CN1177968A - Polyester, polyester composition, polyester laminative, and process for producing biaxially stretched polyester bottles - Google Patents

Abstract

The novel polyester [A] comprises units derived from at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and derived from ethylene glycol and alkylene groups having 2 to 10 carbon atoms The diol component unit of the chain polyalkylene glycol, wherein the proportion of the component unit derived from polyalkylene glycol is 0.001-10% by weight of the diol component unit. [A] has an excellent crystallization rate and can be used alone or in combination with another polyester [B] and/or other polymers to produce molded products with excellent gas barrier properties, transparency and heat resistance. It also discloses the structure of the laminated product and the method for producing the biaxially stretched polyester bottle of the present invention.

Description

Polyesters, compositions and laminates thereof and method for producing biaxially stretched polyester bottles

technical field of invention

The present invention relates to novel polyesters, polyester compositions, polyester laminates and methods of producing biaxially oriented polyester bottles. More specifically, the present invention relates to polyesters and compositions thereof which are excellent in high crystallization rate, high gas barrier properties, high transparency and heat resistance, and also relates to the production of preforms, biaxially oriented bottles and laminates from polyesters Articles, and methods of producing biaxially oriented polyester bottles having excellent gas barrier properties, transparency and heat resistance.

Technical Background of the Invention

Saturated polyesters such as polyethylene terephthalate are widely used for containers such as bottles due to their excellent gas barrier properties, transparency and mechanical strength. In particular, bottles obtained by biaxially oriented blow molding of polyethylene terephthalate have excellent transparency, mechanical strength, heat resistance and gas barrier properties, so they are widely used for filling beverages, such as juices, soft drinks and Containers for carbonated drinks (PET bottles). The process of producing this type of bottle generally includes the following steps, molding saturated polyester to obtain a preform with a bottleneck and a bottle body, and then inserting the preform into a mold of a certain shape to make the preform stretch blow molding to produce a bottle neck And stretch the bottle of the bottle.

Polyester bottles, especially those used for beverages such as juices, are required to have a high enough heat resistance to withstand the temperature of heat sterilizing the contents of the bottle. Therefore, after blow molding, the bottle is generally further heat-treated (heat-set) to improve heat resistance.

However, the neck of the above-mentioned polyester bottle is not stretched, and its heat resistance is inferior to that of the bottle body. Therefore, generally, the neck of the preform is thermally crystallized before blow molding, or the neck of the bottle is obtained by thermal crystallization blow molding, so as to improve the mechanical strength and heat resistance.

In recent years, the size of bottles produced from polyester resins, especially polyethylene terephthalate, has tended to be smaller. For small-sized bottles, the contact area between the substance in the bottle and the bottle body per unit volume increases, so the significant loss of gas in the substance in the bottle or the infiltration of oxygen from the outside of the bottle will affect the substance in the bottle, resulting in a reduction in the shelf life of the substance in the bottle. Therefore, it is required to develop polyester bottles whose gas barrier properties are superior to ordinary bottles.

Recently, it is also required to shorten the time for producing bottles from polyester resins in order to increase productivity. In order to shorten the time of bottle production, the effective method is to shorten the crystallization time of the bottle neck or the heat setting time of the bottle body.

However, shortening the crystallization time of the bottle neck or the heat setting time of the bottle body generally leads to a decrease in the mechanical strength and heat resistance of the product bottle. Therefore, in order to carry out the crystallization of the bottle neck or the heat setting of the bottle body in a short time, it is necessary to use a polyester with a high crystallization rate. An example of a polyester known to have a high crystallization rate is a polyester resin composition composed of virgin polyester and recycled polyester. As used herein, the term "new polyester" refers to polyesters prepared from dicarboxylic acids and diols which have not been passed through molding machines in the molten state to form any bottles or preforms. The term "regenerated polyester" as used herein refers to a polyester obtained by passing virgin polyester in a molten state through a molding machine at least once and pulverizing the resulting polyester molded product.

Although some polyester resin compositions have a high crystallization rate and can be thermally crystallized in a short time, the resulting bottles suffer from a problem of reduced transparency.

Therefore, the development of polyesters capable of producing molded articles such as bottles having excellent transparency and gas barrier properties has been demanded. There is also a need to develop preforms and biaxially stretched bottles, and methods of producing biaxially stretched polyester bottles from such polyesters.

purpose of invention

The present invention has been made under the circumstances described above, and an object of the present invention is to provide a polyester and a polyester composition having a high crystallization rate, excellent gas barrier properties, transparency and heat resistance.

Another object of the present invention is to provide a preform made of the above-mentioned polyester and a biaxially stretched bottle and a polyester laminate having excellent gas barrier properties, transparency and heat resistance.

Still another object of the present invention is to provide a method for producing a biaxially stretched polyester bottle, by which a bottle having excellent gas barrier properties, transparency and heat resistance can be produced, and a bottle having excellent gas barrier properties can be produced at high productivity. Process for biaxially stretching polyester bottles for barrier properties, clarity and heat resistance.

Detailed description of the invention

The novel polyester of the present invention (the first polyester [A]), which comprises:

from at least one dicarboxylic acid component unit selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and

Diol component units derived from polyalkylene glycols comprising ethylene glycol and alkylene chains having 2 to 10 carbon atoms,

The proportion of the component units derived from polyalkylene glycols is in the range of 0.001 to 10% by weight of the diol component units.

The polyester composition of the present invention comprises:

1-99% by weight of the first polyester [A]; and

1-99% by weight of the second polyester [B], [B] comprising units derived from at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid and derived from Diol component units of alcohol, wherein the proportion of component units derived from polyalkylene glycols is less than 0.001% by weight of the diol component units.

Each preform and biaxially stretched bottle of the present invention comprises a first polyester [A].

The polyester laminate of the present invention has the following multilayer structure:

[I] a first resin layer formed from the first polyester [A] or polyester composition of the present invention, and

[II] A second resin layer formed of at least one resin selected from (a) second polyester [B], (b) polyamide and (c) polyolefin.

The method of the present invention for producing a biaxially stretched bottle comprises the steps of producing a preform from the first polyester [A], polyester composition or polyester laminate, heating the preform, biaxially stretch blow molding The preform is obtained as a stretched bottle, and the stretched bottle is kept in a mold not lower than 100°C.

In the above method, the neck of the preform is thermally crystallized before biaxial stretch blow molding, or the neck of the bottle is thermally crystallized after biaxial stretch blow molding.

Best Mode for Carrying Out the Invention

The polyester of the present invention (the first polyester [A]), the preform and the biaxially stretched bottle made of the polyester, the polyester composition, the polyester laminate and the production of the biaxially stretched bottle are described in detail below. Method for stretching polyester bottles.

The first polyester [A]

The first novel polyester [A] of the present invention, it comprises:

from at least one dicarboxylic acid component unit selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and

Diol component units derived from polyalkylene glycols comprising ethylene glycol and alkylene chains having 2 to 10 carbon atoms,

The proportion of the component units derived from polyalkylene glycols is in the range of 0.001 to 10% by weight of the diol component units.

The dicarboxylic acid component unit and the diol component unit are described below.

The dicarboxylic acid component unit in the first polyester [A]

The dicarboxylic acid component unit mainly contains at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid or its ester derivatives (such as lower alkyl esters, phenyl esters) unit.

(1) In the first preferred embodiment of the present invention, the dicarboxylic acid component unit mainly contains a component unit derived from terephthalic acid or an ester derivative thereof.

Among the dicarboxylic acid component units, the content of dicarboxylic acid component units other than terephthalic acid or its ester derivatives is not more than 15 mol%.

Examples of dicarboxylic acid component units other than terephthalic acid are:

Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, diphenyl dicarboxylic acid and diphenoxyethanedicarboxylic acid;

Aliphatic dicarboxylic acids, such as succinic, glutaric, adipic, sebacic, azelaic, and decanedicarboxylic acids; and

Cycloaliphatic dicarboxylic acids, such as cyclohexanedicarboxylic acid.

