JP2018199258A - Multilayer container and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layer container having a gas barrier property using a carbon neutral material. A multilayer container of the present invention is provided with at least a layer containing polyethylene furanoate, wherein the polyethylene furanoate is a polycondensation product of biomass-derived polyethylene glycol and biomass-derived furandicarboxylic acid. To do. [Selection diagram]

Description

  The present invention relates to a multilayer container and a method for producing the same, and more specifically, a multilayer container including a layer containing polyethylene furanoate which is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furan carboxylic acid, and the production thereof. Regarding the method.

  Polyester resins are excellent in mechanical properties, chemical stability, heat resistance, transparency, and the like, and are inexpensive, and are therefore used in the manufacture of containers and the like that contain food and drink. Such containers are required to have gas barrier properties such as oxygen barrier properties, water vapor barrier properties, and carbon dioxide barrier properties from the viewpoint of content preservation, etc., but the gas barrier properties of containers made of polyester resin are sufficient. There was room for improvement. Although the gas barrier property is improved by increasing the thickness of the container, the use amount of the polyester resin is increased by increasing the thickness, which not only increases the weight of the container itself but also increases the manufacturing cost. Therefore, various devices for improving the gas barrier property without increasing the thickness of the container have been studied. For example, the cross section of the container is a multilayer, and in addition to the polyester resin layer, a plastic layer provided with a barrier layer made of a resin such as polymetaxylylene adipamide resin (nylon MXD6), ethylene-vinyl alcohol copolymer resin, polyglycol Containers are known (Japanese Patent Application Laid-Open No. 2003-136057). Moreover, as a barrier layer, it is possible to give an oxygen repair function to a plastic container by using a multilayer container including a barrier layer made of a mixed resin in which nylon and cobalt metal are contained in a polyester resin and a polyester resin layer. It is known (Japanese Patent Publication No. 2-500846).

  By the way, in recent years, with the growing demand for the establishment of a recycling society, in the materials field, it is desired to move away from fossil fuels as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photo-synthesized from carbon dioxide and water, and by using it, it is so-called carbon neutral renewable energy that becomes carbon dioxide and water again. In recent years, biomass plastics using these biomasses as raw materials have been rapidly put into practical use, and attempts have been made to produce polyester resins, which are general-purpose polymer materials, from these biomass raw materials. For example, ethylene glycol is industrially produced using biomass ethanol obtained by fermenting starch and sugars obtained from plants such as corn and sugarcane with microorganisms, and a diol component constituting polyester As some ethylene glycol, polyester resins using biomass-derived ethylene glycol as described above have begun to be used (for example, International Publication 2006/115226 A1).

  Since the multilayer plastic container as described above contains a resin other than the polyester resin as a barrier layer, the amount of the fossil fuel-derived resin can be greatly reduced even if a biomass-derived polyester resin is used. I could not.

JP 2003-136057 A Japanese National Patent Publication No. 2-500846 International Publication No. 2006/115226

The inventors of the present invention unexpectedly used polyethylene furanoate, which is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furandicarboxylic acid, as a constituent material of a layer provided in a multilayer container. It has been found that gas barrier properties can be imparted to the container, and the amount of resin derived from fossil fuel can be greatly reduced, reducing the environmental burden.
In addition, the present inventors can improve the whitening resistance under high temperature and high humidity conditions by using a multilayer container having the above-described configuration, as compared with a multilayer container having a gas barrier layer containing conventional nylon MXD6 or the like. It was found that the dimensional stability can be improved while being able to.
That is, the problem to be solved by the present invention is to provide a multilayer container having a gas barrier property using a carbon neutral material and excellent in whitening resistance and dimensional stability.

  The multilayer container of the present invention includes at least a layer containing polyethylene furanoate, and the polyethylene furanoate is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furan carboxylic acid.

  In the said aspect, it is preferable that 2 mass% or more and 10 mass% or less of polyethylene furanoate are included with respect to the total amount of the resin material contained in a multilayer container.

  In the said aspect, it is preferable that the multilayer container of this invention is provided with a layer containing 3 or more layers and containing a polyethylene furanoate as an intermediate | middle layer.

  In the said aspect, it is preferable that the multilayer container of this invention is equipped with the layer containing biomass origin polyester and / or recycled polyester.

In the said aspect, it is preferable that the oxygen permeability of the multilayer container of this invention is 0.025cc / m < ² > * day or less, when a full capacity is 280 ml.

In the said aspect, it is preferable that the oxygen permeability of the multilayer container of this invention is 0.035cc / m < ² > * day or less, when a full capacity is 350 ml.

  The method for producing a multilayer container of the present invention comprises a step of producing a multilayer preform by co-injecting a resin composition containing polyethylene furanoate and a resin composition containing biomass-derived polyester and / or recycled polyester, And a step of biaxially stretching blow-molding the preform.

