JP2003012907A - Polyester composition and mold made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition excellent in conserving flavor and stopping gas, excellent in thermal stability during the molding process, and causing less blemish on the dies. SOLUTION: The composition comprises a polyester having ethylene terephthalate as the main repeating unit and a polyamide containing a metaxylene group, wherein the amount of phosphorus atoms (X) in the polyamide containing a metaxylene group should satisfy formula (1): 0<X<=400 ppm. It is preferred that the compound containing phosphorus atoms be of a specified structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition which is preferably used as a raw material for molded products such as hollow molded containers such as beverage bottles, films and sheets, and flavor retention (flavor). Properties) and a molded article excellent in transparency. Further, it provides a polyester composition which has good thermal stability when molding a hollow molded article and has little mold fouling. In particular, the molded product obtained from the polyester composition of the present invention is excellent in flavor retention and / or gas barrier property, and is also excellent in heat resistant dimensional stability and in dimensional stability after molding. It gives a sheet and a stretched film.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter referred to as P
Polyester (eg, abbreviated as ET) has excellent mechanical and chemical properties, and thus has high industrial value and is widely used as fibers, films, sheets, bottles and the like.

As a material for containers such as seasonings, oils, beverages, cosmetics and detergents, various resins have been adopted depending on the type of filling contents and the purpose of use thereof.

Of these, polyester is excellent in mechanical strength, heat resistance, transparency and gas barrier property, and therefore, as a raw material for moldings such as containers for filling beverages such as juices, soft drinks and carbonated drinks. Optimal.

Such polyester is supplied to a molding machine such as an injection molding machine to form a preform for a hollow molded body, and the preform is inserted into a mold having a predetermined shape and stretch blow molded. After that, heat the bottle body (heat
In general, it is molded into a hollow molded container, and if necessary, the bottle cap is heat-treated (crystallized in the cap).

However, PET contains acetaldehyde (hereinafter sometimes abbreviated as AA) as a by-product during melt polycondensation. Further, PET produces acetaldehyde by thermal decomposition during thermoforming of a molded body such as a hollow molded body, and the content of acetaldehyde in the material of the molded body thus obtained is large, so that the molded body is filled with the acetaldehyde. Affects the flavor and smell of beverages.

Therefore, various measures have hitherto been taken in order to reduce the content of acetaldehyde in the polyester molded body. Generally, a method of lowering the AA content by solid-phase polymerizing a melt-polycondensed polyester, a method of lowering AA generation at the time of molding by using a copolyester having a lower melting point, and a method of thermoforming at the time of thermoforming A method of reducing the molding temperature as much as possible and a method of minimizing the shear stress during thermoforming are used.

In recent years, polyester containers centered on polyethylene terephthalate have been used in mineral water and water.
It has come to be used as a container for low flavor beverages such as ron tea. In the case of such a beverage, these beverages are generally heat-filled or heat-filled and then sterilized, but if the AA content in the polyester molded material is reduced by the above-mentioned method, the contents of these containers are It has been found that the flavor and odor of syrup are not improved.

Further, for example, a method of using a polyester composition in which 0.05 parts by weight or more and less than 1 part by weight of a metaxylylene group-containing polyamide resin is added to 100 parts by weight of the polyester resin (Japanese Patent Publication No. 6-6662).
Alternatively, a polyester container comprising a polyester composition in which a specific polyamide having a terminal amino group concentration regulated within a certain range is contained in a thermoplastic polyester (Japanese Patent Publication No. 4-7).
No. 1425) is proposed, but mineral water
It has been found that it may be insufficient as a material for a container for low-flavor beverages such as tata.

On the other hand, a polyester molded product mainly composed of PET has excellent gas barrier properties as described above, but a hollow molded product for contents containing a compound which is very sensitive to oxygen such as vitamin C. Is unsatisfactory.

In order to solve such a problem, for example, we have added 100 parts by weight of polyester resin to
Polyester hollow molding containing 1 to 100 parts by weight of a metaxylylene group-containing polyamide resin (Japanese Patent Publication No. 4-54)
No. 702). However, when producing a heat-resistant hollow molded article using such a polyester composition, there is a problem that burn streaks due to thermal deterioration of the metaxylylene group-containing polyamide, unmelted matter occurs, and the appearance of the hollow molded article is impaired. It was There is also a problem that the obtained hollow molded article has insufficient transparency.

[0012]

DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned problems of the prior art, and it is small in the amount of acetaldehyde and the like generated during molding and is transparent, and further, retains flavor and / or flavor. An object of the present invention is to provide a polyester composition which is excellent in gas barrier property and is also excellent in thermal stability at the time of molding and hardly causes mold stain.

[0013]

To achieve the above object, the polyester composition of the present invention comprises a polyester (A) whose main repeating unit is ethylene arylate,
A polyester composition comprising a metaxylylene group-containing polyamide (B), wherein the phosphorus atom content (X) in the metaxylylene group-containing polyamide (B) satisfies the following (formula 1): Is. 0 <X ≦ 400 ppm (Formula 1) In this case, the compound containing a phosphorus atom is at least one selected from compounds represented by the following chemical formulas (C-1) to (C-4). Which is a polyester composition.

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

(However, R _{1 to} R ₇ are hydrogen, an alkyl group,
Aryl group, cycloalkyl group or arylalkyl group, X _{1 to} X ₅ are hydrogen, alkyl group, aryl group, cycloalkyl group, arylalkyl group alkali metal, or X _{1 to} X ₅ and R _{1 to} R in each formula (Each one of ₇ may be connected to each other to form a ring structure)

The main repeating unit of the polyester (A) may be ethylene terephthalate.

In this case, the cyclic ester 3 obtained by melting the polyester (A) whose main repeating unit is ethylene arylate at a temperature of 290 ° C. for 60 minutes
The increment of the monomer can be 0.50% by weight or less.

In this case, the polyester (A) whose main repeating unit is ethylene arylate
Is at least one resin selected from the group consisting of polyolefin resins, polyamide resins, polyacetal resins, polybutylene terephthalate resins, 0.1 ppb-10
It may be polyester blended with 00 ppm.

In this case, the molded product of the present invention is a molded product obtained by molding the polyester composition described in any one of the above.

In this case, the molded body can be a hollow molded body. In this case, the molded body can be a sheet-like material. In this case, the molded body can be a stretched film obtained by stretching a sheet-like material in at least one direction.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the polyester composition of the present invention and a molded article made of the same will be specifically described below. First, the polyester composition of the present invention is a composition comprising a polyester (A) whose main repeating unit is polyethylene arylate and a metaxylylene group-containing polyamide (B). The composition may be a dry blend in which individual chips of polyester (A) and polyamide (B) are mixed, or a blend in which polyester (A) and polyamide (B) are melt mixed. good. Further, the blended body may be in the form of a chip, a hollow molded body, a sheet-shaped body, a molded body such as a film, and the shape thereof does not matter.

Polyester (A) used in the present invention
Is a polyester whose main repeating unit is ethylene arylate. Among polyethylene arylate,
Polyethylene terephthalate and polyethylene 2,6
-Naphthalate is preferred. More preferably, it is a linear polyester containing 85 mol% or more of ethylene terephthalate units or ethylene 2,6-naphthalate units,
More preferably 90 mol% or more, and particularly preferably 95
% Linear polyester. Hereinafter, the case where the polyester (A) is polyethylene terephthalate will be mainly described.