Ester derivatives of other dicarboxylic acids other than terephthalic acid may also be used. These dicarboxylic acids and their ester derivatives can be used alone or in combination.

(2) In the second preferred embodiment of the present invention, the dicarboxylic acid component unit mainly contains component units derived from terephthalic acid or its ester derivatives, and contains a certain proportion of components derived from isophthalic acid or its ester derivatives. Component unit of ester derivatives.

The content of the component unit derived from isophthalic acid or its ester derivative is required to be 1-15% by weight of the dicarboxylic acid component unit, preferably 2-12% by weight, more preferably 4-10% by weight. The first polyester containing the component unit derived from isophthalic acid in an amount within this range has excellent thermal stability during molding and excellent gas barrier properties.

Among the dicarboxylic acid component units, the content of dicarboxylic acid component units not derived from terephthalic acid, isophthalic acid or ester derivatives does not exceed 15 mol%.

Examples of dicarboxylic acids other than terephthalic and isophthalic acids are:

Aromatic dicarboxylic acids such as phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid and diphenoxyethanedicarboxylic acid;

Aliphatic dicarboxylic acids, such as succinic, glutaric, adipic, sebacic, azelaic, and decanedicarboxylic acids; and

Cycloaliphatic dicarboxylic acids, such as cyclohexanedicarboxylic acid.

Ester derivatives of other dicarboxylic acids other than terephthalic acid and isophthalic acid may also be used. These dicarboxylic acids and their ester derivatives can be used alone or in combination.

(3) In a third preferred embodiment of the present invention, the dicarboxylic acid component unit mainly contains component units derived from naphthalene dicarboxylic acid or its ester derivatives, and optionally contains components derived from terephthalic acid or isophthalic acid. Component units of phthalic acid or its ester derivatives.

The content of component units derived from naphthalene dicarboxylic acid or its ester derivatives is required to be 55-100% by weight of the dicarboxylic acid component units, preferably 75-100% by weight, more preferably 85-99% by weight. The first polyester containing the component units derived from naphthalene dicarboxylic acid in an amount within this range has excellent thermal stability during molding and excellent gas barrier properties.

Among the dicarboxylic acid component units, the content of component units not derived from naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid or their ester derivatives shall not exceed 15 mol%.

Examples of dicarboxylic acids other than naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid are:

Aromatic dicarboxylic acids, such as phthalic acid, biphenyl dicarboxylic acid and diphenoxyethanedicarboxylic acid;

Aliphatic dicarboxylic acids, such as succinic, glutaric, adipic, sebacic, azelaic, and decanedicarboxylic acids; and

Cycloaliphatic dicarboxylic acids, such as cyclohexanedicarboxylic acid.

Ester derivatives of other dicarboxylic acids other than naphthalene dicarboxylic acid, terephthalic acid and isophthalic acid may also be used. These dicarboxylic acids and their ester derivatives can be used alone or in combination.

The diol component unit in the first polyester [A]

The diol component unit mainly contains component units derived from ethylene glycol, and contains a certain proportion of component units derived from polyalkylene glycols having an alkylene chain of 2 to 10 carbon atoms.

polyalkylene glycol

Polyalkylene glycols that can form diol structural units and have an alkylene chain of 2 to 10 carbon atoms are generally known polyalkylene glycols. Polyalkylene glycols are obtained by condensing alkylene glycols having 2 to 10 carbon atoms by known methods.

It is required that the degree of polymerization (n) of the polyalkylene glycol is 5-50, preferably 10-45, and its molecular weight is 100-10,000, preferably 200-5,000, most preferably 500-3,000.

Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhepamethylene glycol, polyhexamethylene glycol, and polyoctamethylene glycol. Among them, poly-1,4-butylene glycol is most preferred.

In the present invention, it is required that the content of the polyalkylene glycol component unit in the first polyester is 0.001-10% by weight, preferably 0.01-8% by weight, more preferably based on the glycol component unit. Preferably it is 0.1-6% by weight, more preferably 1-4% by weight.

If the amount of component units derived from polyalkylene glycol is less than 0.001% by weight, gas barrier properties or thermal crystallization rate of polyester cannot be sufficiently improved. If the amount thereof exceeds 10% by weight, the polyester is inferior in transparency, thermal stability and gas barrier properties.

other diols

The diol component unit may contain a diol component unit not derived from ethylene glycol and polyalkylene glycol having an alkylene chain of 2 to 10 carbon atoms in an amount not exceeding 15 mol %.

Examples of glycols other than ethylene glycol and polyalkylene glycol include:

Aliphatic glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol (propylene glycol), butylene glycol, pentanediol, neopentyl glycol, hexamethylene glycol, and dodecamethylene base glycol;

Cycloaliphatic diols such as cyclohexanedimethanol; and

Aromatic diols such as bisphenol and hydroquinone.

Ester derivatives of these diols may also be used. These diols and their ester derivatives may be used alone or in combination.

The first polyester [A] of the present invention may optionally contain a small amount, such as not more than 2 mol%, of component units derived from polyfunctional compounds such as 1,2,4-trimesic acid, 1 , 2,4,5-pyrellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane and pentaerythritol.

The first polyester [A] of the present invention can be prepared from the above-mentioned dicarboxylic acid and diol by a known method. For example, direct esterification of dicarboxylic acid and diol, or when using an alkyl ester of dicarboxylic acid, transesterification of ester and diol, heating the reaction mixture under reduced pressure to remove excess The diol is subjected to a melt polycondensation reaction of the resulting ester to prepare the first polyester [A].

These reactions are carried out in the presence of known common catalysts. Examples of transesterification catalysts include compounds of magnesium, manganese, titanium, zinc, calcium and cobalt. Examples of polycondensation catalysts include compounds of antimony, germanium and titanium.

Any amount of transesterification catalyst or polycondensation catalyst may be used as long as the reactivity and heat resistance of polyester are not lowered.

In the polycondensation step, a phosphorus compound may be added as a stabilizer. Examples of phosphorus compounds include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate and triphenyl phosphate; phosphites such as triphenyl phosphite, tri( Lauryl) esters and trinonyl phosphite; acid phosphates such as methyl acid phosphate, propyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate esters; and other phosphorus compounds such as phosphoric and polyphosphoric acids.

In the polycondensation reaction, it is required that the amount of the polycondensation catalyst is 0.005-0.2 mol%, preferably 0.001-0.1 mol%, in terms of dicarboxylic acid and represented by metal atoms in the catalyst.

The intrinsic viscosity [IV] of the first polyester [A] thus obtained is 0.40-1.0 dl/g, preferably 0.50-0.90 dl/g.

The first polyester [A] obtained by the polycondensation reaction is generally melt-extruded into pellets (chips).

The first polyester [A] obtained by polycondensation can also be subjected to solid phase polycondensation. For example, the polyester sheet obtained above is polymerized in solid state for 8-40 hours, preferably 15-30 hours at a temperature not lower than 160°C but lower than its melting point, preferably 170-220°C.

The process for producing the first polyester [A] comprising an esterification step and a polycondensation step can be carried out batchwise or semicontinuously.

The first polyester [A] is essentially linear, as evidenced by the fact that it is soluble in o-chlorophenol.

The intrinsic viscosity of the first polyester [A] of the present invention is generally 0.3-1.5 dl/g, preferably 0.5-1.5 dl/g, as measured in o-chlorophenol at 25°C.

It is required that the temperature-rising half-crystallization time of the first polyester [A] of the present invention is 10-200 seconds, preferably 20-120 seconds. The temperature-rising half-crystallization time was measured by the method described later.

If necessary, various additives that are generally added to polyester such as colorants, antioxidants, ultraviolet light absorbers, antistatic agents, flame retardants, and lubricants can be added to the first polyester [A] .

The first polyester [A] of the present invention can be used as a molding material for various shaped products such as preforms, bottles and (stretched) films.

The first polyester [A] of the present invention has a high crystallization rate. Therefore, in the production of bottles, it is possible to shorten the thermal crystallization time of the neck of the preform or the neck, and it is possible to efficiently produce a bottle having a neck excellent in mechanical strength and heat resistance.

preforms and bottles

The preform of the present invention can be obtained by, for example, injection molding or extrusion molding of the first polyester [A].

