JPS63265950A - Thermoplastic polyester composition and vessel improved in retentivity of flavor - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in gas barrier property and suitable for a vessel excellent in preservation of food and retentivity of flavor and perfume, by adding an NH2 group-terminated thermoplastic polyamide as an acetaldehyde concentration lowering agent to a specified thermoplastic polyester. CONSTITUTION:A thermoplastic polyester (A), as a gas barrier polyester, containing a terephthalic acid component and an isophthalic acid component at a molar ratio of 95/5-5/95 in the polymer chain and containing an ethylene glycol component and a bis(2-hydroxyethoxy)benzene component at a molar ratio of 99.999/0.001-2.0/98.0 is mixed with 3X10<-7> 10.0wt.% (based on component A) thermoplastic polyamide (B) of a terminal NH2 group concentration of 0.05-50mmol./100g of the resin, as an agent for lowering the concentration of acetaldehyde generated by the heat decomposition of component A and the resulting mixture is melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic polyester composition having excellent gas and wall barrier properties and improved flavor retention, and a container formed from the same. The present invention relates to a composition and a container which have excellent gas barrier properties and which have improved storage stability for foods, flavor retention, aroma retention, etc. by completely reducing the concentration of acetaldehyde contained in the polyester.

(Prior art) Polyethylene terephthalate has excellent mechanical properties such as moldability and IJ-te property, and because it is possible to orient molecules in two directions, it has good creep resistance and impact resistance. It has come to be widely used as a lightweight plastic container with excellent rigidity, gas barrier, lightness, transparency, etc., especially as a beverage pin. However, the gas permeability of polyester bottles is still not negligible compared to glass bottles, and for example, a small polyester bottle of 1 liter or less filled with carbonated drinks such as cola has a shelf life of at most 2 months. It is said that the degree of

Conventionally, thermoplastic polyesters with excellent sparring properties are already known. For example, in US Pat. No. 4,398,017, terephthalic acid and isophthalic acid are used as acid components, and ethylene glycol and bis(2- It has been described that copolyesters containing (hydroxyethoxy)benzene components have excellent gas barrier properties.

(Problems to be Solved by the Invention) However, thermoplastic polyester generates all acetaldehyde due to thermal decomposition during thermoforming, and when used in all containers, the acetaldehyde in the container wall may spread to the contents. However, there is a problem in that the aroma and flavor of the contents are impaired.

As mentioned above, the acetaldehyde concentration contained in polyester is particularly high in sparring polyester.
It was confirmed that it is 2 to 5 times more powerful than polyethylene terephthalate. Thus, when gas-barrier polyester is used as a constituent material for all containers, even though the gas permeation of oxygen and carbon dioxide gas and the permeation of fragrance components are suppressed, the desired effect is not achieved because acetaldehyde transfers to the contents. I can't list them all enough.

Therefore, an object of the present invention is to reduce the concentration of acetaldehyde contained in a gas barrier thermoplastic polyester by a simple means, and to improve the aroma retention and flavor retention of the contents when used in a container. It is in.

(Means for Solving the Problems) According to the present invention, (A) a polymer chain contains a terephthalic acid component and an isophthalic acid component in a molar ratio of 95:5 to 5:95, and an ethylene glycol component. Tobis(2-hydroxyethoxy)benzene component and 't-99.999:
(B) a thermoplastic polyester containing a molar ratio of 0.001 to 2.0:98.0, and (B) a terminal amino group concentration of 0.001 to 2.0:98.0.
3 x 10 to 1 thermoplastic polyamide in the range of 05 to 50 mmol/100 g resin per polyester.
There is provided a thermoplastic polyester composition with improved flavor retention comprising 0.0% by weight of carbon.

According to the present invention, in a container formed by thermoforming of plastic, (4) the polymer chain contains a terephthalic acid component and an isophthalic acid component in a molar ratio of 95:5 to 5:95, and ethylene Glycol component and bis(2-hydroxyethoxy)
Benzene a minute! :′! 1l-99,999:0.00
(B) A thermoplastic polyamide having a terminal amino group concentration in the range of 0.05 to 50 mmol/100.9 m fat per polyester to a thermoplastic polyester containing a molar ratio of 1 to 2.0:98.0. A thermoplastic polyester container with improved flavor retention is provided, characterized in that the container is provided with a layer of a composition comprising from 3.times.10 to 10.0 weight percent.

(Function) The mechanism by which acetaldehyde is produced by thermal decomposition of polyester is the decomposition of the polymer hydroxy end group as shown in the following formula,
It is said to be caused by the decomposition of the polymer main chain as shown in the following formula.

It is recognized that the generation of acetaldehyde due to this thermal decomposition is greater in gas iZ rear polyester, which is a copolymerized polyester, than in polyethylene terephthalate, which has regular molecular chains.

The invention was based on the knowledge that when polyamide gold having a certain terminal amino group and 11 degrees is blended with this gas barrier polyester, the acetaldehyde content in the polyester can be reduced by 1 ffka by adding a relatively small amount of polyamide. It is based on That is, does it contain a terminal amino group used in the present invention? Lyamide acts as a degree-lowering agent for acetaldehyde in gas barrier polyester, and although its mechanism of action has not yet been fully elucidated, acetaldehyde is reduced in polyamide by the reaction shown in the following formula. It is thought that one of the reasons is that the amino group is trapped at the terminal end.

Since the polyamide used in the present invention is a polymeric substance (in polyester) dispersed in the polyester, it does not migrate into the contents of the container by extraction or volatilization like low molecular weight amino compounds. Moreover, the soybean itself has the advantage that it does not adversely affect the flavor of the contents.

The terminal amino group-containing polyamide used in the present invention may contain terminal amino groups to, os to a concentration of 50 mmol/100 g of polyamide side fat, particularly preferably 0.1 to 40 mmol/100 g of polyamide side fat. is important. When the terminal amino group concentration is lower than the above range, the acetaldehyde scavenging ability is insufficient, while when the terminal amino group concentration is higher than the above range, the blending of polyamide tends to cause a problem of deterioration of the flavor of the container. be.