The dicarboxylic acid as a copolymerization component used when the polyester is a copolymer is
Aromatic such as isophthalic acid, 2,6-naphthalenedicarboxylic acid (terephthalic acid when polyester (A) is polyethylene 2,6-naphthalate), diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid Dicarboxylic acids and functional derivatives thereof, oxy acids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid and glutaric acid and functional derivatives thereof, Examples thereof include aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and functional derivatives thereof.

When the polyester is a copolymer, the glycol used as a copolymerization component includes diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol and the like. Aliphatic glycols, alicyclic glycols such as cyclohexanedimethanol, bisphenol A, aromatic glycols such as alkylene oxide adducts of bisphenol A and the like can be mentioned.

Further, as the polyfunctional compound as a copolymerization component used when the polyester is a copolymer, examples of the acid component include trimellitic acid and pyromellitic acid. Examples of the component include glycerin and pentaerythritol. The amount of the above copolymerization component used should be such that the polyester maintains a substantially linear shape. Further, a monofunctional compound such as benzoic acid or naphthoic acid may be copolymerized.

The above-mentioned polyester is obtained by directly reacting terephthalic acid with ethylene glycol and, if necessary, the above-mentioned copolymerization component to distill off water to esterify it, and then use Sb compound, Ge compound, Ti as a polycondensation catalyst. Compound or A
direct esterification method in which polycondensation is carried out under reduced pressure using one or more compounds selected from the above-mentioned compounds, or dimethyl terephthalate and ethylene glycol and optionally the above-mentioned copolymerization component in the presence of an ester exchange catalyst. After reacting under the conditions to distill off methyl alcohol and transesterify, one or more compounds selected from Sb compounds, Ge compounds, Ti compounds or Al compounds are used as polycondensation catalysts, and the pressure is reduced mainly. It is produced by a transesterification method in which polycondensation is performed below. Further, solid phase polymerization may be carried out in order to increase the intrinsic viscosity of the polyester and reduce the acetaldehyde content.

The above-mentioned esterification reaction, transesterification reaction, melt polycondensation reaction and solid phase polymerization reaction may be carried out in a batch reaction apparatus or a continuous reaction apparatus. In any of these methods, the melt polycondensation reaction may be carried out in one step or may be carried out in multiple steps. The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus as in the melt polycondensation reaction. The melt polycondensation and solid phase polymerization may be carried out continuously or may be carried out separately.

The Sb compound used for producing the polyester (A) used in the present invention includes antimony trioxide, antimony acetate, antimony tartrate, potassium antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide. , Triphenyl antimony and the like. The Sb compound is added so that the residual amount of Sb in the produced polymer is in the range of 50 to 250 ppm.

Ge compounds used for producing the polyester (A) used in the present invention include amorphous germanium dioxide, crystalline germanium dioxide, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and phosphorus phosphite. Examples thereof include germanium acid. When a Ge compound is used, the amount used is 5 to 150 ppm, preferably 10 to 100 ppm, and more preferably 15 to 70 ppm as the Ge residual amount in the polyester.
It is ppm.

Examples of the Ti compound used for producing the polyester (A) used in the present invention include tetraethyl titanate, tetraisopropyl titanate and tetra-n.
-Tetraalkyl titanates such as propyl titanate and tetra-n-butyl titanate and partial hydrolysates thereof, titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, potassium titanyl oxalate, calcium titanyl oxalate, and titanyl strontium oxalate. Examples thereof include titanyl oxalate compounds, titanium trimellitate, titanium sulfate, titanium chloride and the like. The Ti compound is added so that the amount of Ti remaining in the produced polymer is in the range of 0.1 to 10 ppm.

Examples of the Al compound used in the production of the polyester (A) used in the present invention include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate and aluminum oxalate, oxides, aluminum hydroxides, Inorganic acid salts such as aluminum chloride, aluminum hydroxide chloride and aluminum carbonate, aluminum alkoxides such as aluminum methoxide and aluminum ethoxide, aluminum acetylacetonate, aluminum chelate compounds with aluminum acetylacetate and the like. , Organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysates thereof. Of these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate are particularly preferable. The Al compound is added so that the amount of Al remaining in the produced polymer is in the range of 5 to 200 ppm.

In the production of the polyester (A) used in the present invention, an alkali metal compound or an alkaline earth metal compound may be used in combination. Examples of the alkali metal compound or the alkaline earth metal compound include carboxylates such as acetate of these elements, alkoxide and the like,
It is added to the reaction system as a powder, an aqueous solution, an ethylene glycol solution or the like. The alkali metal compound or the alkaline earth metal compound is added so that the residual amount of these elements in the produced polymer is in the range of 1 to 50 ppm.

The above-mentioned catalyst compound can be added at any stage of the above-mentioned polyester-forming reaction step. Further, various phosphorus compounds can be used as the stabilizer. Examples of the phosphorus compound used in the present invention include phosphoric acid, phosphorous acid, phosphonic acid and their derivatives. Specific examples thereof include phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, and phosphorous acid. phosphoric acid,
Phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid These include diphenyl ester and the like, and these may be used alone or in combination of two or more kinds. The phosphorus compound is added at any stage of the above-mentioned polyester production reaction step so that the amount of phosphorus remaining in the produced polymer is in the range of 5 to 100 ppm.

In the case of polyethylene terephthalate, the intrinsic viscosity of the polyester (A) used in the present invention is preferably 0.55 to 1.50 deciliters / gram, and the lower limit is more preferably 0.58 deciliters / gram, and further preferably 0.60 deciliter / gram, the upper limit is more preferably 1.10 deciliter / gram, and further preferably 0.90 deciliter / gram.
When the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded product may be poor. If it exceeds 1.50 deciliters / gram, the resin temperature may rise and the thermal decomposition may become more vigorous during melting by a molding machine or the like, and the amount of free low molecular weight compounds that affect the aroma retention may increase. Problems such as yellowing of the molded product may occur. In addition, when the polyester (A) is polyethylene 2,6-naphthalate, 0.2 is obtained from the above.
It is preferably low in deciliter / gram.

The shape of the polyester (A) chips used in the present invention may be any of cylinder type, square type, spherical type, flat plate type and the like. The average particle size is usually 1.3-
The range is 5 mm, preferably 1.5 to 4.5 mm, and more preferably 1.6 to 4.0 mm. For example, in the case of a cylinder type, the length is 1.3 to 4 mm and the diameter is 1.3 to
It is practically about 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. Further, it is practical that the weight of the chip is in the range of 10 to 30 mg / piece.

The polyester (A) used in the present invention has a density of 1.33 to 1.43 g / cm ³ , preferably 1.37 to 1.42 g / cm ³ .

Polyesters generally contain a significant amount of fines generated during the manufacturing process, the copolymerization components and the contents of which are the same as those of the polyester chips.
Such fine has a property of promoting crystallization of polyester, and when present in a large amount, the transparency of a molded article molded from a polyester composition containing such fine becomes extremely poor, Further, in the case of a bottle, there is a problem that the amount of shrinkage at the time of crystallization of the bottle mouth plug does not fall within the range of the specified value and the cap cannot be sealed.

Therefore, the content of fines in the polyester (A) used in the present invention is 500 ppm or less,
It is preferably 300 ppm or less. Content is 50
If it exceeds 0 ppm, the crystallization rate will be high, and for example, the crystallization of the plug portion of the hollow molding container will be excessive, so that the shrinkage amount of the plug portion will not fall within the specified range, and In some cases, the capping becomes defective, the content leaks, and the preform for hollow molding is whitened, which makes normal stretching impossible.

