JP2003082206A - Polyester composition and molded product composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition having excellent transparency, flavor retaining and/or gas barrier properties and further scarcely causing metal mold staining during molding. SOLUTION: This polyester resin composition is obtained by adding 0.01-100 pts.wt. of at least two or more kinds of semiaromatic polyamides (B) to 100 pts.wt. of a polyester (A) having main repeating units which are ethylene terephthalate.

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, the present invention provides a polyester composition which is less susceptible to mold stains when molding a hollow molded article. 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 gives a hollow molded product, a sheet-shaped product and a stretched film which are excellent in transparency.

[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 a heat-resistant hollow molded article is produced using such a polyester composition, there is 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, is excellent in flavor retention and / or gas barrier property, and further causes mold stains during molding. An object is to provide a polyester composition that is difficult to prevent.

[0013]

To achieve the above object, the polyester composition of the present invention comprises a polyester (A) whose main repeating unit is ethylene terephthalate.
It is a polyester composition obtained by adding 0.01 to 100 parts by weight of at least two kinds of semi-aromatic polyamide (B) to 100 parts by weight.

In this case, the semi-aromatic polyamide (B) is selected from semi-aromatic polyamide (B-1) having repeating units derived mainly from an aliphatic dicarboxylic acid and an aromatic ring-containing diamine. At least 1
Of at least one semi-aromatic polyamide selected from the group consisting of semi-aromatic polyamides and semi-aromatic polyamides (B-2) having repeating units derived from aromatic dicarboxylic acids and aliphatic diamines. You can

In this case, the semi-aromatic polyamide (B-1) may be a metaxylylene group-containing polyamide (B-3). In this case, the ratio of the metaxylylene group-containing polyamide (B-3) to the semi-aromatic polyamide (B-2) used was 9
It can be 0:10 to 10:90 (weight ratio).

In this case, the semi-aromatic polyamide (B-2) is a semi-aromatic polyamide comprising an aromatic dicarboxylic acid selected from at least one of terephthalic acid and isophthalic acid and an aliphatic diamine. You can In this case, the semi-aromatic polyamide (B-2) may be a semi-aromatic polyamide composed of terephthalic acid, isophthalic acid and hexamethylenediamine.

In this case, when the polyester (A) whose main repeating unit is ethylene terephthalate is melted at a temperature of 290 ° C. for 60 minutes, the increase amount of the cyclic ester trimer is 0.30 weight. It can be less than or equal to%. In this case, the polyester (A) whose main repeating unit is ethylene terephthalate is at least one selected from the group consisting of a polyolefin resin, a polyamide resin, a polyacetal resin, and a polybutylene terephthalate resin. Resin of 0.1ppb
A polyester blended with up to 1000 ppm is produced. In this case, the haze of the 5 mm-thick molded product molded at 290 ° C. can be 20% or less.

In this case, a molded product is obtained by molding the polyester composition according to any one of claims 1 to 9. In this case, claim 10
The molded article described in 1. can be a hollow molded article. In this case, the molded article according to claim 10 can be a sheet-like material. In this case, claim 1
A molded product according to item 0 is a stretched film obtained by drawing the sheet-like product according to claim 12 in at least one direction.

[0019]

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. The polyester (A) used in the present invention is a polyester whose main repeating unit is ethylene terephthalate, preferably a linear polyester containing 85 mol% or more of ethylene terephthalate units, and more preferably 90 mol% or more, particularly preferably 95%
It is a linear polyester containing the above.

As the dicarboxylic acid as a copolymerization component used when the polyester is a copolymer,
Aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and functional derivatives thereof, p-oxybenzoic acid, oxycaproic acid, etc. Oxyacids and their functional derivatives, adipic acid, sebacic acid, succinic acid, glutaric acid and other aliphatic dicarboxylic acids and their functional derivatives, cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids and their functional derivatives, etc. .

As the glycol used as a copolymerization component when the polyester is a copolymer, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, etc. may be used. 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.

Examples of the Sb compound used in the production of the polyester (A) used in the present invention include 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 in the production of 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 case of an Al compound, an alkali metal compound or an alkaline earth metal compound may be used in combination. Examples of the alkali metal compound or alkaline earth metal compound include carboxylates such as acetates of these elements, alkoxides and the like, and they are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions and 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.