In the invention, 3 x 10'-7 to 10 polyamides per gas barrier thermoplastic polyester.
．． It is contained in an amount of 0% by weight, especially in an amount of 5×10 5 to 5.0% by weight. That is, when the polyamide content is less than the above range, the effect of lowering the acetaldehyde concentration is not sufficient. Generally, as the polyamide content increases, the residual amount of acetaldehyde decreases, but even if the amount ratio is higher than the above, the residual acetaldehyde rate tends to be saturated, and in terms of the transparency and mechanical properties of polyester, a large amount of polyamide The combination of is not desirable.

In the present invention, the concentration of terminal amino groups in the polyamide is set to C mmol/100. F stool fat and d? Riester 100
．． When the number of blended parts of 9i polyamide is S, selection C
polyamide fU2X10-3 to 20 mmol per 100 g of polyester expressed as
In particular, it is most desirable that the amount is in the range of 6 x 10 to 1 mmol.

The terminal amino group concentration can be adjusted by adjusting the molecular weight, adjusting the reaction molar ratio between the noamino component and the dicargenic acid component, and terminal treatment at the time of termination of polymerization.

Gas barrier polyester Gas barrier polyester used in the invention (hereinafter referred to as B
It is also sometimes written as PR. ) contains a terephthalic acid component (T) and an isophthalic acid component (I) in the polymer chain in a molar ratio of T:I=95:5 to 5:95, particularly 75:25 to 25 nia5. and ethylene glycol component (with)
Tohis(2-hydroxyethoxy)benzene component (BH
EB) in a molar ratio of E:BHEB=99.999:0.001 to 2.0:98.0, particularly 99.95:0.05 to 40:60. As BHEB, 1.3-bis(2
-hydroxyethoxy)benzene is preferred.

T-I/E-BHEB polyester (BPR) i' used in the present invention! , the oxygen permeability coefficient (P
O2), the oxygen permeability coefficient has almost no humidity dependence, thermoforming is more stable than other sparring resins, and the adhesion to polyethylene terephthalate is extremely good. It is.

Of course, although it is used in the present invention, sparring polyester (B
PR) may contain small amounts of other dibasic acid components or other SOOL components as long as their essence is not impaired. Naphthalene 2,6-nocarbic acid, diphenoxyethane-4,4'-dicardenoic acid, 5
-Dicarboxylic acid components such as sodium sulfoisophthalic acid, azuvic acid, sebacin it or 34 alkyl esters thereof, fluoropylene gelicol, 1,4-butanediol, neopentyl glycol, 1゜6-hexine glycol , cyclohexane dimetatool, ethylene oxide adduct of bisphenol A, etc. may all be contained.

This polyester (BPR) should have at least a molecular cap sufficient to form a complete film,
Generally 60:40 of phenol and tetrachloroethane
Measured at a temperature of 30°C in a mixed solvent with a weight ratio of 0.
3 to 2.8 dlllg, especially 0.4 to 1,8
all/'! It is desirable to have an intrinsic viscosity [η] of Among these, those with relatively low molecular t are used for injection molding, and those with relatively high molecular weight are used for extrusion molding.

As the polyamide polyamide, all kinds of homopolyamides, co-polyamides, or blends thereof can be mentioned as long as the above-mentioned conditions are satisfied.

As such polyamides, in particular the following may be used for the purposes of the present invention: (1) For example, the following amide repeating units, namely Co-R-NH- (4) or -Co-R, -CONH-R2-NH-... (5) In the formula, R represents a linear alkylene group, and R1 and R2 are alkylene groups, arylene groups, under the condition that at least -1 is an alkylene group. A group consisting of a group or a combination thereof.

Homopolyamides, copolyamides or blends thereof with repeating amide units of can be mentioned.

From the viewpoint of scavenging ability for acetaldehyde, because the amide groups in polyamide have more than 100 carbon atoms, 1
Preference is given to using homopolyamides, copolyamides or blends thereof having between 30 and 30 knots, especially between 2 and 25 knots. Examples of suitable homopolyamides include polycapramide (nylon 6), poly-ω-aminohebutanoic acid (nylon 7),
-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylaurinlactam (nylon 12), ? 2,5
), polytetramethylene adipamide (nylon 4.6)
, polyhexamethyleneazino and mido (nylon 6.6)
, polyhexamethylene dodecamide (nylon 6°10)
, polyhexamethylene dodecamide (nylon 6°12), polyoctamethylene adipamide (nylon 8°6), polydecamethylene upamide (nylon 10°6), polydodecamethylene upamide (nylon 12°6)
, polydodecamethylene sepacamide (nylon 12°8), etc.

Examples of suitable co-polyamides include caprolactam/laurinlactam copolymers, caprolactam/hexamethylene diammonium adipate copolymers, laurinlactam/hexamethylene diammonium adipate copolymers, hexamethylene diammonium adipate/hexamethylene diammonium copolymers. Ammonium sepacate copolymer, ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, caprolactam/hexamethylene diammonium acetate copolymer/hexamethylene diammonium sepacate copolymer, and the like.

Further, as described in, for example, JP-A No. 60-159052, the following formula (6)% formula (6) In the formula, R3 and R4 each mean a hydrogen atom or a lower alkyl group.

1 to 100 moles of the structural unit represented by the following formula (
7) % formula % (7) In the formula, p means all integers from 2 to 11.

A thermoplastic polyamide consisting of a structural unit represented by O to 99 mol. For example, poly[α-(N,N dimethylamino)-6-caprolactam] and a copolymer of α-(N,N dimethylamino)-ε-cabrolatatum and 6-caprolactam.

Furthermore, aromatic polyamides may be used in place of the aliphatic polyamides mentioned above, such as in Japanese Patent Publications No. 50-1156, Japanese Patent Publications No. 5751-1980, Japanese Patent Publications No. 5753-1983, Japanese Patent Publication No. 50-10196, Kaisho 50-296
metaxylylene diamino, or mixed xylylene diamino containing metaxylylene diamino and 30% or less of the total amount of noraxylylene diamino, as described in Publication No. 97, etc., and having 6 to 6 carbon atoms. An aromatic polyamide containing at least 70 moles of structural units formed from 10 α,ω-aliphatic dicardic acids in its molecular chain. For example, polymethaxylylene adipamide.

