization (n) of the polyalkylene glycol is preferably in the range of 5 to 50. In particular, the polyalkylene glycol is preferably polytetramethylene glycol.

The polyester laminate is preferably a preform and a bottle, and the bottle body preferably has a carbon dioxide gas permeability coefficient of 15.0 cc · mm / m ² · day · atm or less.

The method for producing a polyester multilayer bottle according to the present invention comprises: [A] a dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. ,
A diol structural unit derived from a diol comprising ethylene glycol and a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms, wherein the ratio of the structural unit derived from the polyalkylene glycol is based on the diol structural unit. (B) (i) at least one selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid, and a diol structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0 to the diol structural unit. A preform having a multilayer structure is produced from at least one resin selected from the group consisting of less than 0.001% by weight of a second polyester, (ii) a polyamide, and (iii) a polyolefin, and then heating the preform. Thereafter, the stretched bottle is formed by biaxial stretch blow molding, and the stretched bottle is held in a mold at a temperature of 100 ° C. or higher.

In the above manufacturing method, the preform plug may be heated and crystallized before the biaxial stretch blow molding, or the bottle plug may be heated and crystallized after the biaxial stretch blow molding. Good.

The degree of polymerization of the polyalkylene glycol is preferably in the range of 5 to 50, and particularly preferably the polyalkylene glycol is polytetramethylene glycol.

[0018]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a polyester laminate and a polyester multilayer bottle according to the present invention will be specifically described.

The polyester laminate according to the present invention comprises: [A] a dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid;
Consisting of a diol structural unit derived from a diol composed of ethylene glycol and a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms, the ratio of the structural unit derived from the polyalkylene glycol is based on the diol structural unit. 0.001 to 10% by weight
(B) (i) at least one selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid, and a diol structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0 to the diol structural unit. It has a multilayer structure in which less than 0.001% by weight of a second polyester, (ii) a polyamide, and (iii) a second resin layer made of at least one resin selected from the group consisting of polyolefins.

[A] First Resin Layer First, the first resin layer [A] will be described. The first resin layer [A] is composed of the first polyester composed of the dicarboxylic acid structural unit and the diol structural unit as described above.

First polyester Hereinafter, the dicarboxylic acid structural unit and the diol structural unit will be described. Dicarboxylic acid structural unit The dicarboxylic acid structural unit is derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, or an ester derivative thereof (eg, lower alkyl ester, phenyl ester, etc.). Structural units are the main components.

(1) In the first preferred embodiment of the present invention, as the dicarboxylic acid structural unit, a structural unit derived from terephthalic acid or an ester derivative thereof is used as a main component.

The dicarboxylic acid structural unit may contain a structural unit derived from a dicarboxylic acid other than terephthalic acid or its ester derivative in an amount of 15 mol% or less.

Specific examples of such dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; succinic acid, glutaric acid, adipic acid, sebacic acid, and the like. Aliphatic dicarboxylic acids such as azelaic acid and decanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

These dicarboxylic acids other than terephthalic acid may be ester derivatives thereof. These may be a combination of two or more. (2) In the second preferred embodiment of the present invention, as a dicarboxylic acid structural unit, a structural unit derived from terephthalic acid or an ester derivative thereof is used as a main component, and a structural unit derived from isophthalic acid or an ester derivative thereof is specified. Contained in the proportion of

In the present invention, the structural unit derived from isophthalic acid or its ester derivative in the first polyester is 1 to 15% by weight based on the dicarboxylic acid structural unit.
Preferably, it is in the range of 2 to 12% by weight, more preferably 4 to 10% by weight. A laminate in which the first polyester containing a structural unit derived from isophthalic acid in such a range is laminated has excellent heat stability during molding and gas barrier properties.

The dicarboxylic acid structural unit includes terephthalic acid,
Structural units derived from dicarboxylic acids other than isophthalic acid or their ester derivatives may be contained in an amount of 15 mol% or less.

Specific examples of dicarboxylic acids other than terephthalic acid and isophthalic acid include aromatic dicarboxylic acids such as o-phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, and naphthalenedicarboxylic acid; succinic acid, Examples include aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

These dicarboxylic acids other than terephthalic acid and isophthalic acid may be ester derivatives thereof. These may be a combination of two or more. (3) In a third preferred embodiment of the present invention, the dicarboxylic acid structural unit is mainly composed of a structural unit derived from naphthalenedicarboxylic acid or an ester derivative thereof,
If necessary, a structural unit derived from terephthalic acid, isophthalic acid or an ester derivative thereof is contained.

