JP7085150B2 - Polyester container and polyester preform - Google Patents

Description

The present invention relates to a polyester container and a polyester preform used in the manufacture of the polyester container.

Polyesters such as polyethylene terephthalate have excellent mechanical properties, chemical stability, heat resistance, gas barrier properties, transparency, etc., and are inexpensive, so they are widely used in the manufacture of containers for filling beverages, etc. There is.
Further, in recent years, it has been desired to use a polyester container having a high environmental load reducing property.

The present invention has been made in view of the above, and an object thereof is to improve the yield of the polyester container by suppressing the white turbidity of the polyester container, and as a result, resource saving by reducing the amount of waste products is achieved. At the same time, it is intended to provide a polyester container having a high environmental load reducing property by reducing the energy consumption in the production of the polyester container.
It is also to provide a polyester preform used for manufacturing this polyester container.

In the first aspect, the present invention is a polyester container made of polyester.
In polyester, the ratio of isophthalic acid units to terephthalic acid units determined by the nuclear magnetic resonance spectrum is 0.0005 or more and 0.010 or less, which is a polyester container.

In one embodiment, the polyester container has a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes in differential scanning calorimetry. Is.

In one embodiment, the polyester container has a first layer and a second layer constituting an inner layer, the first layer is made of virgin polyester, and the second layer is made of recycled polyester. There is.

In one embodiment, the polyester container further comprises a third layer constituting an outer layer, the third layer being composed of virgin polyester.

In one embodiment, the first layer is provided from the content filling region or from the top to the bottom of the mouth.

In one embodiment, the polyester comprises a copolymer of terephthalic acid and isophthalic acid with ethylene glycol.

In one embodiment, the thickness of the cross section of the polyester container is 0.05 mm or more and 0.54 mm or less.

In the first aspect, the present invention is a polyester preform for producing the polyester container.
Polyester preform is made of polyester,
In polyester, the polyester preform has a ratio of isophthalic acid units to terephthalic acid units determined by a nuclear magnetic resonance spectrum of 0.0005 or more and 0.010 or less.

In the second aspect, the present invention is a polyester container made of polyester.
In the differential scanning calorimetry of the polyester container, the temperature lowering crystallization temperature when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes is 175 ° C. or higher and 200 ° C. or lower.

In one embodiment, the polyester container has a first layer and a second layer constituting an inner layer, the first layer is made of virgin polyester, and the second layer is made of recycled polyester. There is.

In one embodiment, the polyester container further comprises a third layer constituting an outer layer, the third layer being composed of virgin polyester.

In one embodiment, the first layer is provided from the content filling region or from the top to the bottom of the mouth.

In one embodiment, the polyester is polyethylene terephthalate or modified polyethylene terephthalate.

In one embodiment, the thickness of the cross section of the polyester container is 0.05 mm or more and 0.54 mm or less.

In the second aspect, the present invention is a polyester preform for producing the polyester container.
Polyester preform is made of polyester,
In the differential scanning calorimetry of the polyester preform, the polyesterp has a temperature reduction crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature reduction rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes. It is a reform.

According to the present invention, it is possible to provide a polyester container having a high environmental load reducing property.
Further, it is possible to provide a polyester preform used for manufacturing this polyester container.

It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-sectional view which shows one Embodiment of the polyester container of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention. It is a schematic semi-cross-sectional view which shows one Embodiment of the polyester preform of this invention.

First aspect <polyester container>
The polyester container of the present invention is made of polyester. In the present invention, "polyester" means a copolymer of a dicarboxylic acid compound and a diol compound.
As the dicarboxylic acid compound, terephthalic acid and isophthalic acid are used, but a dicarboxylic acid compound other than terephthalic acid and isophthalic acid may be used together with terephthalic acid and isophthalic acid. Examples of dicarboxylic acid compounds other than terephthalic acid and isophthalic acid include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecandionic acid, eikosandionic acid, pimelic acid, azelaic acid, and methylmalon. Acids and ethylmalonic acid, adamantandicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid Acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodiumsulfoisophthalic acid, phenylendandicarboxylic acid, anthracendicarboxylic acid, phenantrangecarboxylic acid, 9, Examples thereof include 9'-bis (4-carboxyphenyl) fluorenic acid and ester derivatives thereof.
Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, and cyclohexane. Diethanol, Decahydronaphthalenedimethanol, Decahydronaphthalenediethanol, Norbornanedimethanol, Norbornandiethanol, Tricyclodecanedimethanol, Tricyclodecaneethanol, Tetracyclododecanedimethanol, Tetracyclododecanediethanol, Decalindiethanol, Decalindiethanol, 5 -Methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis (4-hydroxy) Cyclohexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, adamandiol , Paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, trimethylolpropane, pentaerythritol and the like.
The polyester preferably contains a copolymer of terephthalic acid and isophthalic acid and ethylene glycol.

As long as the characteristics of the present invention are not impaired, the polyester in the polyester container may contain a monomer other than the dicarboxylic acid compound and the diol compound, but the content thereof is 10 mol% or less with respect to all the constituent units. It is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 3 mol% or less.

In the present invention, the polyester in the polyester container is characterized in that the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum is 0.0005 or more and 0.010 or less.
As will be described later, the polyester container can be manufactured by first injection molding polyester to produce a polyester preform and then blow molding the polyester preform. Here, the presence of an isophthalic acid unit in the polyester tends to lower the melting point of the polyester. In the present invention, by setting the ratio of the isophthalic acid unit to the terephthalic acid unit to 0.0005 or more, the melting point of the polyester can be lowered and the injection molding of the polyester preform can be performed at a lower temperature. As a result, the energy consumption in the production of the polyester container is reduced, and the polyester container having a high environmental load reducing property can be obtained.
Further, by setting the ratio of the isophthalic acid unit to the terephthalic acid unit to 0.010 or less, the white turbidity of the polyester container can be suppressed. The reason for this is not clear, but it is considered that the water content of the polyester could be reduced by reducing the ratio of the isophthalic acid unit in the polyester. Therefore, in the polyester container of the present invention, by setting the ratio of the isophthalic acid unit to the terephthalic acid unit to 0.010 or less, the white turbidity of the polyester container can be suppressed and the yield of the polyester container can be improved. As a result, resource saving is achieved by reducing the amount of waste products, the energy consumption in the production of the polyester container is reduced, and the polyester container having a high environmental load reduction property can be obtained.
In the polyester container of the present invention, the more preferable ratio is 0.0008 or more and 0.009 or less, and more preferably 0.001 or more and 0.008 or less.

The nuclear magnetic resonance spectrum of the present invention can be measured by a known method using a nuclear magnetic resonance measuring device ( ¹ H-NMR). In the present invention, the ratio of the isophthalic acid unit to the terephthalic acid unit shall be determined from the ¹ H-NMR spectrum measured under the following conditions.
That is, about 55 mg of the sample was dissolved in a mixed solvent of 0.35 mL of chloroform-d ₁ 0.35 mL and 0.65 mL of 1,1,1,3,3,3,3-hexafluoro-2-propanol (HFIP) at 400 MHz. Use a nuclear magnetic resonance device and measure under the following conditions.
Chemical shift standard TMS: 0ppm
Measurement mode Single pulse Pulse width 30 ° pulse (10 μsec)
Number of points 64k
Measuring range 20ppm (-4 to 16ppm)
Repeat time 5 seconds Total number of times 64 times Measurement temperature 40 ° C
Window function exponential
Peak attribution is calculated from the peak area ratio by referring to the "NMR database of the National Institute for Materials Science (http://polymer.nims.go.jp/NMR/)". be able to.