These homopolyamides and co-polyamides can also be used in the form of so-called blends, for example blends of 2-licapramide and polyhexamethyleneazinogamide, polycapramide and caprolactam/hexamethylene ammonium anovate copolymers. Blend, pricapramide and poly[α-(N,N dimethylamino)
-ε-caprolactam], blends of polyhexamethylene azide/4'mide and polymethaxylylene adipamide, etc., can all be used for the purpose of the present invention.

(11) Isophthalic acid component units 'lr: diamino component units contained in the range of 30 to 100 moles, such as those described in JP-A-60-232952, JP-A-60-240452, etc. is 35 to 50
A substance consisting of 35 to 50 moles of diamino component units mainly composed of molti, metaxylylene diamino component units, and 0 to 30 moles of aminocarboxylic acid component units having carbon atoms in the range of 5 to 12. Superlinear co-condensed polyamide.

GiD A polyamide resin obtained by condensing and polymerizing diamino compounds with a polymerized fatty acid obtained by polymerizing an unsaturated fatty acid (for example, linoleic acid, lyluic acid, etc.) under heating and melting.

Auxiliary polymerized fatty acid polyamide, such as lyluic acid 2
A condensation polymer of mercury and hexamethylene diamino.

Is the molecular weight of these polyamides also related to their general film-forming ability? It can be used without particular restrictions as long as it is within the range of
As described later, the relative viscosity (ηR
It is generally desirable that EL ) be in the range of 0.4 to 4.5.

Blend The blend of the present invention contains the sparring polyester (BPR) and the terminal amino group-containing polyamide as described above, but this blend also contains compounding agents known per se,
For example, one or more of colorants, fillers, surfactants, lubricants, ultraviolet absorbers, antioxidants, nucleating agents, etc. can be blended in a known mixing ratio.

The blend used in the present invention may contain one or more thermoplastic resins other than those mentioned above for the purpose of modification, such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene- 1 copolymer, ionomer (olefin resin such as ionically crosslinked olefin copolymer, other thermoplastic polyester such as polyethylene terephthalate, polycarbonate, polyarylate, etc.).These other resins may be blends. 100 parts by weight or less per 100!f parts, especially 80M
It is recommended to use it in an amount equal to or less than that of Kajibu.

Blends can be prepared by tri-blending pellets or powders of multiple types of resins to be blended, then melt-kneading and pelletizing, but it is desirable to mix both of them homogeneously. Therefore, a method is advantageously employed in which plural types of pellets or powders are intimately mixed in a Henschel mixer or the like and then melt-kneaded. In addition, a small amount of Svalya polyester (BPR) and the polyamide to be blended are blended, or if necessary, the above-mentioned thermoplastic resin such as polyethylene terephthalate is blended, and the mixture is melt-kneaded to prepare a master batch. However, it is advantageous to use a method in which this master patch is blended with the remaining sparring polyester or, if necessary, a thermoplastic resin such as the above-mentioned polyethylene terephthalate, and then melt-kneaded.

Polyester (BPR) composition of the present invention? ! I can be used for various purposes such as film forming, container forming, laminating, extrusion coating, and powder coating.

Containers and Forming Methods Containers according to the invention are produced by means known per se, except for the use of the blends described above.

For example, sheets, pipes, or bottomed preforms for forming hollow containers are easily manufactured by extrusion molding, injection molding, compression molding, blow molding, or a combination thereof. These sheets, no! When manufacturing an eve or a bottomed preform, it is preferable that at least the portion of the polyester to be stretch-molded is substantially amorphous.

Of course, the parts that are not stretch-molded, such as the neck and bottom of the bottle, may be thermally crystallized. The method for forming the container is not particularly limited. For example, by stretch-molding a sheet, a bottomed plastic can body can be obtained which is used by wrapping a cup-shaped container with a side wall oriented uniaxially or a metal lid. In addition, by bottoming out the entire pipe, a preform with a bottom for stretch glow molding can be obtained, and by stretching the pipe in a uniaxial direction or in a biaxial direction, it is possible to obtain a preform with a bottom for stretch glow molding. A plastic can body for sealing with a metal lid is obtained. Furthermore, by stretching the bottomed preform in the axial direction and expanding and stretching it in the circumferential direction, a biaxially oriented plastic can be obtained. In order to improve the heat resistance of these stretch-molded containers, the orientation can be thermally fixed by heat treatment in a mold or the like under conditions of shape restriction.

The blend of the present invention can also be applied to film containers. In this case, the blend is formed into a film by a T-die method or the like, and this film is stretched in the longitudinal direction at a stretching temperature, and then stretched in the transverse direction. The film is stretched in the same direction using a tenter or other means to obtain a biaxially stretched film, and this biaxially stretched film is used for manufacturing containers.

In addition, this blend can also be used as a tray-shaped container for whole-cooking food in a microwave oven and/or open toaster, etc. For example, the blend can be formed into a whole-tray shape and then thermally crystallized. Improves heat resistance.

The sparring polyester (BPR) composition of the present invention can not only be used alone for manufacturing the containers described above, but also in the form of a laminate with other materials, especially other thermoplastic resins. Can be done. In particular, the gas barrier polyester composition (GCP) fd of the present invention has excellent adhesion to polyethylene terephthalate (PET), and is therefore used in the manufacture of containers in the form of a laminate with PET.

As a laminate, the inside of the container 1011 is on the left side, (1) Asymmetric two-layer two-layer GCP/PET, PET/GCP.

BL/PET, PET/BL.

(Δself number BL is a blend of GCP and PET (for example, scrap)) (11) Symmetrical two-type three-layer PET/GCP/PET.

(Iiii) Asymmetric three-layer four-layer PET/BL/GCP/PET.

PET/GCP/BL/PET.

(ψ symmetrical three types five layers PET/BL/GCP/BL/PET.

Attachment) Asymmetric three-layer five-layer PET/BI,/PET/GCP/PE
T.

PET/GCP/PET/BL/PET.

(B) Symmetric three-layer upper layer PET/BL/PET/GCP/PET/BL/PET
The following can be exemplified.