The bottle of the invention can be obtained by biaxially stretching blow-molded preforms followed by heat-setting the resulting shaped product. In making the bottle, the neck of the preform can be thermally crystallized and then biaxially stretch blown the preform, or the preform can be biaxially stretch blow molded before the neck is thermally crystallized, and then the neck is thermally crystallized.

It is required that the carbon dioxide gas permeability rate of the bottle body of the bottle of the present invention is generally not more than 17.5cc.mm/m ^{2 .} m ² ·day·atmospheric pressure.

Particularly when the bottle is made of the first polyester [A] whose dicarboxylic acid component units mainly contain component units derived from terephthalic acid or its ester derivatives, the carbon dioxide gas permeability rate is preferably not more than 17.5 cc. mm/m ² ·day.atmospheric pressure.

When the bottle is composed of its dicarboxylic acid component units mainly containing component units derived from terephthalic acid or its ester derivatives, and also contains a certain amount of component units derived from isophthalic acid or its ester derivatives When the ester [A] is made, the carbon dioxide gas permeability rate is preferably not more than 15 cc·mm/m ² ·day·atmospheric pressure.

When the bottle is composed of dicarboxylic acid component units mainly containing component units from naphthalene dicarboxylic acid or its ester derivatives, and also contains a certain amount of terephthalic acid or isophthalic acid or its ester derivatives component units When the first polyester [A] is made, the carbon dioxide gas permeability rate is preferably not more than 4.0 cc·mm/m ² ·day·atm.

polyester composition

The polyester composition of the present invention is described below.

The polyester composition of the present invention comprises:

1-99% by weight of the first polyester [A], [A] comprising units derived from at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and Diol and diol component units of polyalkylene glycols having an alkylene chain of 2 to 10 carbon atoms, wherein the proportion of component units derived from polyalkylene glycol is in the range of 0.001 of the diol component units -10% by weight; and

1-99% by weight of the second polyester [B], [B] comprising units derived from at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and The diol component unit of the diol, wherein the proportion of the component unit derived from polyalkylene glycol is less than 0.001% by weight of the diol component unit.

The first polyester [A]

The first polyester [A] mentioned above can be used here

Second Polyester [B]

The second polyester [B] is described below.

The second polyester [B] comprises units derived from at least one dicarboxylic acid component selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and diol component units comprising less than Glycol Component Unit 0.001% by weight of a component unit derived from polyalkylene glycol.

The following are examples of the second polyester [B].

(i) Polyethylene terephthalate comprising a dicarboxylic acid component unit derived from terephthalic acid or an ester derivative thereof and a diol component unit derived from ethylene glycol.

In polyethylene terephthalate (i), the content of units derived from other dicarboxylic acids and/or other diol components is less than 20 mol%.

Examples of other dicarboxylic acids include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, biphenyl dicarboxylic acid and diphenoxyethanedicarboxylic acid; aliphatic dicarboxylic acids such as sebacic acid, Azelaic acid and decanedicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid.

Examples of other diols include aliphatic diols such as diethylene glycol, propylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, dodecamethylene glycol, and polyalkylene glycols. diols; alicyclic diols such as cyclohexanedimethanol; bisphenols; and aromatic diols such as hydroquinone and 2,2-bis(4-β-hydroxyethoxyphenyl)propane.

(ii) Polyethylene naphthalate comprising a dicarboxylic acid component unit derived from naphthalene dicarboxylic acid or an ester derivative thereof and a diol component unit derived from ethylene glycol.

In polyethylene naphthalate, the content of component units derived from other dicarboxylic acids and/or other diols is less than 40 mol %.

Examples of other dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethanedicarboxylic acid, and dibromopara Phthalic acid; aliphatic dicarboxylic acids such as adipic, sebacic, azelaic and decanedicarboxylic acids; cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopropane Dicarboxylic acids and hexahydroterephthalic acid; hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-hydroxyethoxybenzoic acid.

Examples of other diols include propylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, neopentamethylene Base glycol, polyalkylene glycol, p-xylylenedimethanol, 1,4-cyclohexanedimethanol, bisphenol A, p, p-diphenoxysulfone, 1,4-bis( β-hydroxyethoxy)benzene, 2,2-bis(p-β-hydroxyethoxyphenyl)propane, p-phenylene bis(dimethylsiloxane) and glycerin.

(iii) Copolyesters comprising dicarboxylic acid component units and diol component units derived from ethylene glycol, wherein the dicarboxylic acid component units mainly contain component units derived from terephthalic acid or its ester derivatives , also contains a certain proportion of component units from isophthalic acid or its ester derivatives.

The content of the component units derived from isophthalic acid or its ester derivatives is required to be 0.5-15 mol%, preferably 0.5-10 mol%, based on the dicarboxylic acid component units in the copolyester (iii).

(iv) Copolyesters comprising dicarboxylic acid component units and diol component units derived from ethylene glycol, wherein the dicarboxylic acid component units mainly contain component units derived from terephthalic acid or its ester derivatives , also contains a certain proportion of component units derived from naphthalene dicarboxylic acid or its ester derivatives.

The component units derived from naphthalene dicarboxylic acid or its ester derivatives are required to be contained in an amount of 0.5-20 mol%, preferably 0.5-10 mol%, based on the dicarboxylic acid component units in the copolyester (iv).

(v) Copolyesters comprising dicarboxylic acid component units and diol component units derived from ethylene glycol, wherein the dicarboxylic acid component units mainly contain component units derived from terephthalic acid or its ester derivatives , also contains a certain proportion of component units derived from adipic acid or its ester derivatives.

The component units derived from adipic acid or its ester derivatives are required to be contained in an amount of 0.5-15 mol%, preferably 0.5-10 mol%, based on the dicarboxylic acid component units in the copolyester (v).

(vi) Copolyesters comprising dicarboxylic acid component units derived from terephthalic acid or its ester derivatives and diol component units, wherein the diol component units mainly contain units derived from ethylene glycol components, and Contains a certain proportion of component units derived from diethylene glycol.

The content of the component unit derived from diethylene glycol is required to be 0.5-5% by weight, preferably 1.0-3.0% by weight, based on the diol component unit in the copolyester (vi).

(vii) Copolyesters comprising dicarboxylic acid component units and diol component units derived from terephthalic acid or its ester derivatives, wherein the diol component units mainly contain ethylene glycol component units, and Contains a certain proportion of component units derived from neopentyl glycol.

The content of the component unit derived from neopentyl glycol is required to be 1-30% by weight, preferably 5-15% by weight, based on the diol component unit in the copolyester (vii).

(viii) Copolyesters comprising dicarboxylic acid component units and diol component units derived from terephthalic acid or its ester derivatives, wherein the diol component units mainly contain ethylene glycol component units, and Contains a certain proportion of component units derived from cyclohexanedimethanol.

The content of the component unit derived from cyclohexanedimethanol is required to be 1-30% by weight, preferably 5-15% by weight, based on the diol component unit in the copolyester (viii).

(ix) copolyesters, which include:

Dicarboxylic acid constituent units which mainly contain constituent units derived from isophthalic acid or its ester derivatives, and optionally contain a proportion of constituent units derived from terephthalic acid or its ester derivatives, and

A diol component unit comprising a component unit derived from dihydroxyethoxylated phenolic resin A and a component unit derived from ethylene glycol.

The content of the isophthalic acid component unit is required to be 20-100% by weight, preferably 50-98% by weight, based on the dicarboxylic acid component unit in the copolyester (ix).

It is also required that the content of units derived from the component A of the dihydroxyethoxy phenolic resin is 5-90% by weight, preferably 10-85% by weight, based on the units of the diol component in the copolyester (ix).

In the copolyester (ix), it is also required to have component units from polyfunctional hydroxyl compounds having at least three hydroxyl groups, based on 100 mole parts of dicarboxylic acid component units, the amount is 0.05-1.0 mole parts, relatively Preferably it is 0.1-0.5 mole part.