In the differential scanning calorimetry, the polyester container of the present invention has a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes. Is preferable.
When the polyester constituting the polyester container is solidified from the fluid state in injection molding, the crystal size tends to increase and becomes spherulite, which may cause the polyester preform or the polyester container to become cloudy. In order to suppress this cloudiness, quenching is required in the crystallization temperature region. By setting the temperature lowering crystallization temperature of the polyester container to 175 ° C. or higher, rapid cooling in the crystallization temperature region can be facilitated, cloudiness of the polyester container can be further suppressed, and the yield of the polyester container can be further improved. As a result, resource saving can be achieved by reducing waste products, energy consumption in the production of polyester containers can be further reduced, and environmental load reduction can be further improved.
Further, by setting the temperature lowering crystallization temperature to 200 ° C. or lower, the energy consumption in the production of the polyester container can be reduced, and the environmental load reduction property can be further improved.
The temperature-lowering crystallization temperature of the polyester container of the present invention is more preferably 178 ° C. or higher and 198 ° C. or lower, and further preferably 180 ° C. or higher and 195 ° C. or lower.

The temperature-decreasing crystallization temperature is measured by using a differential scanning calorimetry device basically in accordance with JIS K7122 (1987), but in the present invention, the temperature-decreasing crystallization temperature is determined as follows. .. First, about 5 to 10 mg of a part of the polyester container is weighed in an aluminum pan. Subsequently, the temperature was raised to 300 ° C. at a temperature rise temperature of 10 ° C./min under a nitrogen stream of 50 ml / min, held for 10 minutes in this state, and then cooled to -50 ° C. at a temperature decrease rate of 10 ° C./min. To crystallize. At this time, the apex of the crystallization peak on the highest temperature side is defined as the temperature-decreasing crystallization temperature.

In one embodiment, the polyester in the polyester container comprises recycled polyester. This makes it possible to further improve the environmental load reduction property of the polyester container.
"Recycled polyester" refers to chemically recycled polyester or mechanically recycled polyester.
Chemically recycled polyester refers to polyester obtained by decomposing a polyester container to the monomer level and polymerizing it again.
Mechanically recycled polyester is a polyester container that is sorted, crushed, and washed to remove contaminants and foreign substances, and flakes are obtained. The flakes are further treated at high temperature and under reduced pressure for a certain period of time to remove contaminants inside the resin. Refers to the polyester obtained by recycling.

In one embodiment, the polyester in the polyester container comprises a virgin polyester. In the present invention, the "virgin polyester" refers to the polyester which has not been recycled as described above, that is, an unused polyester.
Polyester containers are used not only for storing beverages but also for storing non-foods (for example, pesticides and machine oils). When the polyester container used for storage of such non-food is recycled and the removal of contaminants by washing is insufficient, in the polyester container using recycled polyester, the contaminants are added to the filled contents. May elute. Therefore, the hygiene of the polyester container can be improved by including the virgin recycled polyester in the polyester of the polyester container.
Further, the polyester in the polyester container may contain recycled polyester and virgin polyester.

When the polyester container of the present invention contains recycled polyester, the content of the recycled polyester is preferably 30 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container. It is more preferably parts by mass or more and 80 parts by mass or less, and further preferably 60 parts by mass or more and 80 parts by mass or less.
By setting the content of the recycled polyester to 30 parts by mass or more with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container, the environmental load reducing property of the polyester container can be further improved.
By setting the content of the recycled polyester to 95 parts by mass or less with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container, the hygiene of the polyester container can be further improved. Further, when the polyester container includes the second layer as described later, it is possible to prevent the recycled polyester from being exposed to the first layer side or the third layer side in the production of the polyester preform.

The polyester may be polymerized using a polymerization catalyst as long as the characteristics of the present invention are not impaired. Examples of the polymerization catalyst include manganese catalysts, titanium catalysts, aluminum catalysts, lithium catalysts, germanium catalysts, antimony catalysts and the like.
When the polyester container of the present invention is filled with the heated contents, or when the polyester container is heated after the contents are filled, it is preferable to polymerize using a catalyst other than the antimony catalyst. This makes it possible to prevent the elution of antimony into the contents.

Examples of the manganese catalyst include fatty acid manganese salts such as manganese acetate, manganese carbonate, manganese chloride, acetylacetonate salts of manganese, manganese hydroxide and the like.
Examples of the titanium catalyst include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, and tetraphenyl titanate. , Titanium alkoxide such as tetrabenzyl titanate, Titanium oxide obtained by hydrolysis of titanium alkoxide, Titanium acetate, Titanium oxalate, Titanium potassium oxalate, Titanium oxalate, Potassium titanate, Sodium titanate, Titanium acid-water Aluminum Oxide Mixture, Titanium Chloride, Titanium Chloride-Aluminum Chloride Mixture, Titanium Bromide, Titanium Fluoride, Potassium Hexofluoride, Cobalt Titanium Hexoxide, Manganese Titanium Hexoxide, Ammonium Titanium Hexoxide and Examples include titanium acetylacetonate.
Examples of the aluminum catalyst include aluminum tris acetyl acetate, aluminum monoacetyl acetonate bis (ethyl acetoacetate) and ethyl acetoacetate aluminum diisopropyrate.
Examples of the lithium catalyst include ethyl lithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium and phenyllithium.
Examples of the germanium catalyst include germanium dioxide, germanium tetroxide, germanium tetramethoxyde, germanium tetraethoxydo, germanium tetrapropoxide, germanium tetrabutoxide, germanium tetrapentoxide and germanium tetrahexoxide.
Examples of the antimony catalyst include antimony trioxide, antimony pentoxide, antimony acetate, triphenylantimony, antimony glycol and the like.

To the extent that the properties of the present invention are not impaired, the polyester container may contain an additive, for example, an oxygen absorber, a gas barrier resin (nylon 6, nylon 6, 6 and a thermoplastic xylylene adipamide (MXD6)). Polyamide), plasticizers, UV stabilizers, antioxidants, anticolorants, matting agents, deodorants, flame retardants, weatherproofing agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, etc. , Antioxidants, ion exchangers, and colorants.

The polyester container of the present invention may be provided with a vapor-deposited film over the entire inner surface of the container. This makes it possible to improve the gas barrier property of the polyester container.

Examples of the vapor deposition film include metals such as aluminum, inorganic oxides such as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide, and hexamethyldisiloxane. Examples thereof include a vapor-deposited film composed of a hard carbon film such as an organic silicon compound and a DLC (Diamond Like Carbon) film.
The hard carbon film made of a DLC film is a hard carbon film also called an i-carbon film or a hydrogenated amorphous carbon film (a-C: H) ^, and is an amorphous carbon film mainly composed of SP3 bonds. Is.

The thickness of the vapor-film vapor film is not particularly limited, and may be, for example, 1 nm or more and 150 nm or less.

The vapor deposition film can be formed by using a conventionally known method, for example, a physical vapor deposition method (PVD method, PVD method) such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a plasma. Examples thereof include chemical vapor deposition methods (CVD methods, CVD methods) such as chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition.

FIG. 1 is a schematic semi-cross-sectional view showing an embodiment of the polyester container 10 of the present invention. In one embodiment, the polyester container 10 includes a mouth portion 11, a neck portion 12, a shoulder portion 13, a body portion 14, and a bottom portion 15, as shown in FIG.