As polyethylene terephthalate (PET),
In addition to using polyethylene terephthalate alone, it is also possible to use a composition in which polyamide is similarly blended with polyethylene terephthalate for the purpose of reducing the acetaldehyde concentration. In this laminate, GCP
: The thickness ratio of PET is 5:1 to 1:20. Especially 2:1
It can be varied within the range of 1:10 to 1:10,
The thickness of the layer varies from 20 to 500μnn%% to 30 to 100% depending on the shape and internal volume of the container, or the wall thickness of the container.
It is best to be within the range of 0.011m.

The above-mentioned laminate can be manufactured by co-extrusion using extruders and multi-layer dies, the number of which corresponds to the type of resin layer, or by co-extrusion, which uses a number of extruders and multi-layer dies corresponding to the type of resin layer. It can also be carried out by co-injection using a co-injection runner and an injection mold.

The molding into a container is the same as for a single layer.

(Effects of the Invention) According to the present invention, by incorporating a small amount of thermoplastic polyamide into a specific copolyester, this copolyester has an excellent gas barrier property. It is possible to significantly reduce the concentration of acetaldehyde contained in the copolyester while preserving its properties. Therefore, by using this composition as a constituent material for all containers, the aroma and flavor retention properties of the contents can be significantly improved.

Therefore, for example, oil and fat foods such as tempura oil and salad oil; seasonings such as mayonnaise, dressing, and ketchup; various syrups such as ice cream; confectionery such as mizuyokan and jelly; ; Various carbonated drinks including cola, cider, plain soda, etc.;
Straight juice such as lemon juice, orenzo juice, plum juice, grape juice, strawberry juice, etc.
Juice or fruit juice drinks such as fruit juice drinks containing nectar or agar; Retrenchable drinks such as coffee and black tea; Health-oriented drinks such as vitamin-fortified drinks, aloe drinks, herp drinks, healthy vinegar drinks, and isotonic drinks; Green tea, kombucha, Sugar-free beverages such as oolong tea, amachiyazuru tea, barley tea, mamate tea, persimmon leaf tea, ginseng tea, corn potage, consommé soup, shellfish extract drink, mineral water; lactic acid bacteria beverages: fermented milk drinks Sonochi Useful as a container for storing gold.

(Example) The present invention will be explained in more detail in the following examples.

In addition, each measurement in each Example was performed according to the following method.

All Ubbelohde viscometers were used. Phenol/tetrachloroethane = 6/4 (weight ratio) using a mixed solvent of 30
Measured at °C.

(11) Relative viscosity of thermoplastic polyamide (f'A) (
ηREL) 1 g of thermoplastic polyamide resin with 96i of sulfuric acid 100
T! It was dissolved in water and measured at 25°C.

(iiD PA terminal amino group concentration (1m-NH2))
The terminal amino group was determined by potentiometric titration.

That is, approximately II of each sample of the thermoplastic polyamide (PA) used was strained, 50 mg of m-cresol (10μ, 95-96°C distillation) redistilled from the special grade reagent was added, and the mixture was reduced for 24 hours. Dissolved in a desiccator. Next, purified isop as a potential regulator. A special grade perchloric acid reagent (60% ethyl alcohol solution) was added to a mixed solution of beer alcohol and propylene glycol in a volume ratio of 2:1 to adjust the concentration to 0.005N, and this was used as a titration reagent. there was. Quantification of terminal amino groups was determined from the inflection point obtained from a plot of apparent potential versus perchloric acid consumption. Potentiometric titration was performed using a Toa Denpa Kogyo Co., Ltd. HM-S type meter.

(V) Terminal cal of PA? Xyl group concentration ([-COOH'
:l) Quantification of terminal carboxyl group is carried out using approximately 1 g of each sample.
Add 50% of benzyl alcohol (10 parts Hg, 90-93°C distillation) redistilled from whole spirit and special grade reagent,
It was melted at about 150°C. Next, each solution was filled with 0 and 01N potassium hydroxide titration solution using phenolphthalein as an indicator, and the terminal carboxylic group was determined from the amount consumed by subtracting i: consumed by pencil alcohol.

cI/) Acetaldehyde in the material (AA-M
) The amount of acetaldehyde in the material was determined by the Celanese method. That is, about 1 g each of the body and mouth of the sample described in each example was simultaneously ground in liquid nitrogen, 30 to 40 mfi'c of it was filled into a pre-swept glass insert, and then It was directly introduced into the injection section of a gas chromatograph (GC-6A model manufactured by Shimadzu Corporation) and heated at 145°C for 20 minutes to volatilize the acetaldehyde in the material.
ack Q.

Acetaldehyde was analyzed by raising the temperature from room temperature to 140°C. After the measurement, the weight of the test sample was calculated from the difference between the weight of (sample 10 glass insert) and the glass insert weight. The results are the average values of three repeated measurements.

(AA-I(S)) Use a gas exchanger to replace the nitrogen gas at the mouth of the container immediately after molding until the concentration of nitrogen reaches 99.99 vol. After sealing with
H), and after a predetermined period of time, the gas in the space inside the container was sampled from the rubber stopper at the mouth of the container, which was tested using the Mytalosy ring. The amount of acetaldehyde transferred from the container material to the space inside the container was measured using a romatograph. The results are shown as the average of measurements obtained from 5 samples.

Transparency (haze) was measured using a direct reading haze meter manufactured by Toyo Seiki Nosaku, and the haze value (
T(Z) was measured. The results show the average of five measurements for each sample.

(viii) Should oxygen gas permeability (QO2) be measured? After purging the inside of the bottle with nitrogen gas in a vacuum and covering the contact surface between the M tube and the rubber stopper with epoxy adhesive, the bottle was heated to a temperature of 30°C and a relative humidity of 20%.
R.H.

2) Temperature is 30°C and relative humidity is 80% RH.

Each sample was stored in a constant temperature and humidity chamber for 5 weeks.

Then each? The concentration of oxygen that permeated into the tank was measured using a chromatograph, and the oxygen gas permeability (QO
2, units are cc/m-day-atm) All calculations were made; QO2 = [mXCt/Zoo)/1XOPXA.

Here, m: filling of nitrogen gas into the detol (rnt), t;
Storage period (day) in a thermostatic chamber, Ct Oxygen concentration in the bottle after H (vol, %), A: effective surface area of the bottle Cm) OP: oxygen partial pressure C=0.209) (atm )
respectively.