In the copolyesters (iii)-(ix), the content of constituent units of other dicarboxylic acids and/or diols not derived from the above-mentioned dicarboxylic acids and diols should not impair the copolyesters (iii)-(ix) ) properties, for example, its content does not exceed 1 mol%.

Examples of other dicarboxylic acids include phthalic acid and 2-methylterephthalic acid. Examples of other diols include 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxy ethoxybenzene), 2,2-bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfone.

The second polyester [B] used in the present invention contains a small amount (such as no more than 2 mol%) of component units derived from polyfunctional compounds such as 1,2,4-trimesic acid, tris Methylolethane, Trimethylolpropane, Trimethylolmethane, and Pentaerythritol.

In the second polyester [B], it may also contain not more than 2 mol% of component units derived from monofunctional compounds such as benzoylbenzoic acid, diphenyl sulfone monocarboxylic acid, stearic acid , methoxypolyethylene glycol and phenoxypolyethylene glycol.

The temperature-rising crystallization temperature (Tc) of the second polyester [B] is required to be not lower than 150°C, preferably 160-230°C, more preferably 170-220°C. Tc was measured by differential scanning calorimetry (DSC) by heating the sample at a rate of 10°C/min.

The elevated temperature crystallization temperature (Tc) of the polyesters described herein was determined in the following manner. A sample slice of about 10 mg was cut from the center portion of a saturated polyester resin chip dried at about 140°C under a pressure of about 5 mm Hg for more than 5 hours. The samples were sealed in a nitrogen atmosphere aluminum pan for liquids. The DSC-2 differential scanning calorimeter produced by Perkin Elmer Co. was used for the measurement. The measurement conditions were that the sample was rapidly heated from room temperature to 290 ° C. At this temperature, the sample was kept in a molten state for 10 minutes, and then rapidly cooled to room temperature, followed by heating at a rate of 10°C/min to measure the exothermic peak. The temperature at the largest peak among these exothermic peaks was taken as the temperature-rising crystallization temperature (Tc).

The intrinsic viscosity [IV] of the second polyester [B], as measured in o-chlorophenol at 25°C, is generally 0.5-1.5 dl/g, preferably 0.6-1.2 dl/g.

The second polyester [B] can be prepared by known ordinary methods.

The second polyester [B] may be used alone or in a blend of two or more such polyesters. Examples of polyester blends include blends of polyethylene terephthalate (i) and polyethylene naphthalate (ii), polyethylene terephthalate and at least one A blend of the copolyesters of (iii)-(ix), a blend of at least two copolyesters of (iii)-(ix).

Of the blends, preferably used are blends of polyethylene terephthalate (i) with copolyester (iii) and polyethylene terephthalate (i) with copolyester ( ix) blends.

The polyester composition of the present invention comprises:

1-99% by weight of the first polyester [A], preferably 1-50% by weight, more preferably 2-25% by weight, and

99-1% by weight of the second polyester [B], preferably 99-50% by weight, more preferably 98-75% by weight.

When the polyester composition contains the first polyester [A] in an amount within the above range, the composition exhibits sufficiently improved gas barrier property and temperature-rising crystallization rate without lowering thermal stability during molding.

It is required that the temperature-rising half-crystallization time of the polyester composition of the present invention is 10-400 seconds, preferably 60-300 seconds. The temperature-rising half-crystallization time was measured by the method described later.

The polyester composition of the present invention can be prepared from the first polyester [A] and the second polyester [B] by any method.

For example, the first polyester [A] and the second polyester [B] are directly blended using, for example, a drum mixer or a Henschel mixer.

It is also possible to melt-knead the first polyester [A] and the second polyester [B] in advance to prepare a masterbatch containing a high concentration of the first polyester [A], and then properly add the second polyester to the masterbatch. Ester [B].

Various additives generally added to polyester such as colorants, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants and lubricants may be added to the polyester composition of the present invention, if desired. These additives can be pre-prepared with the polyester composition to form masterbatches, and then added to the polyester composition in the form of masterbatches.

The polyester composition of the present invention can be used as a molding material for various shaped products such as preforms, bottles, (stretched) films and sheets because of its good transparency and excellent gas barrier properties.

The polyester compositions of the present invention have a high crystallization rate. Therefore, in the production of bottles, it is possible to shorten the thermal crystallization time of the preform neck or neck, so that bottles having necks excellent in mechanical strength and heat resistance can be efficiently produced.

polyester laminate

The laminated product of the present invention has a multilayer structure comprising:

[I] a first resin layer formed from the first polyester [A] or polyester composition of the present invention, and

[II] A second resin layer formed of at least one resin selected from (a) second polyester [B], (b) polyamide and (c) polyolefin.

second resin layer

The second resin layer is formed of at least one resin selected from (a) the second polyester [B], (b) polyamide and (c) polyolefin.

Each resin is described below.

(a) Second polyester [B]

The present invention can use the second polyester [B] in the polyester composition described above.

(b) Polyamide

Examples of the polyamide (b) include aliphatic polyamides such as nylon 6, nylon 66, nylon 10, nylon 12, and nylon 46, and aromatic polyamides prepared from aromatic dicarboxylic acids and aliphatic diamines. Among them, nylon 6 is particularly preferable. These polyamides may be used alone or in combination.

These polyamides can be prepared by conventional methods.

(c) Polyolefin

Examples of polyolefins include olefin homopolymers such as polyethylene, polypropylene, polybutene-1, polymethylpentene, polymethylbutene, and olefin copolymers such as propylene/ethylene random copolymers. Among them, polyethylene and polypropylene are particularly preferable. These polyolefins may be used alone or in combination.

These polyolefins can be prepared by ordinary methods.

In the present invention, the second resin layer may be formed from a blend of the above resins (a)-(c).

If necessary, the first resin layer and the second resin layer may contain various additives generally added to resin layers, such as colorants, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants and lubricants.

In the polyester laminate of the present invention, the first resin layer and the second resin layer are laminated together. It is required that based on the total thickness of the polyester laminate, the thickness ratio of the first resin layer should be in the range of 5-30%, better 5-20%, preferably 5-15%, and the thickness ratio of the second resin layer should be in the range of It should be 70-95%, more preferably 80-95%, most preferably 85-95%.

In addition to the first and second resin layers, the polyester laminate of the present invention may have a third layer. For example, the third layer may be a layer composed of a composition comprising a resin for forming the first resin layer and a resin for forming the second resin layer, or may contain, for example, a heat stabilizer, a weather stabilizer, a lubricant, Additive layers of dyes, pigments, antifogging agents and antistatic agents, wherein such a layer may be present on at least one surface of a polyester laminate, or may be present as such a layer between first and second resin layers Intermediate layer; an adhesive layer for bonding the first resin layer to the second resin layer, eg as a modified polyolefin layer, this layer may also be constituted by glass, metal or paper.

The above-mentioned resins can be used to prepare the laminate of the present invention according to an ordinary method.

The polyesters constituting the laminates of the present invention have a high crystallization rate. Therefore, in the production of bottles, it is possible to shorten the thermal crystallization time of the preform neck or the neck, so that a bottle having a neck excellent in mechanical strength and heat resistance can be efficiently produced.

When the laminate of the present invention is in the shape of a preform or a bottle, the outer layer is preferably the first resin layer.

When the laminated product of the present invention is in the shape of a bottle, the carbon dioxide gas permeability rate of the bottle body is not more than 17.5cc·mm/m ² ·day·atmospheric pressure, preferably 15.0cc·mm/m ² ·day·atmospheric pressure, more preferably 4.0cc·mm/m ² ·day·atmospheric pressure.

Method for producing biaxially oriented polyester bottles

The method for producing the biaxially stretched polyester bottle of the present invention is described below.

In the method for producing the biaxially stretched polyester bottle of the present invention, a preform can be produced from the first polyester [A], the polyester composition and also from a polyester laminate, the preform is heated, biaxially Stretch the blow molded preform, and keep the obtained stretched bottle in a mold whose temperature is not lower than 100°C.

Preforms can be produced by ordinary molding methods such as extrusion molding or injection molding.