In one embodiment, as shown in FIG. 1, the mouth portion 11 includes a screw portion 16 to which a cap is screwed, a turnip 17 under the screw portion 16, and a support ring 18 under the turnip 17.

In one embodiment, as shown in FIG. 1, the neck portion 12 is located between the support ring 18 and the shoulder portion 13 and has a substantially cylindrical shape having a substantially uniform diameter. Further, the shoulder portion 13 has a cylindrical shape whose diameter gradually increases from the neck portion 12 side to the body portion 14 side.

In one embodiment, the torso 14 is located between the shoulders 13 and the bottom 15, as shown in FIG. Further, the body portion 14 includes a panel portion 21 as shown in FIG. With such a configuration, it is possible to prevent deformation of the container due to an increase or decrease in the internal pressure when the polyester container is filled with the heated contents or when the polyester container is heated after the contents are filled.

In one embodiment, as shown in FIG. 1, the bottom portion 15 includes a recessed portion 19 located at the center and a grounding portion 20 provided around the depressed portion 19, and the grounding portion 20 includes a trunk portion 14 and a body portion 14 in the grounding portion 20. It is connected. With such a configuration, it is possible to prevent the container from being deformed due to an increase or decrease in the internal pressure when the polyester container is filled with the heated contents or when the polyester is heated after the contents are filled.
In one embodiment, the “bottom” means a portion inside from the ground contact portion when the polyester container is made to stand on its own.

The polyester container of the present invention may be composed of a single layer or two or more layers, or may be composed of a combination of a single layer and multiple layers.
Hereinafter, an example of an embodiment in which the polyester container of the present invention has a multi-layer structure will be described with reference to FIGS. 2 to 6.

In one embodiment, the polyester container 10 of the present invention has a first layer 22 and a second layer 23, as shown in FIGS. 2 and 3, and the first layer 22 constitutes an inner layer.

In one embodiment, the polyester container 10 of the present invention has a first layer 22, a second layer 23, and a third layer 24, as shown in the circle A of FIGS. 4 to 6, and the first layer. 22 constitutes an inner layer, and the third layer 24 constitutes an outer layer.
The second layer 23 may be provided, for example, from the upper end of the mouth portion 11 to the bottom portion 15 (see FIGS. 4 and 5).
Further, the second layer 23 may be provided from a part of the polyester container, for example, from the lower end of the mouth portion 11 to the bottom portion 15 (see FIG. 6). When the first layer 22 and the third layer 24 are made of the same material, as shown in FIG. 6, these layers become a single layer at a place where the second layer 23 is not provided.

The details of the mouth portion 11, the neck portion 12, the shoulder portion 13, the body portion 14, the bottom portion 15, the screw portion 16, the turnip portion 17, the support ring 18, the recessed portion 19, the ground contact portion 20, and the panel portion 21 have been described above. , The description is omitted here.

The polyester container of the present invention preferably has a volume / weight of 5 mL / g or more and 50 mL / g or less, and more preferably 8 mL / g or more and 45 mL / g or less.
By setting the capacity / weight of the polyester container to 5 mL / g or more, the blow moldability of the polyester container can be improved, the amount of polyester used can be prevented from becoming excessive, and the discarded polyester can be prevented. Since the amount can be reduced, the reduction of the environmental load can be further improved.
Further, by setting the capacity / weight of the polyester container to 50 mL / g or less, the strength of the polyester container can be improved.

The thickness of the cross section of the polyester container of the present invention is preferably 0.05 mm or more and 0.54 mm or less, and more preferably 0.1 mm or more and 0.5 mm or less.
By setting the thickness of the cross section to 0.05 mm or more, the strength of the polyester container can be further improved.
Further, by setting the thickness of the cross section to 0.54 mm or less, the blow moldability of the polyester container can be improved. In addition, it is possible to prevent the amount of polyester used from becoming excessive, and it is possible to reduce the environmental load.
The thickness of the cross section of the polyester container means, for example, a portion of the body of the polyester container where the thickness of the cross section is the thinnest.

(1st layer)
In one embodiment, the first layer included in the polyester container of the present invention is made of the above-mentioned virgin polyester. As a result, even when recycled polyester is used for the polyester container, it is possible to prevent the recycled polyester from coming into contact with the contents, and it is possible to improve the hygiene of the polyester container.

The virgin polyester constituting the first layer may be polymerized using the above-mentioned polymerization catalyst as long as the characteristics of the present invention are not impaired.
In the case of filling the polyester container of the present invention with the heated contents or in the case of the polyester container to be heated after filling the contents, the virgin polyester of the first layer is polymerized using a catalyst other than the antimony catalyst. Is preferable. This makes it possible to prevent the elution of antimony into the contents.

To the extent that the properties of the present invention are not impaired, the first layer may contain an additive, for example, an oxygen absorber, a gas barrier resin (nylon 6, nylon 6, 6 and a thermoplastic xylylene adipamide (MXD6). ) Etc.) Plasticizers, UV stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, antioxidants , Ion exchangers, colored pigments and the like.

In one embodiment, the first layer of the polyester container is provided in the content filling region. In the present invention, the "content filling region" means a region where the content and the polyester container are in contact with each other in a state where the polyester container is filled with the content and is upright.
In one embodiment, the first layer is provided from a position 5 to 70 mm below the upper end of the mouth to the bottom 15. Preferably, the first layer is provided from a position 5 to 15 mm below the upper end of the mouth portion to the bottom portion 15.
By providing the first layer from a position 5 to 70 mm below the upper end of the mouth to the bottom, the content filling area can be covered by the first layer, even when recycled polyester is used for the polyester container. , It is possible to prevent the recycled polyester from coming into contact with the contents, and it is possible to further improve the hygiene of the polyester container.
In addition, by providing the first layer from a position 5 to 70 mm below the upper end of the mouth to the bottom, it is possible to effectively prevent cracking of the mouth during capping by an automatic machine. Can be done.

In one embodiment, the first layer of the polyester container is provided from a position 70 mm below the upper end of the mouth portion to the bottom portion.
Further, it is preferable that the first layer is provided from a position 15 mm below the upper end of the mouth portion to the bottom portion. As a result, the content filling area can be covered by the first layer, and even when recycled polyester is used for the polyester container, it is possible to prevent the recycled polyester from coming into contact with the contents, and the hygiene of the polyester container can be improved. Can be improved further.
Further, in the polyester container of the present invention, it is more preferable that the first layer is provided from the upper end to the bottom of the mouth portion. As a result, it is possible to further reduce the contact of recycled polyester with the contents even when it is stored under heating in a vending machine or the like, and the hygiene of the polyester container is further improved. be able to.

The thickness of the first layer in the polyester container is preferably 0.01 mm or more and 0.33 mm or less, more preferably 0.025 mm or more and 0.3 mm or less, and 0.025 mm or more and 0.1 mm or less. Is even more preferable.
By setting the thickness of the first layer to 0.01 mm or more, it is possible to effectively prevent the recycled polyester from coming into contact with the contents even when the recycled polyester is used for the polyester container.
Further, by setting the thickness of the first layer to 0.33 mm or less, the proportion of the second layer in the polyester container can be increased, and the environmental load reducing property of the polyester container can be further improved.
The thickness of the first layer means, for example, a portion of the body of the polyester container where the thickness of the first layer is the thinnest.

(2nd layer)
In one embodiment, the second layer included in the polyester container of the present invention is made of the above-mentioned recycled polyester. This makes it possible to further improve the environmental load reduction property of the polyester container.