The intrinsic viscosity of the polyester (A) used in the present invention is preferably 0.55 to 1.30 deciliter / gram, and the lower limit is more preferably 0.58 deciliter / gram, further preferably 0.60 deciliter / gram.
Gram, the upper limit is more preferably 1.10 deciliters /
It is in the range of gram, more 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. On the other hand, if it exceeds 1.30 deciliters / gram, the resin temperature may become high during melting by a molding machine or the like and thermal decomposition may become violent, resulting in an increase in free low molecular weight compounds that affect the aroma retention. Problems such as yellowing of the molded product may occur.

The shape of the polyester (A) chips used in the present invention may be any of cylinder type, square type, spherical type or flat plate type. 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 mg / cm ³ , preferably 1.37 to 1.42 mg / 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 the property of promoting the crystallization of polyester, and when it is present in a large amount, the transparency of the molded product molded from such polyester becomes very poor, and in the case of bottles. Causes a problem that the amount of shrinkage at the time of crystallization of the bottle mouth plug part does not fall within the specified range 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 semi-aromatic polyamide (B) used in the present invention is a semi-aromatic polyamide (B-1) having a repeating unit derived from an aliphatic dicarboxylic acid and an aromatic ring-containing diamine, and an aromatic dicarboxylic acid. It is a semi-aromatic polyamide (B-2) having a repeating unit derived from an acid and an aliphatic diamine. By using the polyamides (B-1) and (B-2), the transparency of the obtained molded article can be improved. The aromatic diamine content is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on all amine components. The aromatic dicarboxylic acid content is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on all carboxylic acid components.

The aliphatic dicarboxylic acid constituting the semi-aromatic polyamide (B-1) preferably has 4 to 1 carbon atoms.
And the aliphatic dicarboxylic acids of 2. Examples of the aliphatic dicarboxylic acid include, for example, succinic acid, adipic acid,
Examples thereof include azelaic acid, sebacic acid, 2-methylglutaric acid, pimelic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid and dimer acid. Of these, adipic acid is particularly preferable.

Examples of the aromatic ring-containing diamine constituting the semi-aromatic polyamide (B-1) include paraxylylenediamine, metaxylylenediamine, orthoxylylenediamine, paraphenylenediamine and metaphenylenediamine. Preferred is metaxylylenediamine.

As the semiaromatic polyamide (B-1) used in the present invention, metaxylylenediamine as the aromatic ring-containing diamine is at least 70 mol% or more, more preferably 75 mol% or more, particularly preferably 80 mol. The semi-aromatic polyamide is contained in an amount of not less than%.

The aromatic dicarboxylic acid constituting the semi-aromatic polyamide (B-2) is preferably a group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, xylylenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. One or more compounds selected from the above, and more preferably terephthalic acid and isophthalic acid.

The aliphatic diamine constituting the semi-aromatic polyamide (B-2) preferably has 6 to 18 carbon atoms.
Consisting of an aliphatic diamine. Such an aliphatic diamine may be a linear alkylenediamine or a branched chain alkylenediamine. As such aliphatic diamine, specifically, for example, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
Units derived from linear alkylenediamines such as decamethylenediamine, undecamethylenediamine and dodecamethylenediamine, and 1,4-diamino-1,1
-Dimethylbutane, 1,4-diamino-1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,
4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-diamino-
2,3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane,
1,6-diamino-3,3-dimethylhexane, 1,6
-Diamino-2,2-dimethylhexane, 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3- Dimethylheptane, 1,7-diamino-
2,4-dimethylheptane, 1,7-diamino-2,5
-Dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2 , 4-dimethyloctane,
1,8-diamino-3,4-dimethyloctane, 1,8
-Diamino-4,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-
3,3-dimethyloctane, 1,8-diamino-4,4
-Dimethyloctane, 1,6-diamino-2,4-diethylhexane, 1,9-diamino-5-methylnonane, and other components derived from a branched chain alkylenediamine can be mentioned. Among such linear or branched chain alkylenediamine components, a linear alkylenediamine component is preferable, and a hexamethylenediamine component is particularly preferable.