  According to the present invention, by using polyethylene furanoate, which is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furandicarboxylic acid, as a material for the layers constituting the multilayer container, the gas barrier performance of the multilayer container is improved. Without damaging the entire multilayer container, the amount of resin used from fossil fuel can be greatly reduced, and the environmental burden can be reduced. Moreover, according to this invention, the whitening resistance and dimensional stability of a multilayer container can be improved.

It is a partial vertical sectional view which shows an example of the multilayer container by this invention. It is a front view which shows an example of the multilayer container bottom part by this invention. It is a partial vertical sectional view which shows an example of the multilayer container by this invention. It is a front view which shows an example of the multilayer container bottom part by this invention.

<Multilayer container>
The multilayer container according to the present invention includes a layer containing polyethylene furanoate (hereinafter, sometimes simply referred to as “polyethylene furanoate layer”). The polyethylene furanoate includes a biomass-derived polyethylene glycol and a biomass-derived flange. It is a polycondensate with carboxylic acid. By providing the multilayer container according to the present invention with a polyethylene furanoate layer, it is possible to impart desirable gas barrier properties to the multilayer container. Moreover, since it is excellent in gas-barrier property, it has high fragrance retention property and can hold | maintain the fragrance of the content for a long period of time. Furthermore, when the multilayer container of the present invention includes the polyethylene furanoate layer, the whitening resistance and dimensional stability of the multilayer container can be improved.
The multilayer container according to the present invention may be provided with two or more polyethylene furanoate layers.

In addition, the multilayer container of the present invention can include a layer containing biomass-derived polyester and / or recycled polyester (hereinafter, simply referred to as “polyester layer”).
The multilayer container according to the present invention may be provided with two or more polyester layers.

  In one embodiment, as shown in FIGS. 1 and 3, the multilayer container 10 comprises a polyethylene furanoate layer 20 as an intermediate layer. In the present invention, the “intermediate layer” refers to a layer other than the innermost layer in contact with the contents and the outermost layer in contact with the outside air.

In one embodiment, the multilayer container 10 of the present invention has a three-layer structure, specifically, a structure of polyester layer 30 / polyethylene furanoate layer 20 / polyester layer 30 with a polyethylene furanoate layer 20 as an intermediate layer. (See FIGS. 1 and 3).
Furthermore, in one embodiment, the multilayer container 10 of the present invention has a five-layer structure, specifically, polyester layer 30 / polyethylene furanoate layer 20 / polyester layer 30 / polyethylene furanoate layer 20 / polyester layer 30. It has a structure.
Since the multilayer container 10 includes the polyethylene furanoate layer 20 as an intermediate layer, acetaldehyde and the like generated from polyethylene terephthalate and the like are eluted into the contents by heating at the time of injection molding for manufacturing a preform described later. Can be prevented.

Oxygen permeability of the multilayer container of the present invention, full Note: If capacity is 280 ml, preferably not more than 0.025cc ^/ m 2 · day, when full delivery volume is 350ml, 0.035cc ^/ m 2 · day The following is preferable.
In the present invention, the oxygen permeability is in accordance with JIS K 7126 (isobaric method) under conditions of 23 ° C. and humidity 40% RH (for example, a product name: OX-, manufactured by MOCON). (TRAN).

The water vapor permeation amount of the multilayer container of the present invention is preferably 0.47 g / 30 day or less when the full capacity is 280 ml, and preferably 0.60 g / 30 day or less when the full capacity is 350 ml. .
In the present invention, the amount of water vapor permeation can be measured using a gravimetric method under the conditions of 22 ° C. and humidity of 40% RH.

  The multi-layer container of the present invention is filled with gas volume 3.4 carbonated water, capped, and the carbon dioxide gas reduction rate after standing for 12 weeks at 22 ° C. and 40% RH is preferably 24% or less. 20% or less is more preferable.

The shape of the multilayer container of the present invention is not particularly limited, and it is preferable to change appropriately according to the type of contents to be filled.
For example, when the content is a carbonated beverage such as natural sparkling water (sparkling water), a container having a petaloid-shaped bottom as shown in FIGS. 1 and 2 is preferable.
Moreover, when heating a container after filling with the contents, it is preferable that the container has a panel part recessed inward of the container as shown in FIG.

  The thickness of the multilayer container is preferably changed as appropriate according to the type of contents to be filled, etc., and can be, for example, 0.15 mm or more and 2 mm or less. Further, the thickness of the container may be uniform or may vary depending on the part.

  Moreover, the multilayer container of this invention can be isolate | separated for every layer by cutting, and has high recyclability.