The metaxylylene group-containing polyamide (B) used in the present invention is metaxylylenediamine,
Alternatively, at least 70 mol% or more, more preferably 75 mol% or more, in the molecular chain, of a constitutional unit formed from a mixed xylylenediamine containing metaxylylenediamine and 30% or less of the total amount of paraxylylenediamine and a dicarboxylic acid. A polyamide resin containing 80 mol% or more is particularly preferable.

Examples of the dicarboxylic acid as a copolymerization component include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid and dimer. Aliphatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, xylylenedicarboxylic acid, and naphthalenedicarboxylic acid can be used.

As the diamine component as a copolymerization component, ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nona. Aliphatic diamines such as methylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, cyclohexanediamine, bis-
Alicyclic diamines such as (4,4′-aminohexyl) methane and aromatic diamines such as para-bis- (2-aminoethyl) benzene can be used. These dicarboxylic acids and diamines can be used alone or in combination of two or more at an arbitrary ratio.

In addition to the above diamines and dicarboxylic acids, lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid. An acid or the like can also be used as a copolymerization component. In particular, the use of ε-caprolactam is desirable.

Examples of these polymers are homopolymers such as polymeta-xylylene adipamide, poly-meta-xylylene sebacamide, poly-meta-xylylene speramide, and meta-xylylene diamine / adipic acid / isophthalic acid co-polymer. Examples thereof include a combination, a metaxylylene / paraxylylene adipamide copolymer, a metaxylylene / paraxylylene piperamide copolymer, a metaxylylene / paraxylylene azeramide copolymer, and the like.

The above metaxylylene group-containing polyamide is prepared by heating an aqueous solution of an aminocarboxylic acid salt formed from a diamine and a dicarboxylic acid under pressure and normal pressure to remove water and water generated by the polycondensation reaction while the polycondensate is melted. It can be produced by a condensation method, a method in which a diamine and a dicarboxylic acid are heated and directly reacted in a molten state under normal pressure to carry out polycondensation. Further, by solid-phase polymerizing the polyamide chips obtained by these melt polycondensation reactions, it is possible to obtain a metaxylylene group-containing polyamide having a higher viscosity. The polycondensation reaction of the above-mentioned metaxylylene group-containing polyamide may be carried out in a batch reactor or a continuous reactor.

Usually, in the production of the metaxylylene group-containing polyamide (B), in order to prevent gelation due to thermal deterioration, a phosphorus-based stabilizer is often added and polymerized.
When the phosphorus atom content in the metaxylylene group-containing polyamide (B) used in the present invention is X, 0 <X ≦ 40.
It is in the range of 0 ppm. The lower limit is preferably 0.01 pp
m, more preferably 0.1 ppm, even more preferably 1 ppm, particularly preferably 3 p.
pm, most preferably 5 ppm. The upper limit is preferably 300 ppm, more preferably 250 p
pm, particularly preferably 230 ppm. When X is 0, that is, when phosphorus atoms are not contained at all, burn streaks and unmelted substances are likely to occur when a heat-resistant hollow molded article is produced using a polyester composition, and thermal deterioration during molding is also caused. large. On the other hand, when X is more than 400 ppm, the thermal stability is excellent, but the transparency of the obtained hollow molded article may deteriorate. In particular, an Sb-based compound is used as a polymerization catalyst,
Alternatively, when added to PET used as an additive, metal S
The blackening that seems to originate from b may occur, and the transparency may be significantly deteriorated.

As the compound containing a phosphorus atom in the metaxylylene group-containing polyamide (B), at least one selected from compounds represented by the following chemical formulas (C-1) to (C-4) is used. Is preferred.

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12]

(However, R₁~ R₇Is hydrogen, an alkyl group,
Aryl group, cycloalkyl group or arylalkyl
Group, X₁~ X_FiveIs hydrogen, alkyl group, aryl group, cyclo
Alkyl group, arylalkyl group or alkali metal,
Or X in each formula₁~ X_FiveAnd R ₁~ R₇1 of each
(These may be linked to each other to form a ring structure.)

Examples of the phosphinic acid compound represented by the chemical formula (C-1) include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite,
Potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite,

[0056]

[Chemical 13] Or

[0057]

[Chemical 14] Compounds and their hydrolysates, and condensates of the above phosphinic acid compounds.

Examples of the phosphonous acid compound represented by the chemical formula (C-2) include phenylphosphonous acid, sodium phenylphosphonous acid, potassium phenylphosphonous acid,
Examples include lithium phenylphosphonite and ethyl phenylphosphonous acid. Examples of the phosphonic acid compound represented by the chemical formula (C-3) include phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate and ethylphosphonate. For example, potassium acid. Chemical formula (C-4)
Examples of the phosphite compound represented by include phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphorous acid. Moreover, when the alkali metal-containing compound represented by the following chemical formula (D) is added, the thermal stability of the polyester composition of the present invention is further improved. Z-OR ₈ (D) (wherein Z is an alkali metal, R ₈ is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, —C (O) C
H ₃ or -C, (O) OZ ', (Z' is hydrogen, an alkali metal))

The alkali compound represented by the chemical formula (D) includes sodium hydroxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium acetate, sodium carbonate, and Examples thereof include alkaline earth compounds containing an alkaline earth metal, but are not limited to these compounds.

Content of total alkali metal in the metaxylylene group-containing polyamide (B) used in the present invention (amount of alkali metal atom contained in phosphorus stabilizer and chemical formula (D))
The total amount of the compound represented by and the amount of alkali metal atoms)
Is 1.0 of the content of phosphorus atoms in the polyamide (B).
It is preferably ˜6.0 times mol. The lower limit is more preferably 1.5, still more preferably 2.0, particularly preferably 2.3, most preferably 2.5 times mol, and the upper limit is more preferably 5.5 times mol, further preferably 5 times. .0
It is twice the mole. When the content of the total alkali metal is less than 1.0 times the phosphorus atom content, the gelation is likely to be promoted. On the other hand, when the total alkali metal content is more than 6.0 times the molar amount of the phosphorus atom content, the polymerization rate becomes slow, the viscosity does not sufficiently increase, and especially in a reduced pressure system, gelation is rather promoted, which is uneconomical. is there.

The above chemical formulas (C-1) to be used in the present invention
The compound represented by (C-4) and the compound represented by the chemical formula (D) may be used alone, but it is particularly preferable to use them in combination.
It is preferable because the thermal stability of the polyester composition is improved. In addition to the compounds described above, conventionally known antioxidants, ultraviolet absorbers, weathering agents, matting agents, lubricants, viscosity stabilizers, etc. are used to impair the flavor retention, gas barrier properties, and transparency of the hollow molded article. It may be used in combination to the extent that it does not exist.

The above-mentioned phosphorus atom-containing compound may be added to the metaxylylene group-containing polyamide (B) used in the present invention by adding the raw material before polymerization of the polyamide, during the polymerization, or by melt-mixing with the polymer. Good.

The content of the tertiary nitrogen in the metaxylylene group-containing polyamide (B) used in the present invention is preferably 2.
It is 0 mol% or less, more preferably 1.5 mol% or less, and further preferably 1.0 mol% or less. A molded product obtained by using the polyester composition containing the metaxylylene group-containing polyamide (B) having a tertiary nitrogen content of more than 2.0 mol% contains a colored foreign substance due to a gelled product and has a poor color. May be. In particular, in a stretched film or a biaxially stretched hollow molded product obtained by stretch molding, the portion where the gel-like material is present is not normally stretched and becomes thick, which causes thickness unevenness and has no commercial value. May increase.