The recycled polyester constituting the second layer may be polymerized using the above-mentioned polymerization catalyst as long as the characteristics of the present invention are not impaired.

The second layer may contain an additive as long as the characteristics of the present invention are not impaired, and may contain, for example, an oxygen absorber, a gas barrier resin (nylon 6, nylon 6, 6 and a thermoplastic xylylene adipamide (MXD6). ) Etc.) Plasticizers, UV stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, antioxidants , Ion exchangers, colored pigments and the like.

The thickness of the second layer in the polyester container is preferably 0.04 mm or more and 0.49 mm or less, more preferably 0.1 mm or more and 0.4 mm or less, and 0.1 mm or more and 0.22 mm or less. Is even more preferable.
By setting the thickness of the second layer to 0.04 mm or more, the environmental load reduction property of the polyester container can be further improved.
Further, by setting the thickness of the second layer to 0.49 mm or less, it is possible to prevent the recycled polyester from being exposed to the contents side in the production of the polyester preform.
The thickness of the second layer means, for example, a portion of the body of the polyester container where the thickness of the second layer is the thinnest.

(Third layer)
In one embodiment, the third layer included in the polyester container of the present invention is made of the above-mentioned virgin polyester. With such a configuration, the heat resistance and strength of the polyester container can be improved.

The virgin polyester constituting the third layer may be polymerized using the above-mentioned polymerization catalyst as long as the characteristics of the present invention are not impaired. Further, the third layer may be made of the same material as the first layer.

To the extent that the properties of the present invention are not impaired, the third layer may contain an additive, for example, an oxygen absorber, a gas barrier resin (nylon 6, nylon 6, 6 and a thermoplastic xylylene adipamide (MXD6). ) Etc.) Plasticizers, UV stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, antioxidants , Ion exchangers, colored pigments and the like.

The thickness of the third layer in the polyester container is preferably 0.01 mm or more and 0.1 mm or less, and preferably 0.025 mm or more and 0.05 mm or less.
By setting the thickness of the third layer to 0.01 mm or more, the heat resistance and strength of the polyester container can be further improved.
Further, by setting the thickness of the third layer to 0.1 mm or less, the proportion of the second layer in the polyester container can be increased, and the environmental load reducing property of the polyester container can be further improved.
The thickness of the third layer means, for example, a portion of the body of the polyester container where the thickness of the third layer is the thinnest.

<Polyester preform>
The polyester preform of the present invention is used for manufacturing a polyester container.
The polyester preform of the present invention is made of polyester.

In the present invention, the polyester of the polyester preform is characterized in that the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum is 0.0005 or more and 0.0100 or less. Thereby, the polyester container as described above can be obtained. The more preferable ratio in the polyester preform of the present invention is 0.0008 or more and 0.009 or less, and more preferably 0.001 or more and 0.008 or less.
In the polyester preform, the ratio of the isophthalic acid unit to the terephthalic acid unit based on the nuclear magnetic resonance spectrum of the polyester can be determined by the same method as that for the polyester container.

The polyester preform of the present invention has a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes in differential scanning calorimetry. It is preferably 178 ° C. or higher and 198 ° C. or lower, and even more preferably 180 ° C. or higher and 195 ° C. or lower. This makes it possible to further improve the environmental load reduction property of the obtained polyester container.
In the polyester preform of the present invention, the temperature-decreasing crystallization temperature can be measured by the same method as that for the polyester container.

With respect to other elements, the polyester constituting the polyester preform may be the same as the polyester in the polyester container described above.

To the extent that the properties of the present invention are not impaired, the polyester preform may contain an additive, for example, an oxygen absorber, a gas barrier resin (nylon 6, nylon 6, 6 and a thermoplastic xylylene adipamide (MXD6). ) Etc.) Polyamides) Plasticizers, UV stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slipping agents, mold release agents, antioxidants , Ion exchangers, colored pigments and the like.

FIG. 7 is a schematic semi-cross-sectional view showing an embodiment of the polyester preform of the present invention. In one embodiment, the polyester preform 30 of the present invention includes a mouth portion 31, a body portion 32, and a bottom portion 33, as shown in FIG. 7.
In one embodiment, as shown in FIG. 7, the mouth portion 31 corresponds to the mouth portion 11 of the polyester container 10 described above, and has substantially the same shape as the mouth portion 11. Further, in one embodiment, the body portion 32 corresponds to the neck portion 12, the shoulder portion 13 and the body portion 14 of the polyester container 10 described above, and has a substantially cylindrical shape. Further, in one embodiment, the bottom portion 33 corresponds to the bottom portion 15 of the polyester container 10 described above, and has a substantially hemispherical shape.
Further, in one embodiment, as shown in FIG. 7, the mouth portion 31 includes a screw portion 34 to which a cap is screwed, a turnip 35 under the screw portion 34, and a support ring 36 under the turnip 35.

The polyester preform of the present invention may be composed of a single layer or two or more layers, or may be composed of a combination of a single layer and multiple layers.
An example of an embodiment in which the polyester preform of the present invention has a multi-layer structure will be described with reference to FIGS. 8 to 12.

In one embodiment, the polyester preform 30 of the present invention has a first layer 37 and a second layer 38, as shown in FIGS. 8 and 9, with the first layer 37 forming an inner layer. ..

In one embodiment, the polyester preform 30 of the present invention has a first layer 37, a second layer 38, and a third layer 39, as shown in FIGS. 10 to 12, and the first layer 37 has a first layer 37. The inner layer is formed, and the third layer 39 constitutes the outer layer.
The second layer 38 may be provided, for example, from the lower end of the bottom portion 33 to the upper end of the mouth portion 31 (see FIGS. 10 and 11).
Further, the second layer 38 may be provided from a part of the polyester preform, for example, from the lower end of the bottom portion 33 to the lower end of the mouth portion 31 (see FIG. 12). When the first layer 37 and the third layer 39 are made of the same material, as shown in FIG. 12, these layers become a single layer at a place where the second layer 38 is not provided.

Since the details of the mouth portion 31, the body portion 32, the bottom portion 33, the screw portion 34, the turnip 35, and the support ring 36 have been described above, the description thereof will be omitted here.

The thickness of the cross section of the polyester preform of the present invention is preferably 1.3 mm or more and 4.7 mm or less, and more preferably 2.1 mm or more and 4.0 mm or less. By setting the thickness of the cross section in the above range, the polyester container as described above can be obtained.
The thickness of the cross section of the polyester preform means, for example, a portion of the body of the polyester preform where the thickness of the cross section is the thinnest.

(1st layer)
In one embodiment, as shown in FIGS. 8 and 10, when the distance from the lower end of the bottom portion 33 to the upper end of the mouth portion 31 is L, the first layer 37 has 0 from the lower end. It is provided in the range of 0.4 L or more and 0.97 L or less.
Since the first layer 37 is provided in a range of 0.4 L or more from the lower end of the bottom portion 33, the polyester preform is blow-molded to form a polyester container, and the first layer covers the content filling area. Even when recycled polyester is used, it is possible to prevent the recycled polyester from coming into contact with the contents, and it is possible to further improve the hygiene of the polyester container.
Further, since the first layer 37 is provided in a range of 0.97 L or less from the lower end of the bottom portion 33, when the polyester preform is blow-molded into a polyester container, when capping is performed by an automatic machine. , It is possible to effectively prevent the mouth from being cracked.

In one embodiment, the first layer may be provided from the lower end of the bottom to the upper end of the mouth, or may be provided from the lower end of the bottom to the lower end of the mouth.