The oxygen permeability (QO2) was measured for five samples each for one type of sample and each of the conditions 1) and 2) above.

In each of the Examples described below, the arithmetic average value of the permeability of five oxygen tubes was used.

Example 1 The polymer chain contains a terephthalic acid component (T) and an isophthalic acid component (I) in a molar ratio of 70:30, and an ethylene glycol component (T) and bis(2-hydroxyethoxy) A thermoplastic polyester containing a benzene component (BI (EB)) in a molar ratio of 95=5 and having an intrinsic viscosity (IV) of 0.69 dl/g (hereinafter, this resin i BPR-A
It is written as ) relative viscosity (ηREL
) is 3.42, and the terminal amino group concentration (C-NH2F)
is 1.637 m-rnol/Zoog, and the terminal carboxyl group concentration ([-COOHI) is 1.669 m-mol/
100 g of polycapramide (nylon 6) was added to 1.0 parts by weight (hereinafter sometimes referred to as PHR). ] All the ingredients were added and tri-blended for 10 minutes at room temperature using a tumbler type dry blender.

The obtained triblend product was manufactured by Nichia Hyashiko Kogyo Co., Ltd.ff.
With the FS-17ON type injection molding machine, the weight is 371
A preform with four thicknesses per wall was molded.

In addition, the injection conditions at this time are: ■ Barrel setting temperature: (rear part 200℃, (middle part) 21
4℃, (front part) 220℃, (nozzle part) 220℃.

■Scree rotation speed: 70 rpm.

■Injection pressure: 40 to 97 2° ■Cooling water temperature = 11℃.

■Molding cycle: 36 seconds.

Met.

For comparison, a preform of BPR-A alone (weight: 3
7fi, wall thickness: 2.6 saa) was also molded using the above injection molding machine and injection conditions.

Two types of BPR-A single preform obtained in this way and a blend preform containing 1.0 PHR of nylon 6 were manufactured by Toyo Food Machinery Co., Ltd.! ! !
A cylindrical tube having a droplet internal volume of approximately 10,351 nt (weight: 37 g) was molded using an OBM-I G type biaxial stretch blow molding machine.

The molding conditions for &) are that the preform temperature is 70℃ and 30℃.
After heating for seconds, blow molding was performed in the mold for 4 seconds.

Two types of biaxially stretched blows obtained? and for comparison, polyethylene terephthalate (hereinafter referred to as PET-A) with an intrinsic viscosity (IV) of 0.75 dllg.

) was molded using the injection molding machine and the stretch blow molding machine, and had the same weight and shape as above. Acetaldehyde-31 (A
A-M) was measured.

AA tr121.5 in BPR-A single bottle material
ppm, while nylon 6 has a pH of 1.0
R-added blend/yl? ) AA in the material is 2.
It was 4 ppm. Moreover, in &tor of the above-mentioned PET-A alone, AA-Ml! It was 5.9 ppm.

By adding nylon 6k 1.0 PHR, the AA in the material is reduced to about 10%, and the acetaldehyde i-(AA-M) in the material is lower than that of polyethylene terephthalate alone (PET-A). known to reduce

On the other hand, 1 and 0 were added to the two types of BPR-A and BPR-A.
PHH nylon 6 added, N) and PET
-A alone? Regarding the total three types of toru, the c
Oxygen gas permeability (QO2
) measurements were carried out.

The oxygen gas permeability of various kinds of samples stored under conditions of a temperature of 30°C and a humidity of 20% RH is that of the BPR-A alone.
Torr is 2.54, and BPR-A & Torr to which 1.0 PHR of nylon 6 is added is 2.11, and the PE'l'
-A alone & Torr is 7.66 (however, the unit is c
c/m-day-atm).

In addition, the oxygen gas permeability of various bottles under storage conditions of 30°C and 80% RH was 2.56 for the BPR-A alone and 1.0 PHR for the BPR-A to which nylon 6 was added.
PR-A? The bottle is 2.29, and the PET-A single FJ%') is 7.70 (however, all units are c
c/m-day*atm).

The oxygen gas permeability under each storage condition is the BPR-
The values for various types of A-type bottles are clearly smaller than the results for PET-A single bottles, indicating that the barrier properties are improved, and that the addition of 1.0 Pl of nylon 6 does not have a negative effect on the barrier properties. known.

Example 2 The polymer chain contained terephthalic component (T) and isophthalic acid component (I) in a molar ratio of 40:60, and also contained ethylene glycol component (with) and bis(2-hydroxyethoxy). ) A thermoplastic polyester containing a benzene component (BHEB) at a molar ratio of 80:20 and having an intrinsic viscosity (IV) of 0.55 dl/g (hereinafter, this resin will be referred to as BPR-B) is On the other hand, polyhexamethyleneazino-4mide (nylon 6.6: ηRE) was ground in liquid nitrogen.
L=1.27, C-NH2)=4.429mmo
l/1009, C-C0OH] = 4.486 and nol
/ 100. ! After adding 10.9 g of the powder of B
PR-B/nylon 6.6 master patch (pellet) 2 obtained*.

The master patch obtained in this way and BPR-B
20 master patches obtained by using the tumbler-type dry blender described in Example 1 with the chips (pellets) to obtain the following three types of tri-blend products: BPR-B
=1:200=0.0005 PHR.

■Masterbatch: BPR-B=1: 100=0
, OOI PHR.

■Masterbatch: BPR-B=1: 10=0,
01 PHR.

In the case of Example 1, a total of four types of materials, including the three types of triblends obtained in this way and BPR-B alone, were processed using the injection molding machine and biaxial stretch blow molding machine described in Example 1. A cylindrical mold with an internal volume of about 1035 m (weight 37 g) was molded under the same injection and blow molding conditions.

Regarding the four types of biaxially stretched blow bottles obtained, the amount of acetaldehyde (AA-M) i in each bottle material was measured according to the method of M mentioned above. The results are shown in Table 1.

Even if the amount of nylon 6.6 added is in such a low concentration range,
It is known from Table 1 that AA in the material was reduced to about 65% or less, and the effect of reducing acetaldehyde was large.

On the other hand, the oxygen gas permeability of the four types of biaxially stretched blow bottles was measured according to the method described in <viii) above. The results are shown in Table 2.