A method for forming a preform from a polyester laminate is, for example, forming the first resin layer from the first polyester [A] or the polyester composition of the present invention, and co-extruding the resin used to form the second resin layer Out-molding forms a multi-layer tube, which then forms the base at one end of the tube and the neck at the other end. It is also possible to co-inject the above-mentioned first layer of resin or composition with the second layer of resin to form a multi-layer preform.

The outer layer of the preform thus prepared is preferably the first resinous layer. The proportion range of the thickness of the first resin layer, based on the total thickness of the preform, is preferably 5-30%, more preferably 5-20%, and most preferably 5-15%. The ratio range of the thickness of the second resin layer, based on the total thickness of the preform, is preferably in the range of 70-95%, more preferably 80-95%, and most preferably 85-95%. In producing bottles, since such a preform can be drawn at a high draw ratio, the overall length of the preform can be shorter than usual, or the diameter of the preform can be smaller than usual.

In the above method, it is required to heat the preform at a temperature in the range of 70-150°C, preferably 80-140°C. The preform can be heated from the outside and from the inside (hollow part). Infrared rays or the like may be used as the heat source. It is preferable to heat from the hollow part as well as from the outside.

In biaxial stretch blow molding, the stretch ratio is 6-15 times, preferably 7-12 times, represented by the area stretch ratio (longitudinal stretch ratio×transverse stretch ratio).

In the present invention, it is also possible to heat set the biaxially stretched bottle. Preferably by keeping the bottle after orientation in a mold with a mold temperature of 100-240°C, preferably a mold temperature of 110-220°C, preferably 140-210°C, for a time of not less than 1 second, preferably not Less than 3 seconds for heat setting. Improve heat resistance and gas barrier properties of stretched bottles by means of heat setting.

In the present invention, the neck of the preform is thermally crystallized before biaxial stretch blow molding, or the neck of the bottle is thermally crystallized after biaxial stretch blow molding.

Thermal crystallization of the neck of the preform or bottle is carried out at 100-200°C, preferably at 120-180°C. Thermal crystallization is required to be performed such that the neck of the preform or bottle has a degree of crystallinity of 25-60%, preferably 25-50%.

The carbon dioxide gas permeability rate of the biaxially stretched polyester bottle body is generally not more than 17.5cc·mm/m ² ·day·atmospheric pressure, preferably 15.0cc·mm/m ² ·day·atmospheric pressure, more preferably 4.0cc· mm/m ² ·day·atmospheric pressure. The haze of the biaxially stretched bottle is generally 1.0-20%, preferably 5-15%.

According to the method of the present invention, it is difficult to impair the transparency of the bottle body, and therefore, a biaxially stretched polyester bottle excellent in transparency, gas barrier properties and heat resistance can be produced.

According to the method of the present invention, thermal crystallization of the preform neck or bottle neck can also be performed at high speed, shortening the bottle molding cycle including neck thermal crystallization, and thus can produce biaxial glass with excellent transparency, gas barrier properties and heat resistance at high productivity. Stretch polyester bottle.

Invention effect

The novel polyesters and polyester compositions of the present invention exhibit high crystallization rates with excellent gas barrier properties, transparency and heat resistance.

The preforms and bottles of the present invention have excellent gas barrier properties, transparency and heat resistance.

The polyester laminate of the present invention has excellent gas barrier properties, transparency and heat resistance. Polyester laminates are suitable for bottles and preforms.

Bottles, sheets and films made from the novel polyesters, polyester compositions and polyester laminates of the present invention are suitable for use in bottles for soft drinks such as water, juice, cola and carbonated drinks, for condiments such as soy sauce, Worcestershire sauce and ketchup bottles, bottles for liquor, such as wine, rice wine and whisky, also suitable for dairy products such as butter and cheese, packaging and plastic wrap for meat and fish, cans and plastic wrap for pesticides or gasoline Pharmaceutical packaging film.

According to the method of the present invention, a biaxially stretched polyester bottle exhibiting excellent gas barrier properties, transparency, and heat resistance and having a neck portion having high mechanical strength and heat resistance can be produced with high productivity.

Example

The present invention will be further described with reference to the following examples, but it should be construed that the present invention is by no means limited by these examples.

In the following examples, various properties were determined according to the methods described below.

intrinsic viscosity

The sample was dissolved in o-chlorophenol solvent to prepare a sample solution of 8 g/dl, and the viscosity of the solution was measured at 25°C. The intrinsic viscosity was calculated from the solution viscosity.

Carbon dioxide gas permeability rate (gas barrier performance)

The gas permeation rate of carbon dioxide was measured at 23° C. and a relative humidity of 60% using a gas permeation rate meter GPM-250 manufactured by G.L.Science K.K.

Films for measurement were prepared in the following manner.

Oriented film (2): A film with a thickness of 0.1 mm was prepared at a molding temperature of 290° C. with a press molding machine, and the film was rapidly cooled at a cooling mold temperature of 0° C. to obtain an amorphous film (1). Simultaneously biaxially stretching the amorphous film (1) at a temperature 15°C higher than the glass transition temperature (Tg) of the polyester forming the amorphous film at a stretching ratio of 3 times in each direction yields stretch film (2).

Heat-setting film (3): The stretched film (2) was mounted on a metal frame, placed in an oven, and heat-cured at 150° C. for 3 minutes to obtain a heat-setting film (3).

Heat-set bottle (4): use an injection molding machine to prepare a preform at a barrel temperature of 280°C and a mold temperature of 10°C. Then, at a temperature 15°C higher than the Tg of the polyester of the preform, the preform was blown biaxially stretched first at a stretch ratio of 3 times in the machine direction and then at a stretch ratio of 3 times in the transverse direction to produce a bottle. The bottle body is thermally cured at 200° C. for 1 minute to obtain a stretched heat-set bottle (4). Cut the heat-set bottle body (4) to obtain a sample.

Transparency (haze)

With an injection molding machine, the temperature of the barrel is 280° C., and the mold temperature is 10° C., and the dried polymer is molded into a square plate with a thickness of 5 mm. According to the method of ASTM D 1003, the transparency of the formed square plate is evaluated by measuring the haze value.

half crystallization time

The crystallization half time was measured with a differential scanning calorimeter (DSC) manufactured by Perkin Elmer Co.

Weigh 10 mg of dry polymer, place it in a sample pan, heat at 290°C for 5 minutes to melt the sample, then rapidly cool to 50°C at a cooling rate of 320°C/min, and let it stand for 5 minutes to prepare an amorphous sample . The sample was heated again to 140°C at a heating rate of 320°C/min and maintained at this temperature. At this temperature the sample crystallizes and a time versus heat release curve is obtained, from which the total calorific value can be obtained. The crystallization half time is defined as the time (in seconds) required to generate heat of 1/2 the total calorific value.

Since the polymer half-crystallization time is shorter, the crystallization of the polymer proceeds more efficiently, which improves the productivity of the bottle.

The heat resistance and appearance of bottles obtained by the method of producing heat-set bottles (4) were evaluated according to the methods described below.

heat resistance

The biaxially stretched bottle having an inner volume of 1.5 liters obtained as above was left to stand at 40°C and a humidity of 90% for 1 week. Fill the bottle with water at 90°C and keep it for 10 minutes. Measure the inner volume of the bottle before and after filling with hot water.

From the measured internal volume, shrinkage (%) was calculated by the following formula.

A: Inner volume before filling with hot water

B: Inner volume after filling with hot water

The heat resistance was evaluated from the degree of shrinkage according to the following criteria.

AA: 0≤shrinkage (%)＜0.5

BB: 0.5≤shrinkage (%)

bottle appearance

The haze of the side of the above-obtained biaxially stretched bottle having an inner volume of 1.5 liters was measured from a position 83 mm from the bottom of the bottle.

The appearance of the bottles was evaluated by haze (%) according to the following criteria.

AA: 0≤haze (%)＜5

BB: 5≤ haze (%)

Example 1

According to an ordinary method, 166 parts by weight of terephthalic acid (a-1) was used as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight of poly(1) with an average molecular weight of 1,000 , 4-Butanediol (b-2) was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.775 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 1.