As a specific example of the semi-aromatic polyamide (B-3) used in the present invention, a semi-aromatic polyamide having a repeating unit derived from metaxylylenediamine and adipic acid is preferable. Specific examples of the semi-aromatic polyamide (B-2) used in the present invention include semi-aromatic polyamides having a repeating unit derived from hexamethylene diamine and terephthalic acid, derived from hexamethylene diamine and isophthalic acid. Semi-aromatic polyamide having repeating units, hexamethylene diamine and semi-aromatic polyamides having repeating units derived from terephthalic acid and isophthalic acid, semi-aromatic polyamide having hexa methylene diamine and repeating units derived from terephthalic acid and adipic acid An aromatic polyamide and the like can be mentioned, but a semi-aromatic polyamide having a repeating unit derived from hexamethylenediamine and terephthalic acid and isophthalic acid is preferable.

When terephthalic acid and isophthalic acid are used as the aromatic dicarboxylic acid constituting the semi-aromatic polyamide (B-2) used in the present invention, the repeating unit derived from isophthalic acid and aliphatic diamine is 10
It is preferably in the range of ˜90 mol%. It is more preferably in the range of 15 to 85 mol%, still more preferably 20 to 80 mol%. When the repeating unit derived from isophthalic acid and aliphatic diamine is less than 10 mol%,
The melting point of the copolyamide may be higher than that of the polyester (A) used in the present invention. In this case, not only the thermal deterioration of the polyester (A) is promoted during the molding process, but also foreign matter such as a deteriorated product may be mixed in the obtained hollow molded body. When the repeating unit derived from isophthalic acid and aliphatic diamine is more than 90 mol%, the softening point temperature of the copolyamide becomes extremely low,
The mechanical strength of the obtained hollow molded article may be weakened.

The semi-aromatic polyamide (B) used in the present invention is a metaxylylene group-containing polyamide (B-3).
And the semi-aromatic polyamide (B-2) having repeating units derived mainly from an aromatic dicarboxylic acid and an aliphatic diamine have a usage ratio of 90:10 to 10:90.
(Weight ratio) is preferable. A more preferable use ratio is 80:20 to 20:80 (weight ratio), and an even more preferable use ratio is 70:30 to 30:70 (weight ratio).
Is. The ratio of the metaxylylene group-containing polyamide (B-3) to the semi-aromatic polyamide (B-2) used was 9
When it does not fall within the range of 0:10 to 10:90 (weight ratio), the transparency of the obtained polyester hollow body may be poor and the practicality thereof may be poor.

The above-mentioned semi-aromatic polyamide (B) can be obtained by heating an aqueous solution of an aminocarboxylic acid salt produced from a diamine and a dicarboxylic acid under pressure and atmospheric pressure to cause a reaction, or by heating the diamine and dicarboxylic acid under atmospheric pressure. It can be produced by a method of directly reacting with the above. Also,
By solid-phase polymerizing the polyamide chips obtained by these melt polycondensation reactions, a semi-aromatic polyamide (B) having a higher viscosity can be obtained. The polycondensation reaction of the semi-aromatic polyamide (B) may be carried out in a batch reactor or a continuous reactor.

In the semi-aromatic polyamide (B) used in the present invention, conventionally known antioxidants, ultraviolet absorbers, weathering agents, matting agents, lubricants, viscosity stabilizers and the like are added to the flavor-retaining properties of hollow molded articles. , May be added to the extent that the gas barrier properties and transparency are not impaired, and may be added before the polymerization of the semiaromatic polyamide (B), during the polymerization, or may be melt-mixed with the polymer. .

If desired, the semiaromatic polyamide (B) used in the present invention may be added with a terminal blocking agent during or after the polymerization. As the terminal blocking agent, one generally used in polyamide can be added.
Specifically, for example, there are monocarboxylic acids, acid anhydrides, and the like, and as the monocarboxylic acids, there are acetic acid, caproic acid, heptanoic acid, octanoic acid, pelargonic acid, stearic acid, lauric acid, benzoic acid, and the like. Examples of the anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, and hexahydrophthalic anhydride.