Usually, polyamide contains an imino compound as an impurity in a diamine compound as a raw material,
The diamine compound is iminated by deammonification during the polymerization or the like to contain an imino group in the resin. Furthermore, when a carboxylic acid reacts with this imino moiety, it becomes a tertiary amide. The content of such imino groups and tertiary amides varies greatly depending on the production method, impurities in the raw materials, the amount of water in the polymerization system, and the like. The tertiary nitrogen referred to in the present application is
It is both nitrogen based on imino groups and nitrogen based on tertiary amides, and the content of tertiary nitrogen is such that secondary amides (--NHCO
-: Content represented by a molar ratio (mol%) to nitrogen based on a usual amide constituting the main chain). As described below, the content of tertiary nitrogen is determined by using an NMR spectrometer. When the polyamide contains a large number of imino groups, the imino group part and the dicarboxylic acid terminal may react during molding to generate a gelled product. When the polyamide contains a large amount of tertiary amide, the gelled product increases.

The lower limit of the content of the tertiary nitrogen is preferably 0.001 mol%, more preferably 0.01 mol%, and further preferably 0.0 because of manufacturing reasons.
It is 5 mol%, particularly preferably 0.1 mol%. When producing a metaxylylene group-containing polyamide having a tertiary nitrogen content of less than 0.001 mol%, a highly purified raw material is used, a large amount of a deterioration inhibitor is required, and the polymerization temperature is kept low. There may be a productivity problem such as need.

The relative viscosity of the metaxylylene group-containing polyamide (B) used in the present invention is preferably 1.3 to 4.0, the lower limit is more preferably 1.6, still more preferably 1.7, and particularly preferably 1. It is 8, and the upper limit is more preferably 3.7, further preferably 1.3.5, and particularly preferably 3.0. When the relative viscosity is 1.3 or less, the molecular weight is too small, and the mechanical properties of the molded product made of the polyester composition of the present invention may be poor. On the other hand, when the relative viscosity is 4.0 or more, it takes a long time to polymerize the polyamide, which not only causes deterioration of the polymer and undesired coloring, but also reduces productivity and causes a cost increase. There are cases.

The shape of the metaxylylene group-containing polyamide (B) used in the present invention may be any of cylinder type, square type, spherical type, flat plate type and the like. The average particle size is usually 1.0 to 5 mm, preferably 1.2 to 4.5
mm, and more preferably 1.5 to 4.0 mm. For example, in the case of a cylinder type, the length is 1.0 to 4
mm, diameter is practically about 1.0 to 4 mm. In the case of spherical particles, the maximum particle size is 1.
1 to 2.0 times, and the minimum particle size is practically 0.7 times or more of the average particle size. In addition, the weight of the chip is 10
A range of 30 mg / piece is practical.

The density of the metaxylylene group-containing polyamide (B) used in the present invention is 1.20 to 1.24 g / c.
m ³ is preferable, and more preferably 1.20 g / cm ³ or more and 1.23 g / cm ³ or less.

In addition, the terminal amino group concentration of the metaxylylene group-containing polyamide (B) used in the present invention (μmol
/ G) is AEG, and the terminal carboxyl group concentration (μmol / g) of the metaxylylene group-containing polyamide is CEG, the ratio of AEG to CEG (AEG / CE
G) is preferably 1.05 or more. The ratio of the terminal amino group concentration to the terminal carboxyl group concentration (AEG / CEG) in the metaxylylene group-containing polyamide is 1.
If it is less than 05, the hollow molded article obtained from the polyester composition of the present invention has poor flavor retention, and such a polyester composition may be impractical as a raw material for a container for low-flavor beverages. . Further, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration in the metaxylylene group-containing polyamide (AEG / CEG)
When it is more than 20, the resulting molded article is colored intensely and loses commercial value, which is not preferable.

The mixing ratio of the polyester (A) and the metaxylylene group-containing polyamide (B) constituting the polyester composition of the present invention is 100% of the above polyester (A).
The amount of the metaxylylene group-containing polyamide (B) is preferably 0.01 to 100 parts by weight based on parts by weight. The amount of the metaxylylene group-containing polyamide (B) added to obtain a molded product having a very low AA content and excellent flavor retention from the polyester composition is 0 based on 100 parts by weight of the polyester (A). 0.01-5 parts by weight is preferable, a more preferable lower limit is 0.1 part by weight, a still more preferable lower limit is 0.5 part by weight, a more preferable upper limit is 4 parts by weight, and a still more preferable upper limit is 3 parts by weight.

Further, when it is desired to obtain a molded product having an excellent gas barrier property, a transparency which does not impair the practical use, and an AA content which is very small and which has an excellent flavor retention, the polyester (A) is used. 1-100 for 100 parts by weight
The preferred lower limit is 3 parts by weight, the more preferred lower limit is 5 parts by weight, and the more preferred upper limit is 6 parts by weight.
0 parts by weight, and a more preferable upper limit is 30 parts by weight. When the mixing amount of the metaxylylene group-containing polyamide (B) is less than 0.01 parts by weight with respect to 100 parts by weight of the polyester (A), the AA content of the obtained molded product is not reduced, and the molded product content The flavor retention may be very poor. Further, the mixing amount of the metaxylylene group-containing polyamide (B) is 1 with respect to 100 parts by weight of the polyester (A).
If it exceeds 100 parts by weight, the transparency of the obtained molded article may be very poor, and the mechanical properties of the molded article may deteriorate.

The content of the cyclic ester trimer of the polyester (A) whose main repeating unit is ethylene arylate used in the present invention is preferably 0.50% by weight or less, more preferably 0.45% by weight or less. , And more preferably 0.40% by weight or less. When molding a heat-resistant hollow molded article or the like from the polyester composition of the present invention,
When a polyester having a content of the cyclic ester trimer of more than 0.50% by weight was used, the oligomer adhesion to the surface of the heating mold was drastically increased depending on the heat treatment conditions. The transparency of the hollow molded article may be extremely deteriorated. In particular, when the main repeating unit is polyethylene terephthalate, cyclic ester trimers are likely to occur, and these problems are remarkable.

The polyester (A) whose main repeating unit used in the present invention is ethylene arylate
It is preferable that the amount of increase of the cyclic ester trimer when melted at a temperature of 290 ° C. for 60 minutes is 0.50 wt% or less. The amount of increase of the cyclic ester trimer is preferably 0.3.
It is desirable that the content be less than or equal to wt%, and more preferably less than or equal to 0.1 wt%. When a polyester in which the amount of increase in the cyclic ester trimer when melted at a temperature of 290 ° C. for 60 minutes exceeds 0.50% by weight, the amount of the cyclic ester trimer during resin melting during molding of the polyester composition is Depending on the heat treatment conditions, the adhesion of the oligomer to the surface of the heating mold rapidly increases, and the transparency of the obtained hollow molded article may be extremely deteriorated. The cyclic ester trimer is a cyclic trimer composed of dicarboxylic acid and ethylene glycol, and in the case of PET, it is a cyclic trimer composed of terephthalic acid and ethylene glycol.

The polyester (A) used in the present invention, which has an increased amount of the cyclic ester trimer of 0.50% by weight or less when melted at a temperature of 290 ° C. for 60 minutes, is used after the melt polycondensation or in the solid phase. It can be produced by deactivating the polycondensation catalyst remaining in the polyester obtained after the polymerization. Examples of the method of deactivating the polycondensation catalyst in the polyester include a method of subjecting the polyester chips to contact treatment with water, steam or a steam-containing gas after melt polycondensation or after solid-state polymerization.