As the material constituting the first layer in the polyester preform, the same material as the material constituting the first layer in the polyester container can be used.

The thickness of the first layer in the polyester preform is preferably 0.1 mm or more and 2.9 mm or less, and more preferably 0.2 mm or more and 2.0 mm or less. When the polyester preform includes a third layer, the thickness of the first layer in the polyester preform is preferably 0.05 mm or more and 1.5 mm or less, and 0.1 mm or more and 1.0 mm or less. Is more preferable. By setting the thickness of the first layer in the polyester preform to the above range, the polyester container as described above can be obtained.
The thickness of the first layer in the polyester preform means, for example, a portion of the body of the polyester preform where the thickness of the first layer is the thinnest.

(2nd layer)
As the material constituting the second layer in the polyester preform, the same material as the material constituting the second layer in the polyester container can be used.

The thickness of the second layer in the polyester preform is preferably 0.5 mm or more and 4.3 mm or less, and preferably 1.9 mm or more and 4.0 mm or less. When the polyester preform includes the third layer, the thickness of the second layer in the polyester preform is preferably 0.4 mm or more and 3.7 mm or less, and 1.6 mm or more and 3.4 mm or less. Is preferable. By setting the thickness of the second layer in the polyester preform within the above range, the polyester container as described above can be obtained.
The thickness of the second layer in the polyester preform means, for example, a portion of the body of the polyester preform where the thickness of the second layer is the thinnest.

(Third layer)
As the material constituting the third layer in the polyester preform, the same material as the material constituting the third layer in the polyester container can be used.

The thickness of the third layer in the polyester preform is preferably 0.05 mm or more and 1.5 mm or less, and preferably 0.1 mm or more and 1.0 mm or less. By setting the thickness of the third layer in the polyester preform to the above range, the polyester container as described above can be obtained.
The thickness of the third layer in the polyester preform means, for example, a portion of the body of the polyester preform where the thickness of the third layer is the thinnest.

<Manufacturing method of polyester container>
In one embodiment, the polyester container shown in FIG. 1 can be manufactured by injection-molding the above-mentioned polyester to produce a polyester preform and then blow-molding the polyester preform.

In one embodiment, the polyester container shown in FIGS. 2 and 3 produces a polyester preform by co-injection molding the materials constituting the first layer and the second layer described above, and blow molding the polyester preform. By doing so, the polyester container of the present invention can be manufactured. The formation position of each layer can be adjusted by injection molding conditions such as resin temperature.

Further, the polyester container shown in FIG. 2 or the like can also be manufactured by using two-color molding or insert molding.
Further, in the polyester container shown in FIG. 2 and the like, virgin polyester is injection-molded in the internal mold to form a first layer, the internal mold is retracted, and a gap is provided between the internal mold and the first layer. Is provided, and recycled polyester is injection-molded in this gap to form a second layer.

In one embodiment, the polyester container shown in FIGS. 4 to 6 prepares a preform by co-injection molding the materials constituting the first layer, the second layer and the third layer described above. The polyester container of the present invention can be manufactured by blow molding.
When the second layer is formed as a part of the preform, it is preferable to use the hot runner nozzle disclosed in Japanese Patent Application Laid-Open No. 2008-94454.

Further, the polyester container shown in FIG. 4 and the like can also be manufactured by using three-color molding or insert molding.
Further, in the polyester container shown in FIG. 4 and the like, virgin polyester is injection-molded in the internal mold to form a first layer, the internal mold is retracted, and a gap is provided between the internal mold and the first layer. Is provided, recycled polyester is injection-molded in this gap, a second layer is formed, the internal mold is retracted, a gap is provided between the internal mold and the first layer and the second layer, and a virgin is provided in this gap. It can be manufactured by injection molding polyester to form a third layer.

Second aspect <polyester container>
The polyester container according to the second aspect of the present invention is made of polyester.
Examples of the dicarboxylic acid compound include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecandionic acid, eicosandionic acid, pimelliic acid, azelaic acid, methylmalonic acid and ethylmalonic acid, and adamantan. Dicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendandicarboxylic acid, anthracendicarboxylic acid, phenanthrangecarboxylic acid, 9,9'-bis Examples thereof include (4-carboxyphenyl) fluorenic acid and ester derivatives thereof.
Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, and cyclohexane. Diethanol, Decahydronaphthalenedimethanol, Decahydronaphthalenediethanol, Norbornanedimethanol, Norbornandiethanol, Tricyclodecanedimethanol, Tricyclodecaneethanol, Tetracyclododecanedimethanol, Tetracyclododecanediethanol, Decalindiethanol, Decalindiethanol, 5 -Methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis (4-hydroxy) Cyclohexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, adamandiol , Paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, trimethylolpropane, pentaerythritol and the like.
The polyester is preferably polyethylene terephthalate, which is a copolymer of terephthalic acid and ethylene glycol, or modified polyethylene terephthalate to which a copolymerization monomer is added.

In the differential scanning calorimetry, the polyester container of the present invention has a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes. It is characterized by that.
As will be described later, the polyester container can be manufactured by first injection molding polyester to produce a polyester preform and then blow molding the polyester preform. When polyester is solidified from a fluid state in injection molding, the crystal size becomes large and tends to form spherulites, which causes the polyester preform and the polyester container to become cloudy. In order to suppress this cloudiness, quenching is required in the crystallization temperature region. In the polyester container of the present invention, by setting the temperature lowering crystallization temperature to 175 ° C. or higher, rapid cooling in the crystallization temperature region can be facilitated, cloudiness of the polyester container can be suppressed, and the yield of the polyester container can be improved. As a result, resource saving is achieved by reducing the amount of waste products, energy consumption in the production of the polyester container is reduced, and the polyester container having a high environmental load reduction property can be obtained.
Further, by setting the temperature lowering crystallization temperature to 200 ° C. or lower, the energy consumption in the production of the polyester container is reduced, and the polyester container having a high environmental load reducing property can be obtained.
In the polyester container of the present invention, the temperature lowering crystallization temperature is more preferably 178 ° C. or higher and 198 ° C. or lower, and more preferably 180 ° C. or higher and 195 ° C. or lower.

As long as the characteristics of the present invention are not impaired, the polyester in the polyester container may contain a monomer other than the dicarboxylic acid compound and the diol compound, but the content thereof is 10 mol% or less with respect to all the constituent units. It is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 3 mol% or less.

The temperature-decreasing crystallization temperature is measured by using a differential scanning calorimetry device basically in accordance with JIS K7122 (1987), but in the present invention, the temperature-decreasing crystallization temperature is determined as follows. .. First, about 5 to 10 mg of a part of the polyester container is weighed in an aluminum pan. Subsequently, the temperature was raised to 300 ° C. at a temperature rise temperature of 10 ° C./min under a nitrogen stream of 50 ml / min, held for 10 minutes in this state, and then cooled to -50 ° C. at a temperature decrease rate of 10 ° C./min. To crystallize. At this time, the apex of the crystallization peak on the highest temperature side is defined as the temperature-decreasing crystallization temperature.

In one embodiment, the polyester in the polyester container comprises recycled polyester. This makes it possible to further improve the environmental load reduction property of the polyester container.
In one embodiment, the polyester in the polyester container comprises a virgin polyester. This makes it possible to improve the hygiene of the polyester container.
Further, the polyester in the polyester container may contain recycled polyester and virgin polyester.