The semi-aromatic polyamide (B) used in the present invention preferably has a relative viscosity of 1.3 to 4.0, the lower limit is more preferably 1.6, still more preferably 1.7, and particularly preferably 1. 8 and the upper limit is more preferably 3.
7, more preferably 3.5, particularly preferably 3.0. If the relative viscosity is 1.3 or less, the molecular weight is too small,
The mechanical properties of the molded product made of the polyester composition of the present invention may be inferior. Conversely, when the relative viscosity is 4.0 or more,
It takes a long time to polymerize the polyamide, which may cause deterioration of the polymer and undesired coloring, and may cause a decrease in productivity and a cost increase.

The shape of the semi-aromatic polyamide (B) chips used in the present invention may be any of cylinder type, square type, spherical type or flat plate type. 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, it is practical that the length is about 1.0 to 4 mm and the diameter is about 1.0 to 4 mm. In the case of spherical particles, the maximum particle size is 1.1 to 2.0 of the average particle size.
It is practical that the minimum particle size is 0.7 times or more the average particle size. The weight of the chip is 10-30 mg /
Practical range is individual.

The density of the semi-aromatic polyamide (B) used in the present invention is preferably 1.06 to 1.24 mg / cm ³ , more preferably 1.09 mg / cm ³ or more and 1.23 mg / cm ^3. It is ³ or less.

The mixing ratio of the polyester (A) and the semi-aromatic polyamide (B) constituting the polyester composition of the present invention is such that the semi-aromatic polyamide (B) is 0 relative to 100 parts by weight of the polyester (A). 0.01 parts by weight to 100
It is preferably part by weight. When it is desired to obtain a molded product having a very low AA content from the polyester composition, the amount of the semi-aromatic polyamide (B) added is 0.01 to 5 parts by weight based on 100 parts by weight of the polyester (A). Is more preferable, the more preferable lower limit is 0.1 part by weight, the still more preferable lower limit is 0.5 part by weight, and the more preferable upper limit is 4 parts by weight.
Parts by weight, more preferably the upper limit is 3 parts by weight.

Further, when it is desired to obtain a molded article having excellent gas barrier properties and transparency which does not impair practicality,
1 to 100 parts by weight of the semi-aromatic polyamide (B) is preferable with respect to 100 parts by weight of the polyester (A), a more preferable lower limit is 3 parts by weight, a still more preferable lower limit is 5 parts by weight, and a more preferable upper limit is 60 parts by weight. Parts, more preferably the upper limit is 30 parts by weight. When the amount of the semi-aromatic polyamide (B) mixed 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 contents The flavor retention may be very poor. Further, when the amount of the semi-aromatic polyamide (B) mixed exceeds 100 parts by weight with respect to 100 parts by weight of the polyester (A), the transparency of the obtained molded article may be very poor, and The mechanical properties of the molded product may also deteriorate.

The polyester composition of the present invention comprises at least two kinds of semi-aromatic polyamide (B) added to the polyester (A) whose main repeating unit is ethylene terephthalate. ) A method of dry blending at least two or more semi-aromatic polyamides (B) with a polyester (A) whose main repeating unit is ethylene terephthalate at the time of molding (2) In advance, at least two or more semi-aromatic polyamides (B) (3) is prepared by melt-mixing a polyamide resin composition, and is dry-blended with the polyester (A) whose main repeating unit is ethylene terephthalate at the time of molding (3) The polyester whose main repeating unit is ethylene terephthalate ( A) and at least two or more The semi-aromatic polyamide (B) in advance to prepare a polyester / polyamide resin mixture composition was melt mixed, and a method of dry blending and the like to the polyester (A) main repeating unit is ethylene terephthalate during molding.

The content of the cyclic ester trimer of polyester (A) whose main repeating unit is ethylene terephthalate used in the present invention is preferably 0.
50 wt% or less, more preferably 0.45 wt% or less,
More preferably, it is 0.40% by weight or less. When a heat-resistant hollow molded article or the like is molded from the polyester composition of the present invention, the cyclic ester trimer content is 0.50% by weight.
When a polyester having a content of more than is used, depending on the heat treatment conditions, the oligomer adhesion to the surface of the heating die may be sharply increased, and the transparency of the obtained hollow molded article may be extremely deteriorated. is there.