In the present invention, the structural unit derived from naphthalenedicarboxylic acid or an ester derivative thereof in the first polyester is 55 to 55 relative to the dicarboxylic acid structural unit.
It is desirably in the range of 100% by weight, preferably 75-100% by weight, more preferably 85-99% by weight. A laminate in which the first polyester containing a structural unit derived from naphthalenedicarboxylic acid in such a range is laminated has excellent heat stability and gas barrier property during molding.

The dicarboxylic acid structural unit may contain a structural unit derived from a dicarboxylic acid other than naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or an ester derivative thereof in an amount of 15 mol% or less.

Specific examples of dicarboxylic acids other than naphthalenedicarboxylic acid and isophthalic acid include o-phthalic acid,
Aromatic dicarboxylic acids such as diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid; alicyclic rings such as cyclohexanedicarboxylic acid Group dicarboxylic acids and the like.

These dicarboxylic acids other than naphthalenedicarboxylic acid and isophthalic acid may be ester derivatives thereof. These may be a combination of two or more.

Diol Structural Unit The diol structural unit mainly comprises a structural unit derived from ethylene glycol, and a specific ratio of a structural unit derived from a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms. Contains.

The polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms which forms the constituent unit of the polyalkylene glycol diol is a conventionally known polyalkylene glycol. Such a polyalkylene glycol has 2 to 10 carbon atoms. Are co-condensed by a known method.

The degree of polymerization (n) of the polyalkylene glycol is preferably in the range of 5 to 50, preferably 10 to 45. The molecular weight of such a polyalkylene glycol is 100 to 10,000, preferably 200
5,000, particularly preferably 500-3000.

Specific examples of such polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, and the like.
Particularly, polytetramethylene glycol is preferable.

In the present invention, the structural unit derived from the polyalkylene glycol in the first polyester is 0.001 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.01 to 8% by weight, based on the diol structural unit. It is desirable that the content be in the range of 0.1 to 6% by weight, particularly preferably 1 to 4% by weight.

When the amount of the structural unit derived from the polyalkylene glycol is less than 0.001% by weight, the gas barrier property and the rate of temperature increase crystallization of the polyester laminate may not be sufficient. If it exceeds, the transparency of the polyester laminate and the thermal stability during molding may not be sufficient.

The other diol diol structural unit may contain a diol other than ethylene glycol and a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms in an amount of 15 mol% or less.

Examples of the diol other than ethylene glycol and polyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol (propanediol), butanediol, pentanediol, neopentyl glycol, and hexamethylene glycol. Aliphatic glycols such as glycol and dodecamethylene glycol; alicyclic glycols such as cyclohexanedimethanol; and aromatic diols such as bisphenols and hydroquinone.

These diols may be ester derivatives thereof. These diols may be a combination of two or more. The first polyester used in the present invention is, if necessary, trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane,
A small amount of a structural unit derived from a polyfunctional compound such as trimethylolmethane or pentaerythritol,
It may be contained in a ratio of not more than mol%.

The first polyester is produced by a conventionally known production method from a dicarboxylic acid and a diol which form the above structural units. Such a first polyester is substantially linear, as confirmed by its dissolution in o-chlorophenol.

The first polyester has an intrinsic viscosity [IV] measured in o-chlorophenol at 25 ° C. of usually 0.3 to
It is desirably 1.5 dl / g, preferably 0.5 to 1.5 dl / g.

The first polyester has a half-crystallization time of 1
It is desirably in the range of 0 to 200 seconds, preferably 20 to 120 seconds. The half-crystallization time is measured as described later.

The first resin layer as described above may contain additives such as a coloring agent, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant and a lubricant, if necessary. Also,
It may contain a polyester other than the first polyester, a polyamide, a polyolefin, or the like. [B] Second Resin Layer Next, the second resin layer [B] will be described.

The second resin layer [B] comprises (i) terephthalic acid,
A dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of isophthalic acid and naphthalenedicarboxylic acid, and a diol structural unit derived from a diol containing ethylene glycol, derived from a polyalkylene glycol It is composed of at least one resin selected from the group consisting of a second polyester, (ii) polyamide, and (iii) polyolefin, in which the proportion of the constituent unit is less than 0.001% by weight based on the diol constituent unit.