Example 2

A polyester having an intrinsic viscosity [IV] of 0.780 dl/g was obtained in the same manner as in Example 1, except that poly-1,4-butylene glycol (b-3) with an average molecular weight of 2,000 was used instead of 1,000 of poly-1,4-butanediol (b-2).

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 1.

Example 3

A polyester having an intrinsic viscosity [IV] of 0.778 dl/g was obtained in the same manner as in Example 1, except that poly-1,4-butylene glycol (b-4) with an average molecular weight of 2,900 was used instead of 1,000 of poly-1,4-butanediol (b-2).

Haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of polyester were measured according to the method described above. The results are listed in Table 1.

Comparative example 1

With 166 parts by weight of terephthalic acid (a-1) as dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) as diol component (b), the preparation intrinsic viscosity [IV] is 0.775 dl/gram of polyester.

Haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of polyester were measured according to the method described above. The results are listed in Table 1.

Comparative example 2

Using 166 parts by weight of terephthalic acid (a-1) as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 8.5 parts by weight of poly-1,4-butanediene with an average molecular weight of 1,000 Alcohol (b-2) was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.776 dl/g.

Haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of polyester were measured according to the method described above. The results are listed in Table 1.

Table 1 (I) (a) dicarboxylic acid component unit (b) diol component unit Haze (%) Tg(°C) Half crystallization time (seconds) type Quantity (parts by weight) Example 1 (a-1) Terephthalic acid (b-1) Ethylene glycol (b-2) Poly-1,4-butylene glycol (Mw=1000) 166681.9 14.5 72 93 Example 2 (a-1) terephthalic acid (b-1) ethylene glycol (b-3) poly-1,4-butanediol (Mw=2000) 166681.9 17.4 71 92 Example 3 (a-1) Terephthalic acid (b-1) Ethylene glycol (b-4) Poly-1,4-butylene glycol (Mw=2900) 166681.9 16.3 70 90 Comparative example 1 (a-1) Terephthalic acid (b-1) Ethylene glycol 16668 9.4 76 202 Comparative example 2 (a-1) Terephthalic acid (b-1) Ethylene glycol (b-2) Poly-1,4-butylene glycol (Mw=1000) 166688.5 25.6 59 Not determined

Table 1(II) Carbon dioxide gas permeability rate (cc·mm/m ² ·day·atmospheric pressure) bottle heat resistance bottle appearance Stretch Film(2) Heat Set Film(3) Heat Set Bottles (4) Example 1 16.8 15.1 13.0 AAA AAA Example 2 18.8 16.2 14.4 AAA AAA Example 3 19.2 16.8 14.2 AAA AAA Comparative example 1 22.8 18.0 15.4 AAA AAA Comparative example 2 25.6 unprepared unprepared BB BB

Example 4

With 148 parts by weight of terephthalic acid (a-1) and 16 parts by weight of isophthalic acid (a-2) as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight Poly(1,4-butylene glycol) (b-2) having an average molecular weight of 1,000 was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.775 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 2.

Example 5

The polyester with intrinsic viscosity [IV] of 0.780dl/gram was prepared in the same manner as in Example 4, except that poly-1,4-butylene glycol (b-3) with an average molecular weight of 2000 was used instead of the average molecular weight of 1000 of 1,4-butanediol (b-2).

Haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of polyester were measured according to the method described above. The results are listed in Table 2.

Example 6

In the same manner as in Example 4, a polyester having an intrinsic viscosity [IV] of 0.778dl/gram was prepared, except that poly-1,4-butylene glycol (b-4) with an average molecular weight of 2900 was used instead of an average molecular weight of 1000 of 1,4-butanediol (b-2).

Haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of polyester were measured according to the method described above. The results are listed in Table 2.

Example 7

With 158 parts by weight of terephthalic acid (a-1) and 8 parts by weight of isophthalic acid (a-2) as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight Poly(1,4-butylene glycol) (b-2) having an average molecular weight of 1,000 was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.775 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 2.

Comparative example 3

With 133 parts by weight of terephthalic acid (a-1) and 33 parts by weight of isophthalic acid (a-2) as dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight Poly(1,4-butylene glycol) (b-2) having an average molecular weight of 1,000 was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.775 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 2.

Table 2 (I) (a) dicarboxylic acid component unit (b) diol component unit Haze (%) Tg(°C) Half crystallization time (seconds) type Quantity (parts by weight) Example 4 (a-1) Terephthalic acid (a-2) Isophthalic acid (b-1) Ethylene glycol (b-2) Poly-1,4-butylene glycol (Mw=1000) 14816681.9 7.2 68 301 Example 5 (a-1) Terephthalic acid (a-2) Isophthalic acid (b-1) Ethylene glycol (b-3) Poly-1,4-butylene glycol (Mw=2000) 14816681.9 8.7 67 295 Example 6 (a-1) Terephthalic acid (a-2) Isophthalic acid (b-1) Ethylene glycol (b-4) Poly-1,4-butylene glycol (Mw=2900) 14816681.9 8.2 66 289 Example 7 (a-1) Terephthalic acid (a-2) Isophthalic acid (b-1) Ethylene glycol (b-2) Poly-1,4-butylene glycol (Mw=1000) 1588681.9 10.8 70 198 Comparative example 3 (a-1) Terephthalic acid (a-2) Isophthalic acid (b-1) Ethylene glycol (b-2) Poly-1,4-butylene glycol (Mw=1000) 13333681.9

Table 2 (II) Carbon dioxide gas permeability rate (cc·mm/m ² ·day·atmospheric pressure) bottle heat resistance bottle appearance Stretch Film(2) Heat Set Film(3) Heat Set Bottles (4) Example 4 11.3 11.0 9.87 AAA AAA Example 5 12.6 11.8 10.9 AAA AAA Example 6 12.9 12.2 10.8 AAA AAA Example 7 14.0 13.0 11.4 AAA AAA Comparative example 3 unprepared unprepared unprepared BB BB

Example 8

With 198 parts by weight of naphthalene dicarboxylic acid (a-3) and 16 parts by weight of isophthalic acid (a-2) as dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight Poly(1,4-butylene glycol) (b-2) having an average molecular weight of 1,000 was used as the diol component (b) to prepare polyester [A-1] having an intrinsic viscosity [IV] of 0.643 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Example 9

The polyester [A-2] that intrinsic viscosity [IV] is 0.648dl/gram is prepared in the same manner as in Example 8, except that poly-1,4-butylene glycol (b-3) with an average molecular weight of 2000 ) instead of poly-1,4-butanediol (b-2) with an average molecular weight of 1000.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Example 10

The polyester with intrinsic viscosity [IV] of 0.648dl/gram was prepared in the same manner as in Example 8, except that poly-1,4-butylene glycol (b-4) with an average molecular weight of 2900 was used instead of the average molecular weight of 1000 of poly-1,4-butanediol (b-2).

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Example 11

With 206 parts by weight of naphthalene dicarboxylic acid (a-3) and 8 parts by weight of isophthalic acid (a-2) as dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight Poly(1,4-butylene glycol) (b-2) having an average molecular weight of 1,000 was used as the diol component (b) to prepare polyester [A-3] having an intrinsic viscosity [IV] of 0.622 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Example 12

Using 214 parts by weight of naphthalene dicarboxylic acid (a-3) as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 1.9 parts by weight of poly-1,4-butanediene with an average molecular weight of 1,000 Alcohol (b-2) was used as the diol component (b), and polyester [A-4] having an intrinsic viscosity [IV] of 0.613 dl/g was prepared.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Comparative example 4

Using 214 parts by weight of naphthalene dicarboxylic acid (a-3) as the dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) and 8.5 parts by weight of poly-1,4-butanediene with an average molecular weight of 1,000 Alcohol (b-2) was used as the diol component (b) to prepare a polyester having an intrinsic viscosity [IV] of 0.673 dl/g.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Comparative Example 5

With 214 parts by weight of naphthalene dicarboxylic acid (a-3) as dicarboxylic acid component (a), 68 parts by weight of ethylene glycol (b-1) as diol component (b), the preparation intrinsic viscosity [IV] is 0.619 dl/gram of polyester.