Conventionally, it has been considered that when a polyamide is blended with a polyester in order to have a gas barrier property or to suppress the amount of aldehyde generated, it becomes opaque. However, by taking the above means, 290 ℃
The haze of a molded product having a thickness of 5 mm formed by can be 20% or less, and when this resin composition is used as a package such as a bottle, it has a high gas barrier property and a high transparency so that the content can be seen. An easy package can be obtained. Further, since it is a blend, a simple molding machine can be used.
The haze of a 5 mm thick molded product molded at 290 ° C is preferably 15% or less, more preferably 10% or less.

Further, when the polyester (A) whose main repeating unit is ethylene terephthalate used in the present invention is melted at a temperature of 290 ° C. for 60 minutes, the increase amount of the cyclic ester trimer is 0.30. It is desirable that the content is not more than weight%. The amount of increase of the cyclic ester trimer is preferably 0.2% by weight or less, more preferably 0.1% by weight or less. When a polyester in which the increase amount of the cyclic ester trimer when melted at a temperature of 290 ° C. for 60 minutes exceeds 0.30% by weight, the amount of the cyclic ester trimer at the time of melting the resin when molding 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 polyester (A) used in the present invention, which has an increased amount of the cyclic ester trimer of 0.30% 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 are contacted with steam or a steam-containing gas to process, 50 to 50
Steam or steam-containing gas or steam-containing air at a temperature of 150 ° C., preferably 50 to 110 ° C. is preferably supplied or present as steam in an amount of 0.5 g or more per 1 kg of granular polyethylene terephthalate. The granular polyethylene terephthalate is contacted with steam. The contact between the polyester chips and steam is usually 10 minutes to 2 days, preferably 20 minutes to 10 days.
Done on time.

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.

When the polyester chips are continuously contacted with steam, granular polyethylene terephthalate is continuously received from the upper part in a tower type processing apparatus, and steam is continuously supplied in cocurrent or countercurrent to contact steam. Can be processed. As described above, when treated with water or steam, the granular polyethylene terephthalate is drained with a draining device such as a vibrating screener or a simon carter, if necessary,
Transfer to the next drying step by a conveyor.

For drying the polyester chips which have been contact-treated with water or steam, a commonly used polyester drying process 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 drying in a batch system, 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.

The polyester (A) whose main repeating unit is ethylene terephthalate used in the present invention is selected from the group consisting of polyolefin resin, polyamide resin, polyacetal resin and polybutylene terephthalate resin. At least one resin selected 0.1 ppb
It may be a polyester characterized by being blended in an amount of up to 1000 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 to 100 ppm, more preferably 0.5 p.
pb to 1 ppm, more preferably 0.5 ppb to 45
It is pbb.

When the compounding amount is less than 0.1 ppb, the crystallization rate becomes very slow and the crystallization of the plug part of the hollow molded article becomes insufficient. Therefore, if the cycle time is shortened, the plug part shrinks. 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 to be blended with the polyester (A) used in the present invention include homopolymers of ethylene, 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.

Examples of the polyamide resin blended with the polyester (A) used in the present invention include:
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 Alicyclic diamines such as 1,4-bis (aminomethyl) cyclohexane and bis (p-aminocyclohexylmethane), diamine units such as aromatic ring-containing diamines such as m- or p-xylylenediamine, and glutaric acid, adipine Acids, suberic acid, sebacic acid and other aliphatic dicarboxylic acids Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic 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 611, Nylon 612, Nylon 6T, Nylon 6
I, nylon MXD6, nylon 6/66, nylon 6
/ 610, nylon 6/12, nylon 6 / 6T, nylon 6I / 6T and the like.

The polyacetal resin blended in the polyester (A) used in the present invention includes, for example, 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
Polyacetal having a melt index (MI) measured at 0 ° C. and a load of 2160 g of 0.5 to 50 g / 10 min is preferable.

Further, as the polyacetal copolymer,
The density measured by the method of ASTM-D792 is 1.
Polyacetal copolymer having a melt index (MI) of 38 to 1.43 g / cm ³ , measured by ASTM D-1238 at 190 ° C. and a load of 2160 g of 0.4 to 50 g / 10 minutes is 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.