Hereinafter, each resin will be specifically described. (i) Second polyester (i) The second polyester contains a dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and ethylene glycol It comprises a structural unit derived from a diol, and the proportion of the structural unit derived from a polyalkylene glycol is less than 0.001% by weight based on the diol structural unit.

As the (i) second polyester, the following polyesters may be mentioned. Polyethylene terephthalate comprising a dicarboxylic acid structural unit derived from terephthalic acid or an ester derivative thereof and a diol structural unit derived from ethylene glycol.

[0050] Such polyethylene terephthalate may contain other dicarboxylic acids and / or
Alternatively, it may contain a structural unit derived from another diol.

Specific examples of other dicarboxylic acids include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, o-phthalic acid, diphenyldicarboxylic acid and diphenoxyethanedicarboxylic acid; and sebacic acid, azelaic acid and decanedicarboxylic acid. Aliphatic dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid;

Examples of other diols include aliphatic glycols such as diethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, dodecamethylene glycol and polyalkylene glycol; alicyclic glycols; Aromatic diols such as hydroquinone and 2,2-bis (4-β-hydroxyethoxyphenyl) propane;

The intrinsic viscosity [IV] (measured in o-chlorophenol at 25 ° C.) of such polyethylene terephthalate is usually 0.6 to 1.5 dl / g, preferably 0.7 to 1.5 dl / g.
It is desirably 1.2 dl / g.

Polyethylene naphthalate comprising a dicarboxylic acid structural unit whose main component is a structural unit derived from naphthalenedicarboxylic acid or an ester derivative thereof, and a diol structural unit whose main component is a structural unit derived from ethylene glycol.

Such polyethylene naphthalates may contain structural units derived from other dicarboxylic acids and / or other diols in amounts of less than 40 mol%.

Examples of other dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid and dibromoterephthalic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decane dicarboxylic acid; 1,4-cyclohexanedicarboxylic acid and cyclopropane dicarboxylic acid Acids, alicyclic dicarboxylic acids such as hexahydroterephthalic acid; and hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-hydroxyethoxybenzoic acid.

Examples of other diols include propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, polyalkylene glycol, and p-xylene. Glycol, 1,4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxysulfone, 1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenol)
And propane, p-phenylenebis (dimethylsiloxane), glycerin and the like.

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

Further, the polyethylene naphthalate used in the present invention contains not more than 2 mol% of structural units derived from monofunctional compounds such as benzoylbenzoic acid, diphenylsulfonemonocarboxylic acid, stearic acid, methoxypolyethylene glycol and phenoxypolyethylene glycol. May be included in quantity.

The intrinsic viscosity [IV] (measured in o-chlorophenol at 25 ° C.) of such polyethylene naphthalate is usually 0.2 to 1.1 dl / g, preferably 0.3 to 0.3 dl / g.
It is desirably in the range of 9 dl / g, particularly preferably in the range of 0.4 to 0.8 dl / g.

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

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

The main component is a structural unit derived from terephthalic acid or an ester derivative thereof, and a dicarboxylic acid structural unit containing a specific ratio of a structural unit derived from isophthalic acid or an ester derivative thereof, and ethylene glycol. And a diol constituent unit.

The structural unit derived from isophthalic acid or an ester derivative thereof is in the range of 0.5 to 15 mol%, preferably 0.5 to 10 mol%, based on the dicarboxylic acid structural unit constituting the copolymerized polyester. Desirably.

A structural unit derived from terephthalic acid or an ester derivative thereof as a main component, a dicarboxylic acid structural unit containing a specific ratio of a structural unit derived from naphthalenedicarboxylic acid or an ester derivative thereof, and a structural unit derived from ethylene glycol And a diol constituent unit.

The structural unit derived from naphthalenedicarboxylic acid or its ester derivative is 0.5 to 0.5 relative to the dicarboxylic acid structural unit constituting the copolymerized polyester.
It is desirably in the range of 20 mol%, preferably 0.5 to 10 mol%.

A structural unit derived from terephthalic acid or an ester derivative thereof is used as a main component, and a dicarboxylic acid structural unit containing a specific unit of a structural unit derived from adipic acid or an ester derivative thereof, and a structural unit derived from ethylene glycol. And a diol constituent unit.