A method of contacting the polyester chips with water, steam or a gas containing steam to achieve the above object will be described below. Examples of the hot water treatment method include a method of immersing in hot water and a method of spraying water on the chips with a shower. The treatment time is 5 minutes to 2 days, preferably 10 minutes to 1 day, more preferably 30 minutes to 10 hours, and the water temperature is 20 to 180 ° C., preferably 40.
To 150 ° C, more preferably 50 to 120 ° C.
The treatment method may be either a continuous method or a batch method, but the continuous method is preferable for industrial use.

When the polyester chips are subjected to water treatment in a batch system, a silo type treatment tank can be used. That is, the polyester chips are received in silos in a batch system and treated with water. When the polyester chips are treated with water continuously, the polyester chips can be continuously or intermittently received from the upper portion of the tower-type treatment tank for water treatment.

When the polyester chips and steam or steam-containing gas are brought into contact with each other for treatment, 50 to 50
Steam or steam-containing gas or steam-containing gas at a temperature of 150 ° C., preferably 50 to 110 ° C., is preferably supplied in the amount of 0.5 g or more as steam per 1 kg of granular polyethylene arylate, or is allowed to be present so that granular polyethylene arylate is present. And contact with steam. This contact between polyester chips and water vapor is usually 1
It is carried out for 0 minutes to 2 days, preferably for 20 minutes to 10 hours.

The treatment method may be either a continuous method or a batch method. When the polyester chips are subjected to a contact treatment with steam in a batch system, a silo type treatment device can be used. That is, the polyester chips are received in a silo, and steam or a steam-containing gas is supplied in a batch method to perform contact treatment.

In the case where the polyester chips are continuously contacted with steam, the tower-type processing apparatus should continuously receive the granular polyethylene arylate from the upper portion, and continuously supply steam in cocurrent or countercurrent to contact with steam. You can As mentioned above, when treated with water or steam,
Granular polyethylene arylate as needed, vibrating screener,
It is drained by a draining device such as a simon cart and transferred to the next drying step by a conveyor.

For drying the polyester chips which have been subjected to contact treatment with water or steam, a commonly used polyester drying treatment can be used. As a method for continuously drying, a hopper-type aeration dryer in which polyester chips are supplied from the upper part and a drying gas is aerated from the lower part is usually used.

As a dryer for batch-type drying, drying may be carried out under atmospheric pressure while ventilating a drying gas. Although atmospheric air may be used as the dry gas, dry nitrogen and dehumidified air are preferable from the viewpoint of preventing a decrease in molecular weight due to hydrolysis or thermal oxidative decomposition of the polyester.

Further, the polyester (A) whose main repeating unit used in the present invention is ethylene arylate
Is at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin, and a polybutylene terephthalate resin.
The polyester may be blended with 00 ppm. The blending ratio of the above-mentioned polyolefin resin and the like in the polyester (A) used in the present invention is 0.1 ppb to 1000 ppm, preferably 0.3.
ppb-100 ppm, more preferably 0.5 ppb-
1 ppm, more preferably 0.5 ppb to 45 pbb
Is.

If the blending amount is less than 0.1 ppb, the crystallization rate will be very slow and the mouthpiece of the hollow molded article will not be sufficiently crystallized. Therefore, if the cycle time is shortened, the mouthpiece will shrink. Since the amount does not fall within the specified value range, capping failure may occur, and the stretch-heat-fixing mold for molding the heat-resistant hollow molded body is heavily contaminated, and it is often attempted to obtain a transparent hollow molded body. You may have to clean the mold. If it exceeds 1000 ppm, the crystallization speed will be high, and the crystallization of the plug part of the hollow molded article will be excessive, and the shrinkage / shrinkage amount of the plug part will not fall within the specified range, resulting in poor capping. In some cases, leakage of the contents may occur, or the preform for a hollow molded body may be whitened, which makes normal stretching impossible. Further, in the case of a sheet-like material, if it exceeds 1000 ppm, the transparency becomes extremely poor, and the stretchability becomes poor so that normal stretching is impossible and only a stretched film with large thickness unevenness and poor transparency is obtained. Sometimes I can't.

Examples of the polyolefin resin blended with the polyester (A) used in the present invention include polyethylene resin, polypropylene resin, and α-olefin resin.

Examples of the polyethylene resin blended in the polyester (A) used in the present invention include ethylene homopolymers, ethylene, propylene and butene.
1,3-methylbutene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-
Other α-olefins having about 2 to 20 carbon atoms such as 1 and copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and styrene. To be Specifically, for example, low / medium / high density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl, etc. Pentene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene −
Examples thereof include ethylene resins such as ethyl acrylate copolymer.

Examples of the polypropylene resin blended in the polyester (A) used in the present invention include homopolymers of propylene, propylene and ethylene, butene-1,3-methylbutene-1, pentene-.
Other α-olefins having about 2 to 20 carbon atoms such as 1,4-methylpentene-1, hexene-1, octene-1, and decene-1, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid. Examples thereof include esters, methacrylic acid esters, and copolymers with vinyl compounds such as styrene. Specifically, for example, propylene propylene, propylene-ethylene copolymer, propylene-ethylene-
Examples of the propylene resin include butene-1 copolymer.

The α-olefin resin blended in the polyester (A) used in the present invention is 4
-Homopolymers of C2-C8 α-olefins such as methylpentene-1, those α-olefins, and ethylene, propylene, butene-1,3-methylbutene-
1, pentene-1, hexene-1, octene-1, decene-1 and the like and copolymers with other α-olefins having about 2 to 20 carbon atoms. Specifically, for example, butene-1 resin such as butene-1 homopolymer, 4-methylpentene-1 homopolymer, butene-1-ethylene copolymer, butene-1-propylene copolymer and 4 -A copolymer of methylpentene-1 and a C2-C18 α-olefin, and the like.

Further, as the polyamide resin to be blended with the polyester (A) used in the present invention, for example,
Polymers of lactams such as butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam and ω-laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, Hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, undecamethylenediamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1 , 4-bis (aminomethyl) cyclohexane, alicyclic diamine such as bis (p-aminocyclohexylmethane), diamine unit such as aromatic diamine such as m- or p-xylylenediamine, glutaric acid, adipic acid, Aliphatic dicarboxylic acids such as suberic acid and sebacic acid Alicyclic dicarboxylic acids such as hexanedicarboxylic acid, terephthalic acid, polycondensates with dicarboxylic acid units such as aromatic dicarboxylic acids such as isophthalic acid, and copolymers thereof, and the like, specifically, for example, , Nylon 4, Nylon 6, Nylon 7, Nylon 8, Nylon 9, Nylon 11, Nylon 12, Nylon 66, Nylon 69, Nylon 610, Nylon 61
1, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/61
0, nylon 6/12, nylon 6 / 6T, nylon 6
I / 6T etc. are mentioned.

Examples of the polyacetal resin blended in the polyester (A) used in the present invention include polyacetal homopolymers and copolymers.
As a polyacetal homopolymer, ASTM-D79
The density measured by the measuring method of 2 is 1.40 to 1.42 g
/ Cm ³ , 19 according to the method of ASTM D-1238
Melt flow ratio (MF measured at 0 ° C, load 2160g)
Polyacetal having R) in the range of 0.5 to 50 g / 10 minutes is preferable.