In the polyester blended with the above-mentioned polyolefin resin or the like used in the present invention, the resin such as the above-mentioned polyolefin is directly added to the polyester and melt-kneaded so that the content thereof is within the above range. 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 resin member such as the above-mentioned polyolefin under flowing conditions, the polyester chip-like member can be prepared in the empty space where the above-mentioned resin member such as the 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 is ethylene terephthalate used in the present invention has an acetaldehyde content of 10 ppm or less, preferably 8 ppm or less, more preferably 6 ppm or less.
More preferably, it is 4 ppm or less, and the formaldehyde content is 6 ppm or less, preferably 5 ppm or less, more preferably 4 ppm or less. If the acetaldehyde content exceeds 10 ppm and the formaldehyde content exceeds 6 ppm, the effect of retaining the flavor of the contents such as a molded product molded from this polyester becomes poor. The lower limit of the acetaldehyde amount and the formaldehyde amount is preferably 0.1 ppb.

The amount of diethylene glycol copolymerized in the polyester (A) whose main repeating unit is ethylene terephthalate used in the present invention is the lower limit of the glycol component constituting the polyester (A). Is preferably 1.0 mol%, more preferably 1.3 mol%, further preferably 1.5 mol%, and the upper limit is preferably 5.0 mol%, more preferably 4.5 mol%, further preferably Is 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 polyester (A) with the 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 simultaneously use a saturated fatty acid monoamide, an unsaturated fatty acid monoamide, a saturated fatty acid bisamide, an unsaturated fatty acid bisamide and the like 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.

Further, a metal salt compound of an aliphatic monocarboxylic acid 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 terephthalate bottle, etc. in an appropriate ratio.

When the polyester composition of the present invention is used for a film, calcium carbonate and magnesium carbonate are 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 stretched film comprising the polyester composition of the present invention is a sheet-like product obtained by injection molding or extrusion molding, and is usually PE.
It is molded by any stretching method of uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching used for stretching T. It is also possible to form 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 producing a 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.

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 body, 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 terephthalate bottles and the like can be mixed and used at an appropriate ratio.

Further, examples of other laminated moldings include:
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.

[0092]

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 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 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) Content of acetaldehyde in polyester (hereinafter referred to as “AA content”) Sample / distilled water = 1 g / 2 cc A glass ampoule with nitrogen substitution was sealed with the upper part and extracted at 160 ° C. for 2 hours. After treatment and cooling, acetaldehyde in the extract was measured by high sensitivity gas chromatography and the concentration was expressed in ppm.

(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 (R
v) A sample (0.25 g) was dissolved in 96% sulfuric acid (25 ml), and 10 ml of this solution was measured with an Ostwald viscous tube at 20 ° C. Rv = t / t ₀ t ₀ : Solvent drop time t : Number of seconds of dropping sample solution

(7) Measurement of fine content 0.5 kg of aromatic polyester chips was measured according to JIS-Z8.
It is placed on a stainless steel plain weave sieve (diameter 20 cm) having an opening of 1.7 mm and a needle diameter of 0.80 mm by 801 and it is 1800r with a teraoka swing type sieving tow machine SNF-7.
Sifted at pm for 1 minute. This operation was repeated to screen 20 kg of aromatic polyester chips in total. The sieved fines were washed with ion-exchanged water, filtered through a G1 glass filter manufactured by Iwaki Glass Co., Ltd., and collected. This was dried with a glass filter in a dryer at 100 ° C. for 2 hours, 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 = fine weight / weight of sieved aromatic polyester chips

(8) Molding of Stepped Molded Plate A dried polyester composition was manufactured by Meiki Seisakusho M-150.
C (DM) injection molding machine, cylinder temperature 290 ℃
In, the molding is performed using a stepped flat plate die cooled to 10 ° C. The obtained stepped molded plate is 2, 3, 4, 5, 6,
Approximately 3 cm x approximately 5 c with a thickness of 7, 8, 9, 10, 11 mm
The square shaped plate is provided stepwise, and the weight of one step forming plate is about 146 g. A plate having a thickness of 5 mm is used for measuring haze (% haze).

(9) Haze (% haze) and haze unevenness The molded body (wall thickness 5 mm) of the above (8) is cut out and measured with a haze meter manufactured by Nippon Denshoku Co., Ltd.