The structural unit derived from adipic acid or an ester derivative thereof is 0.5 to 15 mol% based on the dicarboxylic acid structural unit constituting the copolymerized polyester.
Preferably, it is in the range of 0.5 to 10 mol%.

A dicarboxylic acid structural unit derived from terephthalic acid or an ester derivative thereof and a diol structural unit containing a structural unit derived from ethylene glycol as a main component and a specific ratio of a structural unit derived from diethylene glycol, A copolymerized polyester consisting of

The structural unit derived from diethylene glycol is used in an amount of 0.5 to 5% by weight, preferably 1.0 to 5% by weight, based on the diol structural unit constituting the copolymerized polyester.
Desirably, it is in the range of 3.0% by weight.

A diol composition containing a dicarboxylic acid structural unit derived from terephthalic acid or an ester derivative thereof and a structural unit derived from ethylene glycol as main components, and a structural unit derived from neopentyl glycol in a specific ratio. Copolymerized polyester consisting of units.

The structural unit derived from neopentyl glycol is 1.0 to 30% by weight, preferably 5 to 30% by weight, based on the diol structural unit constituting the copolymerized polyester.
It is desirably in the range of 15% by weight.

A diol component containing a dicarboxylic acid structural unit derived from terephthalic acid or an ester derivative thereof, a structural unit derived from ethylene glycol as a main component, and a specific ratio of a structural unit derived from cyclohexanedimethanol. Copolymerized polyester consisting of units.

The structural unit derived from cyclohexanedimethanol is 1 to 30% by weight, preferably 5 to 30% by weight, based on the diol structural unit constituting the copolymerized polyester.
It is desirably in the range of 15% by weight.

A structural unit derived from isophthalic acid or an ester derivative thereof as a main component, a dicarboxylic acid structural unit containing a structural unit derived from a terephthalic acid or an ester derivative thereof as necessary, and a structural unit derived from dihydroxyethoxyresole. Polyester comprising a structural unit represented by the formula: and a diol structural unit containing a structural unit derived from ethylene glycol.

The structural unit derived from isophthalic acid is
It is desirably in the range of 20 to 100% by weight, preferably 50 to 98% by weight, based on the dicarboxylic acid constituting units constituting the copolymerized polyester.

It is desirable that the constituent unit derived from dihydroxyethoxyresole is in the range of 5 to 90 mol%, preferably 10 to 85 mol%, based on the diol constituent unit of the copolymerized polyester.

Further, the above-mentioned copolymerized polyester includes:
The structural unit derived from the polyfunctional hydroxy compound having at least three hydroxy groups is 0.05 to 1.0 mole part, preferably 0.1 to 0.5 mole, per 100 mole parts of the dicarboxylic acid structural unit. Desirably it is present in parts by volume.

Examples of the polyfunctional hydroxy compound having at least three hydroxy groups include trimethylolmethane, trimethylolethane, and trimethylolpropane. Of these, trimethylolpropane is preferred.

In addition to the above-mentioned dicarboxylic acids and diols, the above-mentioned copolyesters may contain other dicarboxylic acids and / or diols in an amount not to impair the properties of the obtained copolyesters, for example, 1 mol% or less. It may contain structural units derived from other diols.

Other dicarboxylic acids include o-phthalic acid,
2-methylterephthalic acid and the like, and other diols include 1,3-propanediol, 1,4-butanediol,
Cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy)
Benzene, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, bis (4-β-hydroxyethoxyphenyl)
Sulfone and the like.

The intrinsic viscosity (IV: a value measured at 25 ° C. in o-chlorophenol) of such a copolymerized polyester is usually 0.5 to 1.5 dl / g, preferably 0.6 to 1.5 dl / g.
It is desirably 2 dl / g.

The second polyester (i) as described above can be produced by a conventionally known production method. (ii)
Polyamide (ii) As polyamide, nylon-6, nylon-6
6, Nylon-10, Nylon-12, Nylon-46
And polyamides produced from an aromatic dicarboxylic acid and an aliphatic diamine. Nylon-6 is particularly preferred. Such polyamides may be used alone or in combination of two or more.

Such a polyamide can be produced by a conventionally known production method. (iii) Polyolefins (iii) Polyolefins include polyethylene, polypropylene, poly-1-butene, polymethylpentene, olefin homopolymers such as polymethylbutene, and olefin copolymers such as propylene / ethylene random copolymer. And polyethylene and polypropylene are particularly preferred. Such polyolefins may be used alone or in combination of two or more.