It is understood from Table 2 that such an amount of nylon 6.6 added does not adversely affect the barrier properties of the bottle.

Table 1 Table 2 Example 36 Thermoplastic polyester described in Example 1 (BPR-A
), the relative viscosity (ηREL) is 2.24, and the terminal amino group concentration (C-NH2)) is 0.471 m・mo1/1.
00j? , terminal force/Lyk” xyl group concentration ([-COO
Polymethaxylylene adipamide (nylon MXD 6 ) having IO) of 0.483 mmol/100 g was blended using the tumbler-type dry blender described in Example 1 at the following blending ratio (weight ratio). Tri-blended with: ■BPR-A: MXD6= 100: 0.5=
0.5 PI(R.

■BPR-A: MXD6=100: 2. O=2
．． OPHR.

■BPR-A:M) ■6=100: 4.0=4.0
PHR.

■BPR-A: MXD6= 100: 8. O=
8.0 Pf(R.

■BPR-A:M)■6 = 100: 15.0=
15.0 PHR.

Then, these five types of triblend products were prepared in Example 1.
Using the injection molding machine and biaxial stretch blow molding machine described in Example 1, under the same injection and blow molding conditions as in Example 1,
A cylindrical tube with an internal volume of about 1035 d (37 yq) was formed.

The acetaldehyde t(AA-M) in each of the obtained 5 kinds of biaxially stretched 1 oz Torr materials was determined according to the method (V) described above. All results are shown in Table 3. The third column also shows the results obtained when both BPR-A alone and PET-A 13 described in Example 1 were tested.

Within this additive range of nylon MXD 6, the amount of AA in the material is reduced to around 10%, but MXD 6
It is known from this table that even if the addition value of is increased further, the effect of reducing AA-M becomes smaller.

Next, a total of 7 types of these five types of biaxial stretching blows and each biaxially stretching blow g
Transparency (haze,
H2) was measured. The results are also shown in Table 3.

It is known from Table 3 that when the amount of nylon W6 added is about 15.0 PHR, the transparency (H2) of the container is rapidly lost.

On the other hand, BPR-A added with MXD 6 of the above five keyaki species
&) The oxygen gas permeability (QO2) of the sample was measured according to the method described in (viii) above.

These results and B described in Example 1 for comparison
The results for PR-A and PET-A alone are also shown in Table 4.

The oxygen gas permeability of each torr under each storage condition is yj? In Toru, PET-A alone
The value is clearly smaller than the result of k" tor, indicating that the barrier properties are improved, and the addition amount of nylon (C6) below 15.0 PHR does not adversely affect the barrier properties of the gettle. It is clear from Table 4. It is also known from Table 4 that when the amount of nylon added is 15.0 PHR or more: the dependence of oxygen gas permeability on humidity becomes large.

Example 4 The thermoplastic polyesters (BPR-A and BPR-B) of 2P@ode described in Examples 1 and 2, respectively, and the relative viscosity (ηREL) of 0.52 and the terminal amino group strength ([-
NH2)) is 31.08 mrnol/100.9. A piece of polymerized fatty acid polyamide (polymerized fatty acid PA) having a terminal carboxyl group concentration of 31.22 mmol/100 g was mixed with ■BPR-A: Polymerized fatty acid PA=100:10 (M amount ratio) ■BPR-B: Polymerized fatty acid PA= After tri-blending at a ratio of 100:10 (weight ratio), the mixture was pelletized by the pelletizing method described in Example 2 to obtain two types of master patches (pellets) 2: ■ and ■.

And further BPR-A: ■ Master patch = 10:1 = 1.0PH
R.

BPR-B: ■Master patch = 10:1 = 1.0PH
R.

Two types of triblends were prepared using the tumbler-type dry blender described above, and the same injection molding as in Example 1 was carried out using the injection molding machine and biaxial stretch blow molding machine described in Example 1. A cylindrical mold having an inner volume of about 1035 td (heavy load: 37 g) was molded under the conditions of 1 and 2 under plow conditions.

The two types of biaxial stretching rollers obtained? Regarding the torque, each ? according to the method of M mentioned above. Acetaldehyde (AA-M) in the tor material was measured. The results are listed in Table 5. Table 5 shows the BPs described in Examples 1 and 2, respectively.
AA in each gettle material of R-A alone and BPR-B alone
The amounts are also reproduced for reference.

The results in Table 5 indicate that in thermoplastic polyamides with a high concentration of terminal amino groups, such as polymerized fatty acid polyamides, the effect of reducing acetaldehyde is significantly large even when a small amount is added.

In addition, regarding these yN), the above (■II)
Transparency (haze) of the mid-torso according to the method of

Hz)i was measured and all the results are shown in Table 5. It is known that there is virtually no significant difference in transparency.

On the other hand, regarding the two types of biaxial stretching rolls,
The oxygen gas permeability was measured according to the method of VLLO described above. The results are shown in Table 6.

For comparison, Table 6 shows B
The results from PR-A and BPR-B alone and tor are also reproduced.

With such an added amount of polymerized fatty acid polyamide, yjr
) It can be seen from Table 6 that it does not have a negative effect on the barrier properties of the resin.

Example 5゜8 Using an ASB-250TH type co-injection/biaxial stretching professional molding machine manufactured by NPS Machine Co., Ltd., the polyethylene terephthalate B described in Example 1 was injected into the main injection machine of the same machine.
pET-a) t-1 Also, in the sub-injection machine of the same machine, the thermoplastic polyester (BPR-A) described in Example 1 alone, and the BPR-A and the polymethaxylylene described in Example 3, Az/4 A tri-blend product with a weight ratio of 99.5:0.5 (hereinafter referred to as G
It is written as CP. ) were supplied respectively. And, ■Main injection temporary setting temperature: Rear part: 280℃, middle part: 280
°C, nozzle part: 285 °C.

■Sub-injection machine setting temperature: Rear: 195℃, middle: 215
°C, nozzle part; 215 °C.

■Hot runner nozzle temperature setting: 285℃.

■PET primary injection pressure (gusso pressure): 120kl?
/crn9 ■ Injection pressure (r-) pressure of blend of BPR-A or hBPR-A and MxD6 (r-pressure): 145kl? /6n
0■ PET secondary injection pressure (goo pressure): 90 to 97.