When the polyester container of the present invention contains recycled polyester, the content of the recycled polyester is preferably 30 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container. It is more preferably parts by mass or more and 80 parts by mass or less, and further preferably 60 parts by mass or more and 80 parts by mass or less.
By setting the content of the recycled polyester to 30 parts by mass or more with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container, the environmental load reducing property of the polyester container can be further improved.
By setting the content of the recycled polyester to 95 parts by mass or less with respect to 100 parts by mass of the total amount of the resin material contained in the polyester container, the hygiene of the polyester container can be further improved. Further, when the polyester container includes the second layer as described later, it is possible to prevent the recycled polyester from being exposed to the first layer side or the third layer side in the production of the polyester preform.

The polyester may be polymerized using the polymerization catalyst described in the first aspect as long as the characteristics of the present invention are not impaired.

As long as the characteristics of the present invention are not impaired, the polyester container may contain the additives described in the first aspect.

The polyester container of the present invention may be provided with a vapor-deposited film over the entire inner surface of the container. This makes it possible to improve the gas barrier property of the polyester container.

As the vapor deposition film, the vapor deposition film described in the first aspect can be used.

FIG. 1 is a schematic semi-cross-sectional view showing an embodiment of the polyester container 10 of the present invention. In one embodiment, the polyester container 10 includes a mouth portion 11, a neck portion 12, a shoulder portion 13, a body portion 14, and a bottom portion 15, as shown in FIG.
The details of the mouth portion 11, the neck portion 12, the shoulder portion 13, the body portion 14, the bottom portion 15, the screw portion 16, the turnip portion 17, the support ring 18, the recessed portion 19, the grounding portion 20, and the panel portion 21 are described in the first. Since the description has been made in the above aspect, the description thereof is omitted here.

The polyester container of the present invention may be composed of a single layer or two or more layers, or may be composed of a combination of a single layer and multiple layers.
Hereinafter, an example of an embodiment in which the polyester container of the present invention has a multi-layer structure will be described with reference to FIGS. 2 to 6.

In one embodiment, the polyester container 10 of the present invention has a first layer 22 and a second layer 23, as shown in FIGS. 2 and 3, and the first layer 22 constitutes an inner layer.

In one embodiment, the polyester container 10 of the present invention has a first layer 22, a second layer 23, and a third layer 24, as shown in the circle A of FIGS. 4 to 6, and the first layer. 22 constitutes an inner layer, and the third layer 24 constitutes an outer layer.
The second layer 23 may be provided, for example, from the upper end of the mouth portion 11 to the bottom portion 15 (see FIGS. 4 and 5).
Further, the second layer 23 may be provided from a part of the polyester container, for example, from the lower end of the mouth portion 11 to the bottom portion 15 (see FIG. 6). When the first layer 22 and the third layer 24 are made of the same material, as shown in FIG. 6, these layers become a single layer at a place where the second layer 23 is not provided.

The details of the mouth portion 11, the neck portion 12, the shoulder portion 13, the body portion 14, the bottom portion 15, the screw portion 16, the turnip portion 17, the support ring 18, the recessed portion 19, the ground contact portion 20, and the panel portion 21 have been described above. , The description is omitted here.

The polyester container of the present invention preferably has a volume / weight of 5 mL / g or more and 50 mL / g or less, and more preferably 8 mL / g or more and 45 mL / g or less.
By setting the capacity / weight of the polyester container to 5 mL / g or more, the blow moldability of the polyester container can be improved.
Further, by setting the capacity / weight of the polyester container to 50 mL / g or less, the strength of the polyester container can be improved.
In addition, by setting the capacity / weight of the polyester container to 5 mL / g or more, it is possible to prevent the amount of polyester used from becoming excessive, and it is possible to reduce the amount of polyester discarded, thus reducing the environmental load. can do.

The thickness of the cross section of the polyester container of the present invention is preferably 0.05 mm or more and 0.54 mm or less, and more preferably 0.1 mm or more and 0.5 mm or less.
By setting the thickness of the cross section to 0.05 mm or more, the strength of the polyester container can be further improved.
Further, by setting the thickness of the cross section to 0.54 mm or less, the blow moldability of the polyester container can be improved. In addition, it is possible to prevent the amount of polyester used from becoming excessive, and it is possible to reduce the environmental load.
The thickness of the cross section of the polyester container means, for example, a portion of the body of the polyester container where the thickness of the cross section is the thinnest.

(1st layer, 2nd layer, 3rd layer)
As the first layer, the second layer, and the third layer of the polyester container, the first layer, the second layer, and the third layer described in the first aspect can be used.

<Polyester preform>
The polyester preform of the present invention is used for manufacturing a polyester container.
The polyester preform of the present invention is made of polyester.

The polyester preform of the present invention has a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes in differential scanning calorimetry. It is preferably 178 ° C. or higher and 198 ° C. or lower, and even more preferably 180 ° C. or higher and 195 ° C. or lower. This makes it possible to further improve the environmental load reduction property of the obtained polyester container.
In the polyester preform, the temperature lowering crystallization temperature can be measured by the same method as in the polyester container.

With respect to other elements, the polyester constituting the polyester preform may be the same as the polyester in the polyester container described above.

To the extent that the properties of the present invention are not impaired, the polyester preform may contain the additives described in the first aspect.

FIG. 7 is a schematic semi-cross-sectional view showing an embodiment of the polyester preform of the present invention. In one embodiment, the polyester preform 30 of the present invention includes a mouth portion 31, a body portion 32, and a bottom portion 33, as shown in FIG. 7.
In one embodiment, as shown in FIG. 7, the mouth portion 31 corresponds to the mouth portion 11 of the polyester container 10 described above, and has substantially the same shape as the mouth portion 11. Further, in one embodiment, the body portion 32 corresponds to the neck portion 12, the shoulder portion 13 and the body portion 14 of the polyester container 10 described above, and has a substantially cylindrical shape. Further, in one embodiment, the bottom portion 33 corresponds to the bottom portion 15 of the polyester container 10 described above, and has a substantially hemispherical shape.
Further, in one embodiment, as shown in FIG. 7, the mouth portion 31 includes a screw portion 34 to which a cap is screwed, a turnip 35 under the screw portion 34, and a support ring 36 under the turnip 35.

The polyester preform of the present invention may be composed of a single layer or two or more layers, or may be composed of a combination of a single layer and multiple layers.
An example of an embodiment in which the polyester preform of the present invention has a multi-layer structure will be described with reference to FIGS. 8 to 12.

In one embodiment, the polyester preform 30 of the present invention has a first layer 37 and a second layer 38, as shown in FIGS. 8 and 9, with the first layer 37 forming an inner layer. ..

In one embodiment, the polyester preform 30 of the present invention has a first layer 37, a second layer 38, and a third layer 39, as shown in FIGS. 10 to 12, and the first layer 37 has a first layer 37. The inner layer is formed, and the third layer 39 constitutes the outer layer.
The second layer 38 may be provided, for example, from the lower end of the bottom portion 33 to the upper end of the mouth portion 31 (see FIGS. 10 and 11).
Further, the second layer 38 may be provided from a part of the polyester preform, for example, from the lower end of the bottom portion 33 to the lower end of the mouth portion 31 (see FIG. 12). When the first layer 37 and the third layer 39 are made of the same material, as shown in FIG. 12, these layers become a single layer at a place where the second layer 38 is not provided.

Since the details of the mouth portion 31, the body portion 32, the bottom portion 33, the screw portion 34, the turnip 35, and the support ring 36 have been described above, the description thereof will be omitted here.