Such a polyolefin can be produced by a conventionally known production method. In the present invention,
The second resin layer [B] may be formed from a blend of the above resins (i) to (iii), and specifically, a blend of polyethylene terephthalate and polyethylene naphthalate, and a copolymer of polyethylene terephthalate and polyester Blend with polyethylene terephthalate and copolyester, blend with polyethylene terephthalate and copolyester,
A blend of polyethylene terephthalate and a copolymerized polyester is exemplified.

The second resin layer [B] may contain, if necessary, additives usually added to polyester, such as coloring agents, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants,
A lubricant may be contained.

Next, the polyester laminate according to the present invention will be described. In the polyester laminate according to the present invention, the first resin layer [A] and the second resin layer [B] are laminated. Such a polyester laminate has a first thickness relative to the total thickness.
The resin layer [A] has a thickness of 5 to 30%, preferably 5 to 20%, more preferably 5 to 15%, and the second resin layer [B] has a thickness of 70 to 95%, preferably 80 to 95%. More preferably, the thickness is 85 to 95%.

The polyester laminate according to the present invention has a third resin layer other than the first resin layer [A] and the second resin layer [B].
The layers may be stacked. Layers other than the first resin layer [A] and the second resin layer [B] include the first resin layer [A] and the second resin layer [B].
A composition layer of a resin constituting the layer and a resin constituting the second layer, and a layer containing a heat stabilizer, a weather stabilizer, a lubricant, a dye, a pigment, an antifogging agent, an antistatic agent, etc. Or a layer provided as an intermediate layer, or a layer for bonding the first resin layer and the second resin layer, such as a layer made of glass, metal, or paper, such as a modified polyolefin layer.

The laminate according to the present invention can be manufactured by a conventionally known method using the above resin.
Since such a laminate according to the present invention has a high crystallization rate, for example, when molding a bottle, the time for heating and crystallizing the plug portion of the preform or the plug portion of the bottle should be shortened. It is possible to efficiently manufacture a bottle having excellent mechanical strength and heat resistance of the plug portion.

When the polyester laminate according to the present invention is a preform or a bottle, the outer peripheral surface layer is preferably formed of the first resin layer [A]. Furthermore, when the polyester laminate according to the present invention is a bottle, the carbon dioxide permeability coefficient of the body of the bottle is 15.0 cc · mm / m ² · day.
· Atm or less, preferably 13.0 cc · mm / m ² · day · atm or less, more preferably 10.0 cc · mm / m ² · day · atm or less.

Such a bottle is specifically manufactured by the following method. Method for Producing Polyester Multilayer Bottle In the method for producing a polyester multilayer bottle according to the present invention, [A] is derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. A dicarboxylic acid structural unit,
A diol structural unit derived from a diol comprising ethylene glycol and a polyalkylene glycol having an alkylene chain having 2 to 10 carbon atoms, wherein the ratio of the structural unit derived from the polyalkylene glycol is based on the diol structural unit. (B) (i) at least one selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid, and a structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0. A preform having a multilayer structure is produced from at least one resin selected from the group consisting of the second polyester, which is less than 001% by weight, (ii) polyamide, and (iii) polyolefin.

[0092] Such a preform may be formed by a conventionally known molding method of the resins [A] and [B], for example, coextrusion molding, coinjection molding and the like.
The outer peripheral surface layer of the preform is preferably formed of the first resin layer [A]. Further, the first resin layer [A] accounts for 5 to 30%, preferably 5 to 30% of the total thickness of the preform.
The thickness is 20%, more preferably 5 to 15%, and the second resin layer [B] is 70 to 95%, preferably 80 to 95%.
%, More preferably 85 to 95%. In such a preform, since it is possible to form a bottle with high stretching, the length may be shorter than the conventional preform, and the diameter of the preform may be smaller than that of the conventional preform. it can.

Next, in the method for producing a polyester multi-layer bottle according to the present invention, the preform is heated and then biaxially stretched and blow-molded to form a stretched bottle. Hold in a mold at a temperature of 110 ° C. or higher.

The temperature for heating the preform is 70 to 1
It is desirable that the temperature is 50 ° C, preferably 80 to 140 ° C. At this time, the preform is heated from the outside and the hollow portion, and an infrared source or the like can be used as a heat source.
It is preferable that the heating from the hollow portion is performed simultaneously with the external heating of the preform.