Further, as the polyacetal copolymer,
The density measured by the method of ASTM-D792 is 1.
38 to 1.43 g / cm ³ , a polyacetal copolymer having a melt flow ratio (MFR) measured at 190 ° C. and a load of 2160 g by the measuring method of ASTM D-1238 of 0.4 to 50 g / 10 min was obtained. preferable. Examples of these copolymerization components include ethylene oxide and cyclic ethers.

As the polybutylene terephthalate resin to be blended with the polyester (A) used in the present invention, for example, terephthalic acid and 1,4-butanedio-
Polybutylene terephthalate homopolymer consisting of vinyl and naphthalene dicarboxylic acid, diethylene glycol,
Examples thereof include copolymers obtained by copolymerizing 1,4-cyclohexane dimethanol and the like.

The polyester blended with the above-mentioned polyolefin resin or the like used in the present invention is directly added with the above-mentioned resin such as polyolefin so that the content thereof falls within the above range and melt-kneaded. In addition to the conventional method such as a method or a method of adding as a master-batch and melt-kneading, a resin such as the above-mentioned polyolefin is used in the production step of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, and pre-crystallized. Immediately after
During solid phase polymerization, immediately after solid phase polymerization, etc., or directly added as powder or granules between the end of the manufacturing stage and the molding stage, or the flow conditions of polyester chips It is also possible to use a method in which the above is mixed by a method of bringing it into contact with a resin member such as the above-mentioned polyolefin, and then melt-kneading.

Here, as a method for bringing the polyester chip-shaped body into contact with the above-mentioned resin member such as polyolefin under flowing condition, the polyester chip-like member is prepared in the empty space where the above-mentioned resin member such as polyolefin exists. Is preferably brought into collision contact with the member, specifically, for example, immediately after melt polycondensation of polyester, immediately after pre-crystallization,
Pneumatic transportation pipes during manufacturing processes such as immediately after solid-phase polymerization, during filling / discharging of transportation containers during the transportation stage of polyester chips as a product, and during loading of molding machines during the molding process of polyester chips, etc. Gravity transportation pipes, silos, magnet parts of magnet catchers, etc. are made of a resin such as the above-mentioned polyolefin, or a resin such as the above-mentioned polyolefin is lined, or a rod-like or net-like shape in the transfer path. A method of transferring the polyester chips by, for example, installing a resin member such as the above-mentioned polyolefin such as a body is mentioned. The contact time of the polyester chip with the member is usually an extremely short time of about 0.01 seconds to several minutes, but a minute amount of the above-mentioned resin such as polyolefin can be mixed into the polyester.

The polyester (A) whose main repeating unit used in the present invention is ethylene arylate
The acetaldehyde content of 50 ppm or less is preferably 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less. In particular, when the polyester composition of the present invention is used as a material for a container for low flavor beverages such as mineral water, polyester (A)
It is desirable that the acetaldehyde content is 8 ppm or less, preferably 5 ppm or less, more preferably 4 ppm or less. When the acetaldehyde content exceeds 50 ppm, the effect of retaining the flavor of the contents such as a molded product molded from this polyester becomes poor.

The amount of diethylene glycol copolymerized in the polyester (A) whose main repeating unit is ethylene arylate used in the present invention is preferably the lower limit of the glycol component constituting the polyester (A). 1.0 mol%, more preferably 1.3 mol%, further preferably 1.5 mol%, and the upper limit is preferably 5.
It is 0 mol%, more preferably 4.5 mol%, and further preferably 4.0 mol%. When the amount of diethylene glycol is more than 5.0 mol%, the thermal stability may be poor, the molecular weight may be greatly reduced during molding, and the acetaldehyde content and the formaldehyde content may be increased significantly, which is preferable. Absent. When the content of diethylene glycol is less than 1.0 mol%, the transparency of the obtained molded product may deteriorate.

The polyester composition of the present invention can be obtained by mixing the above polyester (A) and the above polyamide (B) by a conventionally known method. For example, the above polyamide chips and the above polyester chips are dry blended with a tumbler, a V-type blender, a Henschel mixer, etc., and the dry blended mixture is melted once or more with a single-screw extruder, a twin-screw extruder, a kneader, etc. Examples thereof include a mixture, and further, a mixture obtained by solid-phase polymerization of a molten mixture under high vacuum or an inert gas atmosphere, if necessary.

It is also possible to use a saturated fatty acid monoamide, an unsaturated fatty acid monoamide, a saturated fatty acid bisamide, an unsaturated fatty acid bisamide and the like at the same time in the polyester composition of the present invention.

Examples of the saturated fatty acid monoamide include lauric acid amide, palmitic acid amide, stearic acid amide and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide ricino-acid amide, and the like. Examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, and hexamethylenebisbehenic acid. Examples include amides. Examples of unsaturated fatty acid bisamides include ethylenebisoleic acid amide and hexamethylenebisoleic acid amide. Preferable amide compounds are saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. The compounding amount of such an amide compound is 1
It is preferably in the range of 0 ppb to 1 × 10 ⁵ ppm.

Metal salt compounds of aliphatic monocarboxylic acids having 8 to 33 carbon atoms such as naphthenic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, behenic acid, montanic acid, melissic acid,
It is also possible to concurrently use a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a cobalt salt or the like of a saturated or unsaturated fatty acid such as oleic acid or linoleic acid. The compounding amount of these compounds is 10 p
It is preferably in the range of pb to 300 ppm.

The polyester composition of the present invention may contain other additives, if necessary, such as known ultraviolet absorbers, antioxidants, oxygen absorbers, oxygen scavengers, lubricants added from the outside or during the reaction. Various additives such as a lubricant, a release agent, a nucleating agent, a stabilizer, an antistatic agent, and a pigment which are deposited inside may be blended. Further, it is also possible to mix an ultraviolet blocking resin, a heat resistant resin, a product recovered from a used polyethylene arylate bottle, etc. in an appropriate ratio.

When the polyester composition of the present invention is used for film use, calcium carbonate or magnesium carbonate is added to the polyester composition in order to improve handling properties such as slipperiness, winding property and blocking resistance. Inorganic particles such as barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, and magnesium phosphate, organic salt particles such as terephthalate salts such as calcium and calcium oxalate, barium, zinc, manganese, and magnesium, and divinylbenzene, Inert particles such as cross-linked polymer particles such as styrene, acrylic acid, methacrylic acid, vinyl monomers of acrylic acid or methacrylic acid, homopolymers or copolymers, can be contained.

The polyester composition of the present invention can be used to form films, sheets, containers and other packaging materials by using a commonly used melt molding method. The sheet-like material comprising the polyester composition of the present invention can be produced by a method known per se. For example, it can be manufactured using a general sheet forming machine equipped with an extruder and a die. Further, the sheet-like material can be formed into a recup shape or a tray shape by pressure forming or vacuum forming.

In producing a stretched film, the stretching temperature is usually 80 to 130 ° C. The stretching may be uniaxial or biaxial, but biaxial stretching is preferable from the viewpoint of practical physical properties of the film. In the case of uniaxial stretching, the stretching ratio is usually 1.1 to 10 times, preferably 1.5 to 8 times, and in the case of biaxial stretching, it is usually 1.1 to 8 times in each of the machine direction and the transverse direction. , Preferably 1.5 to 5 times. Also, the vertical / horizontal ratio is usually 0.5.
˜2, preferably 0.7 to 1.3. The obtained stretched film can be further heat-fixed to improve heat resistance and mechanical strength. Heat fixation is usually under tension, 120 ° C
~ 240, preferably 150 ~ 230 ℃, usually several seconds ~
It is performed for several hours, preferably several tens of seconds to several minutes.