The thickness of the cross section of the polyester preform of the present invention is preferably 1.3 mm or more and 4.7 mm or less, and more preferably 2.1 mm or more and 4.0 mm or less. By setting the thickness of the cross section in the above range, the polyester container as described above can be obtained.
The thickness of the cross section of the polyester preform means a portion of the body of the polyester preform where the thickness of the cross section is the thinnest.

(1st layer, 2nd layer, 3rd layer)
As the first layer, the second layer, and the third layer of the polyester preform, the first layer, the second layer, and the third layer described in the first aspect can be used.

<Manufacturing method of polyester container>
The polyester container can be manufactured by the manufacturing method described in the first aspect.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<< Example of the first aspect >>
<Measurement conditions of nuclear magnetic resonance spectrum ( ¹ H-NMR)>
Equipment AVANCEIIIHD 400MHz (manufactured by Bruker)
Probe PA BBO 400S1 BBF-HD05 Z SP (manufactured by Bruker)
Chemical shift standard TMS: 0ppm
Measurement mode Single pulse Pulse width 30 ° pulse (10 μsec)
Number of points 64k
Measuring range 20ppm (-4 to 16ppm)
Repeat time 5 seconds Total number of times 64 times Measurement temperature 40 ° C
Window function exponential
Solvent Chloroform-d ₁ / HFIP mixed solvent

Example 1-1
A mechanically recycled polyester having a ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum of 0.006, which was stored in the storage for 6 months, was prepared. The temperature-decreasing crystallization temperature of this mechanically recycled polyester was 193.8 ° C.
Using an injection molding machine, a polyester preform having a mouth, a body, and a bottom was produced from this mechanically recycled polyester. The mouth of the polyester preform is provided with a male thread, a turnip and a support ring in order from the upper end of the mouth.
The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g.

Next, the polyester preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a polyester container having the shape shown in FIG. 1 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the nuclear magnetic resonance spectrum of the obtained polyester container was measured.
For the measurement, first, the body of the polyester container was cut to prepare a sample of about 55 mg, which was placed in a screw tube bottle. In a screw tube bottle containing a sample, 0.35 mL of chloroform-d ₁ and 0.65 mL of 1,1,1,3,3,3,3-hexafluoro-2-propanol (HFIP) are micro-micro. Addition was made using a pipetter to fully dissolve the sample. The solution in which the sample was dissolved was transferred to an NMR sample tube, and measurement was performed under the above conditions.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.006.

Subsequently, the temperature-decreasing crystallization temperature of the polyester container was measured. As the differential scanning calorimetry device, DSC Q200 manufactured by TA Instruments was used.
First, 5 to 10 mg of a part of the obtained polyester container was weighed in an aluminum pan. Subsequently, the temperature was raised to 300 ° C. at a temperature rise temperature of 10 ° C./min under a nitrogen stream of 50 ml / min, held for 10 minutes in this state, and then cooled to -50 ° C. at a temperature decrease rate of 10 ° C./min. And crystallized. The temperature-decreasing crystallization temperature was 188.8 ° C.

In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 1-2
A mechanically recycled polyester having a ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum of 0.003, which was stored in the storage for 6 months, was prepared. The temperature-decreasing crystallization temperature of this mechanically recycled polyester was 192.0 ° C.
A polyester preform was produced in the same manner as in Example 1-1 except that this mechanically recycled polyester was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this example, a polyester container was prepared in the same manner as in Example 1-1, and the nuclear magnetic resonance spectrum was measured and the temperature-decreased crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.002. The temperature-decreasing crystallization temperature of the polyester container was 186.0 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 1-3
Mechanically recycled polyester in which the ratio of isophthalic acid units to terephthalic acid units determined by the nuclear magnetic resonance spectrum, which was stored in the storage for 6 months, was 0.006, and the nuclei stored in the storage for 6 months. A non-recycled polyester having an isophthalic acid unit ratio of 0.013 to the terephthalic acid unit determined by the magnetic resonance spectrum was prepared. The temperature-lowering crystallization temperature of this mechanically recycled polyester was 193.8 ° C., and the temperature-lowering crystallization temperature of this non-recycled polyester was 157.3 ° C.
These are co-injected using an injection molding machine, and the multilayer (2) shown in FIG. 9 is provided with a first layer made of unrecycled polyester and a second layer made of mechanically recycled polyester. Seed 2 layers) Preform was created.
The amount of mechanically recycled polyester used was adjusted to be 80 parts by mass with respect to 100 parts by mass of the resin material constituting the multilayer preform.
The thickness of the cross section of the body of the multilayer preform was 3.5 mm, and the basis weight was 22 g.

Next, the multilayer preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a multilayer container having the shape shown in FIG. 3 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the nuclear magnetic resonance spectrum of the polyester container and the temperature-decreasing crystallization temperature were measured in the same manner as in Example 1-1.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.007. The temperature-decreasing crystallization temperature of the polyester container was 187.5 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 1-4
Mechanically recycled polyester in which the ratio of isophthalic acid units to terephthalic acid units determined by the nuclear magnetic resonance spectrum, which was stored in the storage for 6 months, was 0.006, and the nuclei stored in the storage for 6 months. A non-recycled polyester having an isophthalic acid unit ratio of 0.013 to the terephthalic acid unit determined by the magnetic resonance spectrum was prepared. The temperature-lowering crystallization temperature of this mechanically recycled polyester was 193.8 ° C., and the temperature-lowering crystallization temperature of this non-recycled polyester was 157.3 ° C.
These are co-injected using an injection molding machine, and are composed of a first layer composed of non-recycled polyester, a second layer composed of mechanically recycled polyester, and non-recycled polyester. A multi-layer (2 types, 3 layers) preform shown in FIG. 11 having a third layer was created.
The amount of mechanically recycled polyester used was adjusted to be 50 parts by mass with respect to 100 parts by mass of the resin material constituting the multilayer preform.
The thickness of the cross section of the body of the multilayer preform was 3.5 mm, and the basis weight was 22 g.

Next, the multilayer preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a multilayer container having the shape shown in FIG. 5 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the nuclear magnetic resonance spectrum of the polyester container and the temperature-decreasing crystallization temperature were measured in the same manner as in Example 1-1.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.008. The temperature-decreasing crystallization temperature of the polyester container was 183.6 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Comparative Example 1-1
A non-recycled polyester having a ratio of isophthalic acid units to terephthalic acid units determined by a nuclear magnetic resonance spectrum of 0.013, which was stored in a storage for 6 months, was prepared. The temperature-decreasing crystallization temperature of this non-recycled polyester was 157.3 ° C.
A polyester preform was produced in the same manner as in Example 1-1 except that this polyester was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this comparative example, a polyester container was prepared in the same manner as in Example 1-1, and the nuclear magnetic resonance spectrum was measured and the temperature-decreased crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.012. The temperature-decreasing crystallization temperature of the polyester container was 165.5 ° C.
In this comparative example, the number of polyester containers in which cloudiness occurred was 3 out of 100.

Comparative Example 1-2
A mechanically recycled polyester having a ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum of 0.016, which was stored in the storage for 6 months, was prepared. The temperature-decreasing crystallization temperature of this mechanically recycled polyester was 170.2 ° C.
A polyester preform was produced in the same manner as in Example 1-1 except that this polyester was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this comparative example, a polyester container was prepared in the same manner as in Example 1-1, and the nuclear magnetic resonance spectrum was measured and the temperature-decreased crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm.
In the polyester container, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum was 0.015. The temperature-decreasing crystallization temperature of the polyester container was 172.8 ° C.
In this comparative example, the number of polyester containers in which cloudiness occurred was 2 out of 100.