The stretching ratio at the time of biaxial stretch blow molding is as follows:
Area stretch ratio (longitudinal stretch ratio × transverse stretch ratio) of 6 to 15
Times, preferably 7 to 12 times. In the present invention, the obtained stretched bottle may be further heat-set. The heat setting is 100 to 240 ° C, preferably 110 to 220 ° C, particularly preferably 140 to 210 ° C.
It is desirable that the temperature is maintained at a mold temperature of 1 ° C. for 1 second or more, preferably 3 seconds or more. The stretch bottle is
Heat setting improves heat resistance and gas barrier properties.

In the present invention, the plug portion of the preform may be heated and crystallized before the biaxial stretch blow molding, or the biaxial portion may be heated and crystallized without heating the plug portion of the preform. After stretching blow molding, heat the stopper of the stretch bottle
It may be crystallized.

The heating and crystallization of the plug portion of the preform and the heating and crystallization of the plug portion of the stretched bottle are 100 to 20.
It is carried out at a temperature of 0 ° C, preferably 120-180 ° C.
By this heating and crystallization, the crystallinity of the plug of the preform or the crystal of the plug of the bottle is 25 to 60%,
Preferably, it is desirable to be in the range of 25 to 50%.

[0098] The carbon dioxide gas transmission coefficient of the body of the polyester multi-layer bottle thus obtained is usually 15 cc · mm / m
²・ day ・ atm or less, preferably 13cc ・ mm / m ²・ day ・ atm
Or less and more preferably not more than ^{10cc · mm / m 2 · day} · atm. The haze of the obtained polyester multilayer bottle is usually 1.0 to 20%, preferably 5 to 20%.
It is desirable to be in the range of １５15%.

According to the method of the present invention, since the transparency of the bottle body is hardly reduced, a polyester multilayer bottle excellent in transparency, gas barrier properties and heat resistance can be produced.

Further, according to the method of the present invention, since the heating and crystallization of the preform plug or the bottle plug can be performed at a high speed, the bottle molding cycle including the step of heating and crystallizing the plug is performed. Can be shortened, and a polyester multilayer bottle excellent in gas barrier properties, transparency and heat resistance can be manufactured with high productivity.

[0101]

The polyester laminate according to the present invention has an excellent crystallization rate, and is excellent in gas barrier properties, transparency and heat resistance. Further, the polyester laminate according to the present invention is suitable for bottles and preforms.

According to the method for producing a polyester multi-layer bottle according to the present invention, a multi-layer bottle excellent in gas barrier properties, transparency and heat resistance, and having excellent mechanical strength and heat resistance of a plug portion can be produced with high productivity. can do.

[0103]

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

In the examples, each characteristic was measured as follows. Intrinsic viscosity [IV] A sample solution of 8 g / dl was prepared using o-chlorophenol solvent, and calculated from the solution viscosity measured at 25 ° C.

Carbon dioxide gas permeability coefficient (gas barrier property) The obtained bottle body section was cut out and used as a carbon dioxide gas permeability coefficient measuring film using a gas permeability measuring device GPM-250 manufactured by GL Sciences Corporation. ℃,
The measurement was performed under the condition of a relative humidity of 60%.

The half-crystallization time was measured using a differential scanning calorimeter (DSC) manufactured by Perkin Elmer. 10 mg of the body section of the multi-layer bottle was weighed into a sample pan, melted by heating at 290 ° C. for 5 minutes, then rapidly cooled to 50 ° C. at a cooling rate of 320 ° C./min and left for 5 minutes to remove the amorphous sample. Make it. 320 ° C
/ Min at a heating rate of / min and maintained at that temperature. The sample crystallized at this temperature to give a time-heat curve, from which the total heat value was determined. The half-crystallization time was defined as the time (seconds) required to generate half the amount of heat generated.

The shorter the half-crystallization time, the more efficiently the crystallization proceeds, and the higher the productivity of the bottle. Evaluation of heat resistance 40 ° C. for the multilayer bottle obtained as described above,
After leaving for 1 week under the condition of 90% humidity, 9
Hot water at 0 ° C. was filled for 10 minutes, and the contents before and after filling were measured.

From the contents before and after filling, the shrinkage (%) was determined by the following equation.

[0109]

(Equation 1)

From the value of the shrinkage (%) thus determined, the heat resistance was evaluated according to the following criteria. : 0 ≦ shrinkage ratio (%) <0.5 ×: 0.5 ≦ shrinkage ratio (%) Bottle appearance The haze value of the body of the obtained multilayer bottle was measured.