Under the co-injection conditions, the weight was 59I, the total thickness was 4.1mm, inner layer (PET): middle layer (BPR-A or GCP).
): Outer layer (PET) (7) Thickness ratio Kao, 5:1
: A multilayer preform of 1.5 is molded, and then in a glow zone, the heating temperature of the multilayer preform is 100'C0, the stretching ratio in the longitudinal (axial) direction is 2.5 times, and the stretching ratio in the lateral (circumferential) direction is 2.5 times. ) All biaxial stretching blowing was carried out with a stretching ratio of 3.5 times, and the weight was 59! ? Two types of cylindrical multilayer tors with an internal volume of 15,201 nt were molded.

Further, only the main injection machine of the co-injection/biaxial stretch glow molding machine is used, and the polyethylene terephthalate (PE)
T-A) Using a simple substance and a tri-blend product having a composition ratio of 99.5:0.5 by weight of the BPR-A and the W6, the BPR-A and the W6 have the same weight and shape as above.
A type of yN tor was molded.

Hereinafter, (&): the above PET alone, (b): the co-injection of the PET/BPR-A/PET configuration/biaxially stretched prodator, (c): the co-injection of the PET/GCP/PET configuration/ Biaxially stretched probetle, (d) + @described BPR-A k @described ■■6 are described as blendbuttle having a weight ratio of 99.5:0.5.

For the four types of biaxially stretched blowhidles obtained in this way, acetaldehyde migration (1 (AA-H8)) into the inner space of the container was measured according to the method of VD described above. Measurements were carried out for a maximum of 13 weeks. The results are shown in Figure 1.

From Figure 1, polymethaxylylene adipamide (nylon M
XD6) The bottles containing i (C and d) are the same (MX
Compared to hiddles (1 and b) that do not contain D 6 ,
It is understood that the amount of acetaldehyde transferred to the space within the container is clearly small.

On the other hand, <vii) and <viii described above
The transparency and oxygen gas permeability of these four types of hiddles were completely measured in accordance with the method described in the following. The results are shown in Table 7.

The transparency (H2) of the hidr is substantially unchanged compared to PET alone (a), and the oxygen permeability of the hidr under each storage condition is different from each [& In (b, c and d), PET alone &) le (,)
It can be seen from Table 7 that the value is clearly smaller than the result shown in Table 7, indicating that the barrier properties are improved, and that such added amounts of nylon 1 and 6 do not adversely affect the barrier properties.

Example 6 Composition using the thermoplastic polyester (BPR) described in Example 5 ``vIJ Zettle and Tafu Gottle samples, and for comparison, a total of 4 types of molded PET single samples (a, b , e and d6 bottles are described in Example 5. ) was filled with a commercially available square can of salad oil, the mouth was sealed, and then heated at 22°C and 60% R).
They were stored for 2 weeks and 4 weeks, respectively, in a constant temperature and humidity chamber (in the dark). Then, in each storage area, about 200 of the salad oil was transferred to a 300-gallon beaker and kept at about 60°C on a hot plate.

A flavor test using a paired comparison method was then conducted on a panel of 21 people (11 men and 10 women). This is a method in which two types are selected from among the four flavors a to d, and it is determined which of the salad oil flavors filled in each flavor is preferable. One point was given to the bottle filled with the salad oil that the respondents answered as preferable. In addition, if the answer was that there was no difference in flavor between the two, 0.5 points were given to each.

Table 8 shows the results of a flavor test on salad oil stored for 2 weeks in an atmosphere of 22° C. and 60% RH, and Table 9 shows the results of a flavor test on salad oil stored for 4 weeks in the same atmosphere as above.

In these tables, "winning points" means the points obtained by the method described above. Also, it is the value obtained by dividing the "winning rate" by the total number of winning points for each panel (=21 people).

Furthermore, the symbols ◎, ○, △, shi, and × written in each column of Annaka have the following meanings: Reference books (in this case, [Toshio Nonaka, Toshio Sasai Co-authored “Complete Book of Mathematics Exercises-9, Exercises on Probability and Statistics, Chapter 7-Engineer Hypothesis Testing”, pp. 173-178, Morikita Publishing Co., Ltd., Tokyo (1
961) According to J), the hypothesis (null hypothesis) is that ``The probability that each sample in each pair in contrastive teaching is scored is 1/2 (=0.5). There is no significant difference in the scores of each sample within a pair.)". The region where the hypothesis is rejected (that is, denied) when the risk rate is α, R1, is expressed by the formula, R=P±V〒7U [where, P; probability of occurrence (= 0.5), t: the point at which the risk rate is α% (normal distribution), N: the number of base channels (in this case, N=21), respectively.

Table 10 shows the rejection ranges, R1, and their corresponding judgment symbols for the four no-hypotheses calculated from the above formula, with the risk rate α ranging from 0.1% to 10.0%.

Therefore, each symbol listed in Tables 8 and 9 is
The corresponding "winning rate" means where in the rejection region R in Table 10 it belongs.

From Table 8, the flavor of salad oil stored for two weeks is:
There was no significant difference between the four types of sample hiddles mentioned above, and there was a slight significant difference between the multilayer containing a small amount of nylon MXD 6k (e) and the control (a). , eyk') The flavor of the salad oil filled in the bottle was determined to be better.

However, when the storage period reaches 4 weeks, the salad oil filled in the &)le (C and d) containing nylon W■6 is the same as the salad oil (y not containing MXD6')? ) le (a and b
) showed a significant difference in flavor, and the flavor of the former bottles (C and d) was more obvious than that of the latter bottles (a and b). Table 9 shows that the flavor was good. In addition, from Table 9, the blend of Multilayer & Toru (C) containing MXD 6 in the intermediate layer and W ■ 6, which is the same as BPR-A described in Example 5, is Toru (d).
It is known that there is no significant difference in flavor between the salad oils filled with and.

Example 7゜Thermoplastic polyester (BPR) described in Example 5
A total of 4 samples (a, b, c, and d; details of the bottles are described in Example 5) were prepared for each sample of a composition bottle and a multilayer bottle using PET and a sample of a single PET molded for comparison. After packing commercially available carbonated water in a glass bottle and sealing the mouth, store at 22℃ and 60%RH.
The samples were stored in a constant temperature and humidity chamber (dark place) for 2 weeks and 4 weeks, respectively.