(10) Evaluation of mold contamination 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
Heat setting was performed for about 7 seconds in the mold set as above to obtain a hollow molded body of 1000 cc. 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 2000 pieces was visually observed and evaluated as follows. ⊚: Transparent ○: Transparent in the practical range, no unmelted substance is observed ×: Poor transparency or unmelted substance is observed

(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, flavor, odor and other tests were conducted. 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 rate (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 residual amount = about 40 to 50 ppm, phosphorus residual amount = about 3
The characteristics of 0 to 35 ppm) are shown in Table 1. These are all polymerized by a continuous melt polycondensation-solid state polymerization apparatus. PET (a) is about 9 in ion-exchanged water after solid state polymerization.
It was treated with hot water at 0 ° C. for 3 hours. In addition, PET
The DEG contents of (a) to PET (b) are all about 2.7.
The mol% and fine content were all about 30 ppm or less.

[0107]

[Table 1]

(Semi-Aromatic Polyamide Used in Examples and Comparative Examples) Semi-aromatic polyamide (A): Polyamide MXD6 manufactured by Toyobo Co., Ltd. T-600, Rv = 2.10 Semi-aromatic polyamide (B): Composition ratio 6T / 6I = 30
/ 70 (mol%), Rv = 2.07 Semi-aromatic polyamide (C): composition ratio 6T / 6I = 80
/ 20 (mol%), Rv = 2.23

In the above semi-aromatic polyamide, "6T" represents a repeating unit derived from hexamethylenediamine and terephthalic acid, and "6I" represents a repeating unit derived from hexamethylenediamine and isophthalic acid. . (Example 1) A stepped molding plate is molded by using 1.4 parts by weight of a semi-aromatic polyamide (A) and 0.6 part by weight of a semi-aromatic polyamide (B) with respect to 100 parts by weight of PET (a). Then
The haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded article had an AA content of 8 ppm, a sensory test evaluation of 0.7, the appearance was transparent in a practical range, and no mold stain was observed. The haze value was 7.4%.

(Example 2) Step-molding using 1.0 part by weight of semi-aromatic polyamide (A) and 1.0 part by weight of semi-aromatic polyamide (B) per 100 parts by weight of PET (a). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.
The hollow molded article had an AA content of 9 ppm, a sensory test evaluation of 0.7, the appearance was transparent in a practical range, and no mold stain was observed. The haze value was 5.1%.

Example 3 Step molding using 1.2 parts by weight of semi-aromatic polyamide (A) and 0.8 parts by weight of semi-aromatic polyamide (B) per 100 parts by weight of PET (b). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.
The hollow molded product has a low AA content of 8 ppm and has no problem with transparency within a practical range, but the sensory test evaluation is 2.0, which is different from blank distilled water, and the mold stain is considerably attached. Admitted. The haze value was 5.8%.

Example 4 Step molding using 1.0 part by weight of semi-aromatic polyamide (A) and 1.0 part by weight of semi-aromatic polyamide (C) per 100 parts by weight of PET (a). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.
The hollow molded article had an AA content of 9 ppm, a sensory test evaluation of 0.7, the appearance was transparent in a practical range, and no mold stain was observed. The haze value was 6.1%.

Example 5 Step molding using semi-aromatic polyamide (A) in an amount of 1.6 parts by weight and semi-aromatic polyamide (C) in an amount of 0.4 parts by weight per 100 parts by weight of PET (a). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.
The hollow molded article had an AA content of 8 ppm, a sensory test evaluation of 0.6, the appearance was transparent in a practical range, and no mold stain was observed. The haze value was 7.2%.

Example 6 A stepped molding plate was molded using 20.0 parts by weight of semi-aromatic polyamide (A) and 5.0 parts by weight of polyamide 6T6I with respect to 100 parts by weight of PET (a), The haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded article had an AA content of 7 ppm and a sensory test evaluation of 0.
6. Oxygen permeation rate is 0.20 cc / container 24 hrs at
m, the appearance was transparent in a practical range, and no mold stain was observed. The haze value was 15.7%.

(Comparative Example 1) A stepped molded plate was molded by using 2.0 parts by weight of semi-aromatic polyamide (A) with respect to 100 parts by weight of PET (a), and molded by the method of evaluation method (9). The haze of the plate was measured. Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded article had a low AA content of 9 ppm and a sensory test evaluation of 0.8, which was not different from the blank distilled water, but the transparency was poor. No mold stain was observed. The haze value was 23.6%.