In manufacturing the hollow molded article, a briform molded from the PET of the present invention is stretch blow molded, and an apparatus conventionally used for blow molding of PET can be used. Specifically, for example, a preform is once molded by injection molding or extrusion molding, and as it is or after processing the plug portion and the bottom portion, it is reheated, and biaxial stretch blow molding such as hot parison method or cold parison method. The law applies. The molding temperature in this case, specifically the temperature of each part of the cylinder and nozzle of the molding machine, is usually in the range of 260 to 290 ° C. The stretching temperature is usually 70 to 120 ° C, preferably 90 to 110 ° C,
The stretching ratio is usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded article,
Although it can be used as it is, it is generally used for beverages requiring heat filling, such as fruit juice and oolong tea.
Further, it is heat-set in a blow mold to give it heat resistance before use. The heat setting is usually 100 to 200 ° C., preferably 120 to 180 ° C. under tension such as compressed air.
At a temperature of several seconds to several hours, preferably several seconds to several minutes.

Further, in order to impart heat resistance to the spout,
The plug part of the preform obtained by injection molding or extrusion molding is crystallized in an oven equipped with a far infrared or near infrared heater, or the plug part is molded with the above heater after bottle molding. Crystallize.

The polyester composition of the present invention can also be used as a constituent layer of a laminated molded product, a laminated film or the like. In particular, it is used for manufacturing containers and the like in the form of a laminate with PET. As an example of the laminated molded article, a two-layer structure composed of an outer layer composed of the polyester composition of the present invention and a PET inner layer, or a two-layer structure composed of an inner layer composed of the polyester composition of the present invention and a PET outer layer A two-layered molded article, a three-layer structure composed of an intermediate layer containing the polyester composition of the present invention and an outer layer and an innermost layer of PET, or an outer layer containing the polyester composition of the present invention and an intermediate layer of PET A three-layer structure formed of layers, an intermediate layer containing the polyester composition of the present invention, and P
Examples include a molded article having a five-layer structure composed of the innermost layer, the central layer, and the innermost layer of ET. For the PET layer, other gas barrier resin, ultraviolet blocking resin, heat resistant resin, recovered products from used polyethylene arylate bottles and the like can be mixed and used at an appropriate ratio.

Further, as an example of other laminated moldings,
Examples thereof include a laminated molded body with a resin other than polyester such as polyolefin, and a laminated molded body with a different kind of base material such as paper or a metal plate. There is no particular limitation on the thickness of the laminated molded body and the thickness of each layer. Further, the laminated molded body is a sheet-like material,
It can be used in various shapes such as a film-shaped material, a plate-shaped material, a hollow body and a container.

The above-mentioned laminated body can be manufactured by coextrusion using the number of extruders corresponding to the type of the resin layer and the multi-layer multi-die, and the number of injections corresponding to the type of the resin layer. It can also be carried out by co-injection using a machine and a co-injection runner and injection mold. The polyester composition of the present invention can be preferably used as a hollow molding, a tray, a packaging material such as a biaxially stretched film, a film for coating a metal can, and the like. In addition, the composition of the present invention can be used as a tray-shaped container for cooking food in a microwave oven and / or an oven, or for heating frozen food. In this case, the sheet-like material from the polyester composition is molded into a tray shape and then thermally crystallized to improve heat resistance. In addition, the measuring method of the main characteristic value in this invention is demonstrated below.

[0109]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the main characteristic value in this specification is demonstrated below.

(Evaluation Method) (1) Intrinsic Viscosity (IV) of Polyester Obtained from Solution Viscosity at 30 ° C. in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent. It was

(2) Content of diethylene glycol copolymerized in polyester (hereinafter referred to as "DEG content") Decomposition with methanol and quantification of the DEG amount by gas chromatography, based on all glycol components Expressed as a ratio (mol%).

(3) Content of cyclic ester trimer of polyester (hereinafter referred to as "CT content") 300 mg of a sample was dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixture (volume ratio = 2/3). , And then add 30 ml of chloroform to dilute.
15 ml of methanol was added to this to precipitate the polymer, and the polymer was filtered. The filtrate was evaporated to dryness, the volume was adjusted to 10 ml with dimethylformamide, and the cyclic ester trimer was quantified by high performance liquid chromatography.

(4) Acetaldehyde content of polyester (hereinafter referred to as "AA content"), formaldehyde (hereinafter referred to as "FA content"). Sample / distilled water = 1g / 2cc Put in a glass ampoule with nitrogen replaced and seal the upper part, and perform extraction treatment at 160 ° C for 2 hours, and after cooling, extract acetaldehyde and formaldehyde in the extract by high sensitivity gas chromatography. It was measured and the concentration was displayed in ppm. When the sample was a bottle, the bottle body was cut off and cut into a piece of about 3 mm square.

(5) Increasing amount of cyclic ester trimer during melting of polyester (ΔCT amount) 3 g of dried polyester chips were placed in a glass test tube and immersed in an oil bath at 290 ° C. for 60 minutes under a nitrogen atmosphere. Melt. The cyclic ester trimer increase amount at the time of melting is calculated by the following formula. Cyclic ester trimer increase amount (% by weight) during melting = cyclic ester trimer content after melting (% by weight) -cyclic ester trimer content before melting (% by weight)

(6) Relative Viscosity (Rv) of Polyamide Containing Metaxylylene Group 0.25 g of a sample was dissolved in 25 ml of 96% sulfuric acid, and 10 ml of this solution was measured with an Ostwald viscosity tube at 20 ° C. Rv = t / t ₀ t ₀ : Solvent drop time t : Number of seconds of dropping sample solution

(7) Phosphorus atom content in metaxylylene group-containing polyamide (ppm) Whether the sample is subjected to dry ash decomposition in the presence of sodium carbonate,
Wet decomposition in sulfuric acid / nitric acid / perchloric acid system or sulfuric acid / hydrogen peroxide water system to convert phosphorus into orthophosphoric acid. Then 1
Measure the absorbance at 830 nm of heteropoly blue produced by reacting molybdate in mol / L sulfuric acid solution with phosphomolybdic acid and reducing it with hydrazine sulfate using an absorptiometer (Shimadzu UV-150-02). , Colorimetrically quantify.

(8) Gelation time of metaxylylene group-containing polyamide In a branched test tube having an internal capacity of about 20 ml, 3 g of the metaxylylene group-containing polyamide dried under reduced pressure at 100 ° C. for 24 hours was put, and nitrogen decompression under pressure was repeated three times. It was immersed in an oil bath at a constant temperature of 260 ° C. and heated for a predetermined time while flowing 30 ml / min of nitrogen gas. Heat treated resin 0.25
g was dissolved in 25 ml of 96% sulfuric acid at room temperature for 16 hours,
The time required to see the insoluble matter.

(9) Measurement of fine content About 0.5 kg of resin was placed on a sieve (diameter 30 cm) covered with a wire mesh having a nominal size of 1.7 mm according to JIS-Z8801, and a swing type manufactured by Terraoka Co., Ltd. Sieving tow machine SNF-7 1
Sifted at 800 rpm for 1 minute. This operation was repeated, and a total of 20 kg of the resin was sieved. The fines sieved off under the sieve were washed with ion-exchanged water, filtered with a G1 glass filter manufactured by Iwaki Glass Co., Ltd., and collected. These were dried together with the glass filter in a dryer at 100 ° C. for 2 hours, then cooled and weighed. Again, the same operation of washing with ion-exchanged water and drying was repeated, and it was confirmed that the weight became constant, and the weight of the glass filter was subtracted from this weight to obtain a fine weight. Fine content is Fine weight / Sieved total resin weight.