In the examples and comparative examples of the first aspect, the polyester container in which the ratio of the isophthalic acid unit to the terephthalic acid unit in the polyester is 0.0005 or more and 0.010 or less has an improved yield and a high environmental load reducing property. It turns out that it is a polyester container.

<< Example of the second aspect >>
Example 2-1
Using an injection molding machine, a polyester preform having a mouth, a body, and a bottom was produced from mechanically recycled polyester having a temperature-decreasing crystallization temperature of 193.8 ° C. The mouth of the polyester preform is provided with a male thread, a turnip and a support ring in order from the upper end of the mouth.
The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g.

Next, the polyester preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a polyester container having the shape shown in FIG. 1 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the temperature-decreasing crystallization temperature of the polyester container was measured. As the differential scanning calorimetry device, DSC Q200 manufactured by TA Instruments was used.
First, 5 to 10 mg of a part of the obtained polyester container was weighed in an aluminum pan. Subsequently, the temperature was raised to 300 ° C. at a temperature rise temperature of 10 ° C./min under a nitrogen stream of 50 ml / min, held for 10 minutes in this state, and then cooled to -50 ° C. at a temperature decrease rate of 10 ° C./min. And crystallized. The temperature-decreasing crystallization temperature was 188.8 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 2-2
A polyester preform was produced in the same manner as in Example 2-1 except that a mechanically recycled polyester having a temperature lowering crystallization temperature of 192.0 ° C., which was different from Example 1, was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this example, a polyester container was prepared in the same manner as in Example 2-1 and the temperature lowering crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm. The temperature-decreasing crystallization temperature was 186.0 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 2-3
A mechanically recycled polyester having a temperature-decreasing crystallization temperature of 193.8 ° C. and a non-recycled polyester having a temperature-decreasing crystallization temperature of 157.3 ° C. were prepared.
These are co-injected using an injection molding machine, and the multilayer (2) shown in FIG. 9 is provided with a first layer made of unrecycled polyester and a second layer made of mechanically recycled polyester. Seed 2 layers) Preform was created.
The amount of mechanically recycled polyester used was adjusted to be 80 parts by mass with respect to 100 parts by mass of the resin material constituting the multilayer preform.
The thickness of the cross section of the body of the multilayer preform was 3.5 mm, and the basis weight was 22 g.

Next, the multilayer preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a multilayer container having the shape shown in FIG. 3 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the temperature-decreasing crystallization temperature of the polyester container was measured in the same manner as in Example 1-1. The temperature-decreasing crystallization temperature was 187.5 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Example 2-4
A mechanically recycled polyester having a temperature-decreasing crystallization temperature of 193.8 ° C. and a non-recycled polyester having a temperature-decreasing crystallization temperature of 157.3 ° C. were prepared.
These are co-injected using an injection molding machine, and are composed of a first layer composed of non-recycled polyester, a second layer composed of mechanically recycled polyester, and non-recycled polyester. A multi-layer (2 types, 3 layers) preform shown in FIG. 11 having a third layer was created.
The amount of mechanically recycled polyester used was adjusted to be 50 parts by mass with respect to 100 parts by mass of the resin material constituting the multilayer preform.
The thickness of the cross section of the body of the multilayer preform was 3.5 mm, and the basis weight was 22 g.

Next, the multilayer preform was heated to 110 ° C. and biaxially stretched and blow molded in a blow molding die to obtain a multilayer container having the shape shown in FIG. 5 and having an internal volume of 500 mL. The thickness of the cross section in the body of the polyester container was 0.32 mm.

Next, the temperature-decreasing crystallization temperature of the polyester container was measured in the same manner as in Example 1-1. The temperature-decreasing crystallization temperature was 183.6 ° C.
In this example, the number of polyester containers in which cloudiness occurred was 0 out of 100.

Comparative Example 2-1
A polyester preform was produced in the same manner as in Example 2-1 except that non-recycled polyester having a temperature-decreasing crystallization temperature of 157.3 ° C. was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this comparative example, a polyester container was prepared in the same manner as in Example 2-1 and the temperature lowering crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm. The temperature-decreasing crystallization temperature was 165.5 ° C.
In this comparative example, the number of polyester containers in which cloudiness occurred was 3 out of 100.

Comparative Example 2-2
A polyester preform was produced in the same manner as in Example 2-1 except that the mechanically recycled polyester having a temperature-decreasing crystallization temperature of 170.2 ° C. was used. The thickness of the cross section of the body of the polyester preform was 3.5 mm, and the basis weight was 22 g. Further, using the polyester preform of this comparative example, a polyester container was prepared in the same manner as in Example 2-1 and the temperature lowering crystallization temperature was measured. The thickness of the cross section in the body of the polyester container was 0.32 mm. The temperature-decreasing crystallization temperature was 172.8 ° C.
In this comparative example, the number of polyester containers in which cloudiness occurred was 2 out of 100.

In the examples and comparative examples of the second aspect, it can be seen that the polyester container having a temperature lowering crystallization temperature of 175 ° C. or higher and 200 ° C. or lower is a polyester container having improved yield and high environmental load reducing property.

10: Polyester container 11: Mouth 12: Neck 13: Shoulder 14: Body 15: Bottom 16: Screw 17: Kabula 18: Support ring 19: Sinking 20: Ground 21: Panel 22: First layer 23: 2nd layer 24: 3rd layer 30: Polyester preform 31: Mouth 32: Body 33: Bottom 34: Screw 35: Kabula 36: Support ring 37: 1st layer 38: 2nd layer 39: 1st 3 layers

Claims (8)

A polyester container made of mechanically recycled polyester.
In the mechanically recycled polyester, the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum is 0.0005 or more and 0.010 or less.
The container capacity (capacity / weight) with respect to the container weight is 5 mL / g or more and 50 mL / g or less.
A polyester container having a cross-sectional thickness of 0.05 mm or more and 0.54 mm or less at the thinnest part of the body of the container. According to the claim, in the differential scanning calorimetry of the polyester container, the temperature lowering crystallization temperature when cooled at a temperature lowering rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes is 175 ° C. or higher and 200 ° C. or lower. The polyester container according to 1. The polyester container has a first layer and a second layer constituting an inner layer, and has a second layer.
The first layer is made of virgin polyester.
The polyester container according to claim 1 or 2, wherein the second layer is made of the mechanically recycled polyester. The polyester container further has a third layer constituting the outer layer.
The polyester container according to claim 3, wherein the third layer is made of virgin polyester. The polyester container comprises a mouth, a neck, a shoulder, a body, and a bottom.
The polyester container according to claim 3 or 4, wherein the first layer is provided from the content filling region or the upper end of the mouth portion to the bottom portion. The polyester container according to any one of claims 1 to 5, wherein the mechanically recycled polyester contains a copolymer of terephthalic acid, isophthalic acid, and ethylene glycol. A polyester preform for producing the polyester container according to any one of claims 1 to 6.
The polyester preform is composed of mechanically recycled polyester.
A polyester preform in which the ratio of the isophthalic acid unit to the terephthalic acid unit determined by the nuclear magnetic resonance spectrum in the mechanically recycled polyester is 0.0005 or more and 0.010 or less. In the differential scanning calorimetry of the polyester preform, the temperature-decreasing crystallization temperature when cooled at a temperature-decreasing rate of 10 ° C./min after being held in a molten state at 300 ° C. for 10 minutes is 175 ° C. or higher and 200 ° C. or lower. Item 7. The polyester preform according to Item 7.

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