From the haze value (%), the appearance of the bottle was evaluated as follows. : 0 ≦ Haze value (%) <5 ×: 5 ≦ Haze value (%)

[0112]

Example 1 Polyester [A-1] 198 parts by weight of naphthalenedicarboxylic acid and 16 parts by weight of isophthalic acid as a dicarboxylic acid component, 68 parts by weight of ethylene glycol as a diol component and an average molecular weight of 100
Polyester [A-1] having an intrinsic viscosity [IV] of 0.643 dl / g was obtained by using 1.9 parts by weight of polytetramethylene glycol of No. 0.

Polyester [A-1] forming the first resin layer and polyester [B-1] forming the second resin layer (polyethylene terephthalate, diethylene glycol content; 1.95% by weight, intrinsic viscosity [ IV] = 0.835dl / g) and the cylinder temperature is 280 ° C
Is melted using an extruder, and supplied to the two-layer two-layer die in the order of [A-1] and [B-1] from the outer peripheral surface of the preform, and the thickness of [A-1] Is 0.6mm, the thickness of [B-1] is 5.4mm,
A two-layer pipe with a total thickness of 6 mm was formed. At this time, the temperature of the cooling water was 50 ° C., and the outer diameter of the obtained pipe was 2 mm.
It was 2 mm.

The obtained pipe was cut off, one end was heated and melted to form a bottom portion, and the other end was similarly heated and melted to form a plug portion. The total length was 70 mm and the weight was 23 g.
Was obtained.

Preparation of Bottle This multilayer preform was heated to a stretching temperature of 100 to 130 ° C., and was blown at a blowing pressure of 25 using a biaxial stretch blow molding machine.
The preform was successively biaxially stretched and blow-molded three times vertically and three times horizontally at kg / cm ² to produce a bottle. The obtained bottle body was heat-set at 150 ° C. for 1 minute.

The half-crystallization time, carbon dioxide permeability coefficient, heat resistance and appearance of the bottle were evaluated.
Table 1 shows the results.

[0117]

Embodiment 2 In Embodiment 1, the thickness of [A-1] is 0.9 m.
A bottle was prepared and evaluated in the same manner as in Example 1 except that the preform was formed so that the thickness of m and [B-1] was 5.1 mm. Table 1 shows the results.

[0118]

Example 3 Polyester [A-2] 198 parts by weight of naphthalenedicarboxylic acid and 16 parts by weight of isophthalic acid as a dicarboxylic acid component, 68 parts by weight of ethylene glycol as a diol component and an average molecular weight of 200
Polyester [A-1] having an intrinsic viscosity [IV] of 0.648 dl / g was obtained by using 1.9 parts by weight of polytetramethylene glycol of No. 0.

[0119] In Example 1, the above-mentioned
A bottle was prepared and evaluated in the same manner as in Example 1 except that [A-2] was used. Table 1 shows the results.

[0120]

Fourth Embodiment In the first embodiment, the above-mentioned method is adopted in place of [A-1].
Example 1 was repeated except that [A-2] was used and the preform was formed so that the thickness of [A-2] was 0.9 mm and the thickness of [B-1] was 5.1 mm. Similarly, a bottle was prepared and evaluated.
Table 1 shows the results.

[0121]

Example 5 Polyester [A-3] 206 parts by weight of naphthalenedicarboxylic acid and 8 parts by weight of isophthalic acid as a dicarboxylic acid component, 68 parts by weight of ethylene glycol as a diol component and an average molecular weight of 1000
And 1.9 parts by weight of the polytetramethylene glycol of Example 1 to obtain a polyester [A-3] having an intrinsic viscosity [IV] of 0.622 dl / g.

In Example 1, instead of [A-1], the above
A bottle was prepared and evaluated in the same manner as in Example 1 except that [A-3] was used. Table 1 shows the results.

[0123]

[Embodiment 6] In Embodiment 1, the above-mentioned method was used instead of [A-1].
Example 1 was repeated except that [A-3] was used and the preform was formed so that the thickness of [A-3] was 0.9 mm and the thickness of [B-1] was 5.1 mm. Similarly, a bottle was prepared and evaluated.
Table 1 shows the results.