The haze, Tg, half-crystallization time and carbon dioxide gas permeability rate of the polyester were measured according to the method described above. The results are listed in Table 3.

Table 3 (I) (a) dicarboxylic acid component unit (b) diol component unit Haze (%) Tg(°C) Half crystallization time (seconds) type Quantity (parts by weight) Example 8 (a-3) naphthalene dicarboxylic acid (a-2) isophthalic acid (b-1) ethylene glycol (b-2) poly-1,4-butanediol (Mw=1000) 19816681.9 3.6 111 290 Example 9 (a-3) naphthalene dicarboxylic acid (a-2) isophthalic acid (b-1) ethylene glycol (b-3) poly-1,4-butanediol (Mw=2000) 19816681.9 3.9 110 278 Example 1 0 (a-3) naphthalene dicarboxylic acid (a-2) isophthalic acid (b-1) ethylene glycol (b-4) poly-1,4-butanediol (Mw=2900) 19816681.9 4.2 109 275 Example 11 (a-3) naphthalene dicarboxylic acid (a-2) isophthalic acid (b-1) ethylene glycol (b-2) poly-1,4-butanediol (Mw=1000) 2068681.9 5.1 113 186 Example 12 (a-3) naphthalene dicarboxylic acid (b-1) ethylene glycol (b-2) poly-1,4-butanediol (Mw=1000) 214681.9 7.5 115 192 Comparative example 4 (a-3) naphthalene dicarboxylic acid (b-1) ethylene glycol (b-2) poly-1,4-butanediol (Mw=1000) 214688.5 23.5 102 58 Comparative Example 5 (a-3) naphthalene dicarboxylic acid (b-1) ethylene glycol 21468 7.6 120 450

Table 3 (II) Carbon dioxide gas permeability rate (cc·mm/m ² ·day·atmospheric pressure) bottle heat resistance bottle appearance Stretch Film(2) Heat Set Film(3) Heat Set Bottles (4) Example 8 0.88 0.75 0.69 AAA AAA Example 9 0.91 0.78 0.70 AAA AAA Example 10 0.93 0.81 0.75 AAA AAA Example 11 1.29 0.79 0.73 AAA AAA Example 12 2.5 0.83 0.80 AAA AAA Comparative example 4 6.5 7.8 7.2 AAA BB Comparative Example 5 4.3 2.8 2.4 AAA AAA

Example 13

With the polyester [A-1] of embodiment 8 as the first polyester and the second polyester [B-1] (polyethylene terephthalate, diethylene glycol content: 1.95% by weight, characteristic Viscosity [IV]: 0.835 dl/g) was used to prepare a polyester composition in a weight ratio of [A-1]:[B-1] of 5:95. The polyester compositions were melted and injection molded into square plates, films and bottles in the manner described above. Haze, crystallization half time, carbon dioxide gas permeability, heat resistance and bottle appearance were then evaluated in the manner described above. The results are listed in Table 4.

Example 14

A polyester composition was prepared in the same manner as in Example 13, except that the weight ratio of [A-1]:[B-1] was changed to 10:90. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 15

A polyester composition was prepared in the same manner as in Example 13, except that the weight ratio of [A-1]:[B-1] was changed to 15:85. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 16

A polyester composition was prepared in the same manner as in Example 13, except that polyester [A-2] of Example 9 was used instead of polyester [A-1]. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 17

The polyester composition was prepared in the same manner as in Example 13, except that polyester [A-2] was used instead of polyester [A-1], and the weight ratio of [A-2]: [B-1] was 10:90. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 18

The polyester composition was prepared in the same manner as in Example 13, except that polyester [A-2] was used instead of polyester [A-1], and the weight ratio of [A-2]: [B-1] was 15:85. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 19

A polyester composition was prepared in the same manner as in Example 13, except that polyester [A-3] of Example 11 was used instead of polyester [A-1]. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 20

The polyester composition was prepared in the same manner as in Example 13, except that polyester [A-3] was used instead of polyester [A-1], and the weight ratio of [A-3]: [B-1] was 10:90. Various properties were then evaluated as previously described. The results are listed in Table 4.

Example 21

The polyester composition was prepared in the same manner as in Example 13, except that the polyester [A-4] of Example 12 was used instead of the polyester [A-1], and [A-4]: [B-1] The weight ratio is 10:90. Various properties were then evaluated as previously described. The results are listed in Table 4.

Comparative Example 6

The second polyester [B-1] was melted and injection molded into square plates, films and bottles as described above. The haze, crystallization half time, carbon dioxide gas transmission rate, heat resistance and bottle appearance were then evaluated in the manner previously described. The results are listed in Table 4.

Comparative Example 7

The polyester composition was prepared in the same manner as in Example 13, except that the second polyester [B-2] (polyethylene terephthalate, diethylene glycol content: 1.33% by weight, intrinsic viscosity [IV]: 0.775 dl/g) instead of polyester [A-1], and the weight of [B-2]:[B-1] was 20:80. Various properties were then evaluated as previously described. The results are listed in Table 4.

Table 4 [A] first polyester [B] second polyester Haze (%) Half crystallization time (seconds) Carbon dioxide gas permeability rate (cc·mm/m ² ·day·atmospheric pressure) bottle heat resistance bottle appearance Quantity (parts by weight) Oriented Film(2) Heat Set Film(3) Heat Set Bottles (4) Example 13 [A-1]5[B-1]95 6.5 161 10.7 8.7 6.8 AAA AAA Example 14 [A-1]10[B-1]90 7.2 155 6.7 5.8 4.2 AAA AAA Example 15 [A-1]15[B-1]85 8.3 132 4.9 3.9 3.2 AAA AAA Example 16 [A-2]5[B-1]95 7.1 161 11.6 9.5 7.2 AAA AAA Example 17 [A-2]10[B-1]90 7.9 140 7.4 6.1 4.8 AAA AAA Example 18 [A-2]15[B-1]85 8.6 117 5.5 4.6 4.0 AAA AAA Example 19 [A-3]5[B-1]95 8.3 122 13.3 11.2 8.3 AAA AAA Example 20 [A-3]10[B-1]90 9.5 124 8.9 7.5 5.6 AAA AAA Example 21 [A-4]10[B-1]90 9.8 115 13.5 11.1 8.5 AAA AAA Comparative example 6 [B-1] 100 9.4 202 18.5 15.3 12.3 BB BB Comparative Example 7 [B-1]80[B-2]20 17.8 156 18.8 16.1 12.4 BB BB

Example 22

With an extruder, at a barrel temperature of 280°C, melt the polyester [A-1] used to form the first resin layer and the polyester [B-1] (polyparaphenylene) used to form the second resin layer. Ethylene glycol diformate, diethylene glycol content: 1.95% by weight, intrinsic viscosity [IV]: 0.835 dl/g), these polyesters were fed into a two-layer calibrator, and prepared from [A-1] as the outer layer layer (thickness: 0.6 mm) and a [B-1] layer (thickness: 5.4 mm) as an inner layer, a tube (total wall thickness: 6 mm) of a two-layer structure. The cooling water temperature is 50°C. The outer diameter of the tube is 22 mm.

Cut the resulting tube. One end of the cut tube is heated and melted to form the base of the bottle, and the other end is heated and melted to form the neck of the bottle. In this way, a preform with a total length of 70 mm and a weight of 23 g is obtained.

Heat the preform at 100-130°C, and use a biaxial stretch blow molding machine under a blow molding pressure of 25 kg/cm2, first in the longitudinal direction with a stretch ratio of 3 times, and then in the transverse direction with a stretch ratio of 3 times Biaxially stretch blow molded preforms to make bottles. The bottles were thermoformed at 150°C for 1 minute.

The bottles were evaluated for half crystallization time, carbon dioxide gas transmission rate, heat resistance and appearance in the manner previously described. The results are listed in Table 5.