(10) Evaluation of mold stain Using a predetermined amount of polyester dried in a dryer using nitrogen gas and a predetermined amount of metaxylylene group-containing polyamide chips dried in a dryer using nitrogen gas, each machine was used. A preform was molded at a resin temperature of 285 ° C. using a M-150C (DM) injection molding machine manufactured by Seisakusho. The plug part of this preform was heated and crystallized by a homemade plug part crystallization device, and then biaxially stretch blow molded using a LB-01E stretch blow molding machine manufactured by Co-Poplast Co., Ltd. About 145 ° C
By heat fixing in a mold set to, a hollow molded body of 1000 cc was obtained. 2000 hollow moldings were continuously stretch-blow-molded under the same conditions, and the state of the die surface before and after the stretch-blooming was visually observed and evaluated as follows. ○: No change before and after the continuous molding test △: Significant deposits after the continuous molding test ×: Very large deposits after the continuous molding test

(11) Transparency of Hollow Molded Body (10) The appearance of the hollow molded body obtained after molding was visually observed and evaluated as follows. Short-term transparency was evaluated after molding 10 pieces, and continuous molding transparency was evaluated after 2000 pieces. ⊚: Transparent ○: Transparent in the practical range, and no foreign matter such as unmelted material is seen. Δ: Transparent in the practical range, but foreign matter such as unmelted matter is recognized. X: Poor transparency, coloration is recognized, or poor transparency and unmelted material is seen

(12) Sensory test Boiled distilled water was placed in the above hollow molded article, sealed and held for 30 minutes, cooled to room temperature and allowed to stand at room temperature for 1 month. After opening, the flavor, odor, etc. were tested. It was Distilled water is used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared. (Evaluation criteria) 0: No off-taste or odor 1: Slight difference from blank 2: Slight difference from blank 3: Sensible difference from blank 4: Very large difference from blank feel

(13) Oxygen permeation amount (cc / container x 2
4hr ・ atm) Modern Controls Oxygen Permeability Meter OX-TRAN
The permeation amount per 100 cc bottle was measured at 20 ° C. and 0% RH.

(Polyethylene terephthalate (PET) used in Examples and Comparative Examples) PET used in the test
(Ge remaining amount = about 40 ppm, phosphorus remaining amount = about 33 pp
The characteristics of m) are shown in Table 1. These are all polymerized by a continuous melt polycondensation-solid state polymerization apparatus. PET
In (a), after the solid phase polymerization, hot water treatment is performed in ion-exchanged water at about 90 ° C. for 3 hours. In addition, PET (a) ~ P
The DEG contents of ET (b) were all about 2.7 mol%, and the fine contents were all about 30 ppm or less.

[0124]

[Table 1]

(Metaxylylene Group-Containing Polyamide (Ny-MXD6) Used in Examples and Comparative Examples) Properties of Ny-MXD6 (c) to Ny-MXD6 (f) used in the test are shown in Table 2. Ny-MXD6 (c) is obtained by a batch method in which an aqueous solution of meta-xylylenediamine-adipate is heated in a polymerization kettle under pressure and under normal pressure for polycondensation. Further, as the phosphorus atom-containing compound,
Sodium hypophosphite was added as an alkaline compound, sodium hydroxide before polymerization. The total amount of sodium atoms of sodium hypophosphite and sodium hydroxide was 3.8 times the molar amount of phosphorus atoms. Ny-MXD6 (d) is obtained by a method in which metaxylylenediamine and adipic acid are heated and polycondensed in a polymerization kettle under normal pressure. Further, sodium hypophosphite was added as a phosphorus atom-containing compound and sodium hydroxide was added as an alkali compound before polymerization. The total amount of sodium atoms of sodium hypophosphite and sodium hydroxide was 3.2 times that of phosphorus atoms. Ny-MXD6 (e) is Ny
—A product obtained by the same polymerization method as MXD6 (c). Further, sodium hypophosphite was added as a phosphorus atom-containing compound and sodium hydroxide was added as an alkali compound before polymerization. The amount of sodium was adjusted to 3.0 times the molar amount of phosphorus atoms as the total amount of sodium atoms of sodium hypophosphite and sodium hydroxide. Ny-
MXD6 (f) is also obtained by the same polymerization method as Ny-MXD6 (c). The phosphorus atom-containing compound and the alkaline compound were not added.

[0126]

[Table 2]

Example 1 Using 2 parts by weight of Ny-MXD6 (c) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of the evaluation method (10), and the mold was soiled. An evaluation was also conducted. Table 3 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded body had an AA content of 8 ppm, an FA content of 3 ppm, and a sensory test evaluation of 0.
7. The appearance was transparent in a practical range, and no mold stain was observed.

(Example 2-5, Comparative Example 1-5) Example 1
Similarly to the above, a molded body was molded and various evaluations were performed. The results are shown in Table 3.

[0129]

[Table 3]

[0130]

According to the polyester composition of the present invention,
Excellent transparency, low increase in acetaldehyde, low increase in formaldehyde, excellent flavor retention and / or gas barrier properties, and excellent dimensional stability after heat treatment and dimensional stability after molding Excellent performance
Strips and stretched films are obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Makoto Ito             Toyobo Co., Ltd. 10-24 Toyocho, Tsuruga City, Fukui Prefecture             Ceremony company Tsuruga factory (72) Inventor Hidekazu Yoshida             2-8 Dojimahama 2-chome, Kita-ku, Osaka City, Osaka Prefecture             Toyobo Co., Ltd. F-term (reference) 4F071 AA45 AA54 AF08 AF30 AH05                       BA01 BB05 BB06 BB07 BC01                       BC04                 4J002 BB003 CB003 CF041 CF053                       CL002 EW036 EW126 EW136                       FD206 GG00

Claims (9)

[Claims] 1. A polyester composition comprising a polyester (A) whose main repeating unit is ethylene arylate and a metaxylylene group-containing polyamide (B), wherein the phosphorus atom content in the metaxylylene group-containing polyamide (B). A polyester composition wherein (X) satisfies the following formula (Formula 1). 0 <X ≦ 400 ppm (Equation 1) 2. The compound containing a phosphorus atom is
Selected from compounds represented by chemical formulas (C-1) to (C-4)
At least one of which is exposed, Claim 1
The polyester composition described. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] (However, R₁~ R₇Is hydrogen, an alkyl group, an aryl group,
Cycloalkyl group or arylalkyl group, X₁~ X_Five
Is hydrogen, an alkyl group, an aryl group, a cycloalkyl group,
Arylalkyl group or alkali metal, or each formula
X inside₁~ X_FiveAnd R ₁~ R₇One of each is connected to each other
(May be bonded to form a ring structure) 3. The polyester resin composition according to claim 1, wherein the main repeating unit of the polyester (A) is ethylene terephthalate. 4. The increase in cyclic ester trimer when melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less, and the increase in cyclic ester trimer according to any one of claims 1 to 3. Polyester resin composition. 5. The polyester (A) whose main repeating unit is ethylene arylate is at least one resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin and a polybutylene terephthalate resin. The polyester composition according to any one of claims 1 to 4, which is a polyester blended with 0.1 ppb to 1000 ppm. 6. A molded product obtained by molding the polyester composition according to any one of claims 1 to 5. 7. The molded product according to claim 6, which is a hollow molded product. 8. The molded product according to claim 6, which is a sheet-shaped product. 9. A stretched film obtained by stretching the sheet-like material according to claim 8 in at least one direction.