(Comparative Example 2) A stepped molding plate was molded using 2.0 parts by weight of semi-aromatic polyamide (B) with respect to 100 parts by weight of PET (a), and was molded according to the evaluation method (9). The haze of the plate was measured. Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded article had a low AA content of 8 ppm and a sensory test evaluation of 0.7, which was not different from blank distilled water, but the transparency was poor. No mold stain was observed. The haze value was 36.4%.

(Comparative Example 3) Step molding using 1.9 parts by weight of semi-aromatic polyamide (A) and 0.1 part by weight of semi-aromatic polyamide (B) per 100 parts by weight of PET (b). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.
Although the hollow molded article had a low AA content of 9 ppm, the sensory test evaluation was 2.1, which was different from the blank distilled water, and the transparency was poor. In addition, a considerable amount of deposits was found on the mold stains.
The haze value was 24.7%.

(Comparative Example 4) Stepwise molding using 19.0 parts by weight of semi-aromatic polyamide (A) and 1.0 part by weight of semi-aromatic polyamide (B) per 100 parts by weight of PET (a). The plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains. The hollow molded article had a low AA content of 8 ppm and a sensory test evaluation of 0.7, which was not different from blank distilled water, but the transparency was poor. No mold stain was observed. The haze value was 62.9%.

(Comparative Example 5) Using only PET (b),
The stepped molded plate was molded, and the haze of the molded plate was measured by the evaluation method (9). Further, a hollow molded body was molded by the method of the evaluation method (10), and evaluation of mold stain was also performed. Table 2 shows the characteristics of the obtained hollow molded article and the results of evaluation of mold stains.

[0120]

[Table 2]

[0121]

According to the polyester composition of the present invention,
It is possible to obtain a hollow molded article, a sheet-shaped material and a stretched film which are excellent in flavor retention and / or gas barrier property and are also excellent in transparency.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/00 CFG C08L 77/00 C08L 77/00 101: 00 // (C08L 67/02 B29K 67:00 101: 00) 77:00 B29K 67:00 B29L 7:00 77:00 B65D 1/00 A B29L 7:00 F term (reference) 3E033 AA01 BA18 BA21 BB02 CA16 CA18 FA02 FA03 GA02 3E086 AD04 BA02 BA15 BB01 BB22 CA11 4F071 AA46 AA54 AF08 AF30 AF53 AH05 BA01 BB05 BB06 BB07 BC01 BC04 BC05 4F210 AA24 AA29 AA30 AG01 QC05 QG01 QG18 4J002 BB023 BB113 BB163 CB003 CF053 CF061 CL002 CL003 GG01

Claims (9)

[Claims] 1. To 100 parts by weight of a polyester (A) whose main repeating unit is ethylene terephthalate, 0.01 to at least two kinds of semi-aromatic polyamide (B).
A polyester composition obtained by adding 100 parts by weight. 2. The semi-aromatic polyamide (B) having a repeating unit derived mainly from an aliphatic dicarboxylic acid and an aromatic ring-containing diamine (B).
-1) at least one semi-aromatic polyamide selected from among, and at least one selected from semi-aromatic polyamide (B-2) having a repeating unit derived from an aromatic dicarboxylic acid and an aliphatic diamine. The polyester composition of claim 1 which is a class of semi-aromatic polyamides. 3. The semi-aromatic polyamide (B-1).
Is a metaxylylene group-containing polyamide (B-3), The polyester composition according to claim 1 or 2, wherein 4. The amount of increase in cyclic ester trimer when the polyester (A) whose main repeating unit is ethylene terephthalate is melted at a temperature of 290 ° C. for 60 minutes is 0.30% by weight or less. The polyester composition according to any one of claims 1 to 3, wherein 5. The polyester (A) whose main repeating unit is ethylene terephthalate is at least selected from the group consisting of polyolefin resin, polyamide resin, polyacetal resin and polybutylene terephthalate resin. It is polyester which mix | blended one type of resin 0.1 ppb-1000 ppm, It is characterized by the above-mentioned.
4. The polyester composition according to any one of 4 above. 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. The molded body according to claim 6,
A molded product, which is a stretched film obtained by stretching the sheet-like material according to 1. in at least one direction.