Example 23

Bottles were prepared in the same manner as in Example 22, except that preforms were prepared in which the [A-1] layer had a thickness of 0.9 mm and the [B-1] layer had a thickness of 5.1 mm. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 24

A bottle was prepared in the same manner as in Example 22, except that polyester [A-2] was used instead of polyester [A-1]. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 25

Bottles were prepared in the same manner as in Example 22, except that polyester [A-2] was used instead of polyester [A-1], the layer thickness of [A-2] of the preform was 0.9 mm, and [B-1] The layer thickness is 5.1 mm. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 26

A bottle was prepared in the same manner as in Example 22, except that polyester [A-3] was used instead of polyester [A-1]. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 27

Bottles were prepared in the same manner as in Example 22, except that polyester [A-3] was used instead of polyester [A-1], the preform [A-3] had a layer thickness of 0.9 mm, and [B-1] The layer thickness is 5.1 mm. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 28

A bottle was prepared in the same manner as in Example 22, except that polyester [A-4] was used instead of polyester [A-1]. The bottles were evaluated as previously described. The results are listed in Table 5.

Example 29

Bottles were prepared in the same manner as in Example 22, except that polyester [A-4] was used instead of polyester [A-1], and the layer thickness of [A-4] of the preform was 0.9 mm, [B-1] The layer thickness is 5.1 mm. The bottles were evaluated as previously described. The results are listed in Table 5.

Comparative Example 8

A bottle was prepared in the same manner as in Example 22, except that only polyester [B-1] was used instead of polyester [A-1] to prepare a preform, and the layer thickness of [B-1] was 6 mm. The bottles were evaluated as previously described. The results are listed in Table 5.

table 5 components Layer structure (mm) Half crystallization time (seconds) Carbon dioxide gas permeability rate (cc·mm/m ² ·day·atmospheric pressure) bottle heat resistance bottle appearance Example 22 [A-1][B-1] 0.65.4 185 10.2 AAA AAA Example 23 [A-1][B-1] 0.95.1 162 6.5 AAA AAA Example 24 [A-2][B-1] 0.65.4 179 11.3 AAA AAA Example 25 [A-2][B-1] 0.95.1 158 7.5 AAA AAA Example 26 [A-2][B-1] 0.65.4 163 12.9 AAA AAA Example 27 [A-3][B-1] 0.95.1 151 8.7 AAA AAA Example 28 [A-4][B-1] 0.65.4 154 13.5 AAA AAA Example 29 [A-4][B-1] 0.95.1 138 9.1 AAA AAA Comparative Example 8 [B-1] 6.0 202 18.5 BB AAA

Claims (24)

1. polyester, it comprises:

Be selected from the dicarboxylic acid component unit of terephthalic acid, m-phthalic acid and naphthalene dicarboxylic acids from least one, with from comprising ethylene glycol and the diol component unit of the polyalkylene glycol of 2-10 carbon atom alkylidene chain being arranged, it is characterized in that from the unitary proportional range of the component of polyalkylene glycol be the 0.001-10% of diol component unit weight.

2. polyester as claimed in claim 1, its feature are that also described dicarboxylic acid component unit is from the dicarboxylic acid component unit that mainly contains terephthalic acid.

3. polyester as claimed in claim 1, its feature is that also described dicarboxylic acid component unit mainly contains the dicarboxylic acid component unit from terephthalic acid and m-phthalic acid, and is the 1-15% of dicarboxylic acid component's unit weight from the unitary proportional range of isophthalic acid component.

4. polyester as claimed in claim 1, its feature is that also described dicarboxylic acid component unit mainly contains the dicarboxylic acid component unit from naphthalene dicarboxylic acids and m-phthalic acid, and is the 100-55% of dicarboxylic acid component's unit weight from the unitary proportional range of naphthalene dicarboxylic acids component.

5. as the described polyester of arbitrary claim among the claim 1-4, its feature is that also the polymerization degree (n) of described polyalkylene glycol is 5-50.

6. as the described polyester of arbitrary claim among the claim 1-5, its feature is that also described polyalkylene glycol is to gather 1, the 4-butyleneglycol.

7. prefabrication that forms by the described polyester of arbitrary claim among the claim 1-6.

8. biaxial stretching bottle, it comprises the described polyester of arbitrary claim among the claim 1-6.

9. biaxial stretching bottle as claimed in claim 8, its feature are that also the carbonic acid gas ventilative speed of described bottle is no more than 17.5ccmm/m ²It normal atmosphere.

10. biaxial stretching bottle as claimed in claim 8, its feature are that also the carbonic acid gas ventilative speed of described bottle is no more than 15.0ccmm/m ²It normal atmosphere.

11. biaxial stretching bottle as claimed in claim 8, its feature are that also the carbonic acid gas ventilative speed of described bottle is no more than 4.0ccmm/m ²It normal atmosphere.

12. a polymer blend, it comprises:

The polyester of [A] 1-99 weight % by arbitrary claim definition among the claim 1-6, as first kind of polyester and

Second kind of polyester of [B] 1-99 weight %, described second kind of polyester comprises the dicarboxylic acid component unit that is selected from terephthalic acid, m-phthalic acid and naphthalene dicarboxylic acids from least one, with from the diol component unit that comprises ethylene glycol, it is characterized in that should be less than 0.001% of diol component unit weight from the component unit ratio of polyalkylene glycol.

13. the polyester layer stampings with multilayered structure, it comprises:

The first layer resin layer that [I] formed by the polymer blend of the polyester of arbitrary claim definition among the claim 1-6 or claim 12 definition and

[II] is by second kind of polyester of at least a being selected from (a) [B], (b) polymeric amide and (c) second resin layer of polyolefinic resin formation, described second kind of polyester [B] comprises the dicarboxylic acid component unit that is selected from terephthalic acid, m-phthalic acid and naphthalene dicarboxylic acids from least one, with from the diol component unit that comprises ethylene glycol, it is characterized in that should be less than 0.001% of diol component unit weight from the component unit ratio of polyalkylene glycol.

14. polyester layer stampings as claimed in claim 13, its feature are that also it is the prefabrication form.

15. polyester layer stampings as claimed in claim 13, its feature are that also it is the form of bottle.

16. polyester layer stampings as claimed in claim 15, its feature are that also the carbonic acid gas ventilative speed of bottle is no more than 17.5ccmm/m ²It normal atmosphere.

17. polyester layer stampings as claimed in claim 15, its feature are that also the carbonic acid gas ventilative speed of bottle is no more than 15.0ccmm/m ²It normal atmosphere.

18. polyester layer stampings as claimed in claim 15, its feature are that also the carbonic acid gas ventilative speed of bottle is no more than 4.0ccmm/m ²It normal atmosphere.

19. method of producing the biaxial stretching polyester bottles, it may further comprise the steps, Accessory Right requires the polyester of arbitrary claim definition among the 1-6, the polyester layer stampings of the polymer blend of claim 12 definition or claim 13 definition are produced prefabrication, the heating prefabrication, biaxial stretching blowing prefabrication makes oriented bottle, and the bottle after stretching is remained in the mould that is not less than 100 ℃.

20. the method for production biaxial stretching polyester bottles as claimed in claim 19, its feature also are before biaxial stretching blowing, the neck of thermal crystalline prefabrication.

21. the method for production biax orientation polyester bottles as claimed in claim 19, its feature also are after biaxial stretching blowing, the thermal crystalline bottleneck.

22. as the method for the described production biaxial stretching of arbitrary claim polyester bottles among the claim 19-21, its feature is that also the carbonic acid gas ventilative speed of the bottle that makes is no more than 17.5ccmm/m ²It normal atmosphere.

23. as the method for the described production biaxial stretching of arbitrary claim polyester bottles among the claim 19-21, its feature is that also the carbonic acid gas ventilative speed of the bottle that makes is no more than 15.0ccmm/m ²It normal atmosphere.

24. as the method for the described production biaxial stretching of arbitrary claim polyester bottles among the claim 19-21, its feature is that also the carbonic acid gas ventilative speed of the bottle that makes is no more than 4.0ccmm/m ²It normal atmosphere.