[0124]

Example 7 Intrinsic viscosity using 214 parts by weight of naphthalenedicarboxylic acid as a first polyester [A-4] dicarboxylic acid component and 1.9 parts by weight of polytetramethylene glycol having an ethylene glycol of 68 parts by weight and an average molecular weight of 1000 as a diol component A first polyester [A-4] having an [IV] of 0.613 dl / g was obtained.

In Example 1, the above-mentioned method was used instead of [A-1].
A bottle was prepared and evaluated in the same manner as in Example 1 except that [A-4] was used. Table 1 shows the results.

[0126]

[Embodiment 8] In Embodiment 1, the above-mentioned method was used instead of [A-1].
Example 1 was repeated except that [A-4] was used and the preform was formed such that the thickness of [A-4] was 0.9 mm and the thickness of [B-1] was 5.1 mm. Similarly, a bottle was prepared and evaluated.
Table 1 shows the results.

[0127]

Comparative Example 1 In Example 1, without using [A-1],
6m thick consisting only of polyethylene terephthalate [B-1]
A bottle was prepared and evaluated in the same manner as in Example 1 except that a preform of m was formed. Table 1 shows the results.

[0128]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 67:00 C08G 63/181 B29L 9:00 63/672 22:00

Claims (14)

[Claims] [A] a dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; ethylene glycol; A diol structural unit derived from a diol comprising a polyalkylene glycol having an alkylene chain, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0.001 to 10 relative to the diol structural unit.
(B) (i) at least one resin selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid and a diol structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0 to the diol structural unit. A polyester laminate having a multilayer structure in which a second resin layer of at least one resin selected from the group consisting of a second polyester, which is less than 0.001% by weight, (ii) a polyamide, and (iii) a polyolefin is laminated. 2. The polyester laminate according to claim 1, wherein the dicarboxylic acid in the first polyester is terephthalic acid. 3. The dicarboxylic acid in the first polyester is terephthalic acid and isophthalic acid, and the ratio of the structural unit derived from isophthalic acid is in the range of 1 to 15% by weight based on the dicarboxylic acid structural unit. The polyester laminate according to claim 1, wherein: 4. The dicarboxylic acid in the first polyester comprises naphthalenedicarboxylic acid and, if necessary, isophthalic acid, and the ratio of the structural unit derived from naphthalenedicarboxylic acid is 100 to the dicarboxylic acid structural unit.
2. The polyester laminate according to claim 1, wherein the amount is in a range of from about 55% by weight to about 55% by weight. 3. 5. The polyester laminate according to claim 1, wherein the degree of polymerization (n) of the polyalkylene glycol is in the range of 5 to 50. 6. The polyester laminate according to claim 1, wherein said polyalkylene glycol is polytetramethylene glycol. 7. The polyester laminate according to claim 1, wherein the polyester laminate is a bottle. 8. The bottle body has a carbon dioxide gas permeability coefficient of 15.0 c.
The polyester laminate according to claim 7, wherein the thickness is not more than c · mm / m ² · day · atm. 9. The polyester laminate according to claim 1, wherein said polyester laminate is a preform. 10. A dicarboxylic acid structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, ethylene glycol and a compound having 2 to 10 carbon atoms. A diol structural unit derived from a diol comprising a polyalkylene glycol having an alkylene chain, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0.001 to 10 relative to the diol structural unit.
(B) (i) at least one selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid;
A dicarboxylic acid structural unit derived from a kind of dicarboxylic acid, and a diol structural unit derived from a diol containing ethylene glycol, wherein the ratio of the structural unit derived from the polyalkylene glycol is 0. A second polyester that is less than 001% by weight,
A preform having a multilayer structure is produced from at least one resin selected from the group consisting of (ii) polyamide and (iii) polyolefin, and then the preform is heated, and then biaxially stretched and blow-molded to form a stretch bottle. , And holding the stretched bottle in a mold at a temperature of 100 ° C or higher. 11. The method for producing a polyester multilayer bottle according to claim 10, wherein the preform plug is heated and crystallized before the biaxial stretch blow molding. 12. The method for producing a polyester multilayer bottle according to claim 10, wherein the bottle plug is heated and crystallized after the biaxial stretch blow molding. 13. The method for producing a polyester multilayer bottle according to claim 10, wherein the degree of polymerization of the polyalkylene glycol is in the range of 5 to 50. 14. The method for producing a polyester multilayer bottle according to claim 10, wherein the polyalkylene glycol is polytetramethylene glycol.