In each conservation area, a panel of 21 people (one male
A flavor test was conducted using the paired comparison method on 10 participants (one female and one female). this is.

From the four types of bottles a to d above, select type 2a as a pair, drink the carbonated water filled in each bottle, and judge which bottle of carbonated water has a better taste. This is the way to do it. One point was given to the bottle filled with carbonated water, which the respondents answered as preferable. -Also, if it was answered that there was no difference in flavor between the two, 0.5 points were given to both.

Table 11 shows the flavor test results for carbonated water stored for two weeks in an atmosphere of 22°C and 60% RH, and Table 12 shows the results of carbonated water stored for four weeks in the same atmosphere as above. Each is shown below.

In these tables, "winning points", "winning percentage", and "◎, ○"
, 61 and × symbols” are all the same as described in Example 6.

From Table 11, the flavor of carbonated water stored for two weeks is:
There was not much difference observed between the four types of sample bottles mentioned above; the multilayer bottle and blend & tor (C and d) containing nylon ■■6 described in Example 5, and the one containing the above ■■6. There was a slight significant difference between the bottles (a and b) without carbonated water, and the carbonated water filled in bottles C, d, and f was judged to have a slightly better flavor.

However, when the storage area reaches 4 weeks, the carbonated water filled in each yN) containing nylon 6 described in Example 5 (C and d) is the same as the y not containing MXD 6.
There was a significant difference in flavor between the carbonated water filled in j=')le (a and b), and the former's ylr)le(
Table 12 shows that the carbonated water filled in C and d) clearly has a better flavor than the latter (a and b) carbonated water filled with K. Also, the 12th
From the table, it can be seen that the multilayer containing the MXD 6 as an intermediate layer is the same as that of Tor (e) and BPR-A described in Example 5 (MX
It is known that there is no significant difference in flavor between the carbonated water filled in the blend bottle (d) with D6.

Example 8 - Samples of compositions and multilayer bottles using heat-labile polyester (BPR) described in Example 5, and samples of PET alone molded for comparison, total of Class 4a (a, b , c and d. For details of the tettle, see Example 5.
Described in. ), pour a full amount of mineral water in a commercially available glass bottle. After sealing the opening of the rack,
They were stored in a constant temperature and humidity chamber (in the dark) at 2°C and 60% Rf for 2 weeks and 4 weeks, respectively.

In each conservation area, a panel of 21 people (one male
A flavor test using the paired comparison method was conducted on 1 person (1 female). this is.

From the four types of bottles a to d, select two types as a pair, put the mineral water filled in each bottle in your mouth, and have the students decide which bottle has the better taste. It's a method. and,
One point was given to bottles filled with mineral water that were answered as preferable. In addition, if the answer was that there was no difference in flavor between the two, 0.5 points were given to both.

Table 13 shows the flavor test results for mineral water stored for 2 weeks in an atmosphere of 22°C and 60% RH, and Table 14 shows the results of mineral water stored for 4 weeks in the same atmosphere as above. show.

In these tables, "winning points", "winning percentage", and [◎, ○
, Δ1 and × have the same meanings as described in Example 6.

From Tables 13 and 14, it can be said that the results for mineral water are almost the same as in the case of carbonated water (Example 7). However, this tendency is true for carbonated water (Example 7)
Even in storage for two weeks, the multi-layered material not containing nylon MXD6 described in Example 5 was even more remarkable than the above. The 13th fi. known from.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between the storage period and the amount of acetaldehyde released into the inner space of the container (AA-H8) for various plastics and torsions in Example 5, where symbols x and Δ indicate thermoplastic Those without polyamide are marked with the symbol ○.
and . indicate those containing thermoplastic polyamide. Patent Applicant Toyo Seikan Co., Ltd. Agent Patent Attorney Ikuo Suzuki 13,\ Agent Patent Attorney Yukio Shoko -'1, :) ゛・,;-゛' AA-1-15 [ppb] Hand Itopugo Yu11 Original text (spontaneous) 1986 6
June 19th, Commissioner of the Japan Patent Office, Kuro 1) Mr. Yu Akira 1, Indication of the case, Patent Application No. 98596 of 1988 2, Name of the invention Thermoplastic polyester composition and container with improved flavor retention 3, Person making amendment case Relationship with Patent applicant address 1-3-1 Uchisaiwai-cho, Chiyoda-ku, Tokyo Name (37
6) Toyo Seikan Co., Ltd. 4, Agent 105 5, No date of amendment order 7, Contents of amendment ■-5-(1
) In the 7th line of page 32 of the specification, ``The wall thickness is 4 mmj'' is corrected to ``The wall thickness is 2.6 mmj.'' (2) In the 2nd line of page 55, rR=Pf, PX 1- Correct P/NJ to !'R=PftXPX (1-P)/N:.

Claims (2)

[Claims] (1) (A) The polymer chain contains a terephthalic acid component and an isophthalic acid component in a molar ratio of 95:5 to 5:95, and an ethylene glycol component and a bis(2-hydroxyethoxy)benzene component of 99%. .999:0.001 to 2.0:98.0 molar ratio, (B) a terminal amino group concentration of 0.05 to 50 mmol/
A thermoplastic polyester composition with improved flavor retention comprising a thermoplastic polyamide in the range of 100 g resin in an amount of 3 x 10^-^7 to 10.0% by weight per polyester. (2) In a container formed by thermoforming or stretch molding of plastic, (A) the polymer chain contains a terephthal component and an isophthalic acid component in a molar ratio of 95:5 to 5:95, and an ethylene glycol component; and bis(2-hydroxyethoxy)benzene component from 99.999:0.001 to 2.0:
Thermoplastic polyester containing at a molar ratio of 98.0, (B) a terminal amino group concentration of 0.05 to 50 mmol/
A flavor characterized in that the container is provided with a layer of a composition comprising a thermoplastic polyamide in the range of 100 g resin in an amount of 3 x 10^-^7 to 10.0% by weight per polyester. Thermoplastic polyester container with improved retention.