<Polyethylene furanoate layer>
The polyethylene furanoate contained in the polyethylene furanoate layer provided in the multilayer container of the present invention is a polycondensate of biomass-derived polyethylene glycol and biomass-derived furan carboxylic acid, and is a 100% biomass-derived compound. By using such a compound, the amount of fossil fuel used can be greatly reduced, and the environmental load can be reduced.
The biomass-derived furandicarboxylic acid can be produced from glucose. Specifically, it can be obtained by isomerizing glucose into fructose, dehydrating it, alcoholating it, and then oxidizing it. .
Biomass-derived ethylene glycol is obtained from ethanol (biomass ethanol) produced using biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide.

  The polycondensation of furandicarboxylic acid and polyethylene glycol can be performed by a conventionally known method. Specifically, after performing esterification reaction and / or transesterification reaction of furandicarboxylic acid and polyethylene glycol, the pressure is reduced. It can be produced by a general method of melt polymerization in which a polycondensation reaction is carried out, or a known solution heating dehydration condensation method using an organic solvent.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.

  Examples of the polymerization catalyst include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. And compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof.

  Further, the content of polyethylene furanoate with respect to the total amount of the resin material contained in the multilayer container is preferably 2% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 6% by mass or less. . Thereby, the gas barrier property of a multilayer container can be improved more. Moreover, the recyclability after use of a multilayer container can be improved more.

  The polyethylene furanoate layer may contain a resin material other than polyethylene furanoate as long as the properties of the present invention are not impaired. For example, the polyester furanoate layer may include a polyester resin, a (meth) acrylic resin, a polyolefin resin, a vinyl resin, a cellulose resin, Examples of the resin material include nylon resin, phenol resin, polyurethane resin, epoxy resin, and ionomer resin.

  The polyethylene furanoate layer is an oxygen absorber, a carbon dioxide absorber, a plasticizer, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, and a weathering agent as long as the characteristics of the present invention are not impaired. , Antistatic agents, yarn friction reducing agents, slip agents, mold release agents, antioxidants, ion exchange agents, dispersants, UV absorbers, acetaldehyde absorbers (for example, AA Scavengers manufactured by Color Matrix) and coloring pigments, etc. The additive may be included.

  Examples of the oxygen absorbent include iron-based oxygen absorbents and non-ferrous oxygen absorbents, and non-ferrous oxygen absorbents are more preferable because the transparency of the container body can be maintained.

  Examples of the iron-based oxygen absorbent include iron powders such as reduced iron powder, interfacial iron powder, sprayed iron powder, iron grinding powder, electrolytic iron powder, and pulverized iron.

  Examples of the non-ferrous oxygen absorber include an ethylenically unsaturated group-containing copolymer. Examples of the ethylenically unsaturated group-containing copolymer include polydienes such as polybutadiene, polychloroprene, poly (2-ethylbutadiene), and poly (2-butylbutadiene), which are mainly polymerized at positions 1 and 4, Ring-opening metathesis polymer of cycloolefin such as polyoctenylene, polypentenylene, polynorbornene, styrene-diene block copolymer such as styrene-isoprene block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer Examples include coalescence.

  The content of the oxygen absorbent in the polyethylene furanoate layer is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less.

  The thickness of the polyethylene furanoate layer is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. By setting the pressure of the polyethylene furanoate layer within the above numerical range, the gas barrier property of the multilayer container can be further improved.

<Polyester layer>
The multilayer container of the present invention may include a layer containing biomass-derived polyester and / or recycled polyester. Biomass-derived polyester and recycled polyester, like polyethylene furanoate, have high environmental suitability and can reduce the amount of fossil fuel used.
In the present invention, “biomass-derived polyester” is a polycondensate of biomass-derived diol and dicarboxylic acid derived from biomass or fossil fuel.
Further, “recycled polyester” refers to a material that is collected and reused after using a resin product made of polyester derived from biomass or fossil fuel.

  Examples of the diol include ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol. Can be used.

Although it does not specifically limit about dicarboxylic acid, Aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used without a restriction | limiting.
Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. Examples include chain or alicyclic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of aliphatic dicarboxylic acid, and cyclic acid anhydrides of aliphatic dicarboxylic acid such as succinic anhydride. Can be mentioned.

  Polycondensation of diol and dicarboxylic acid can also be carried out by a conventionally known method. Specifically, after performing the esterification reaction and / or transesterification reaction of dicarboxylic acid and diol described above, It can be produced by a general method of melt polymerization such as performing a polycondensation reaction in the above, or a known solution heating dehydration condensation method using an organic solvent. The polycondensation reaction is preferably performed in the presence of the polymerization catalyst as described above.

  The polyester layer may contain two or more kinds of biomass-derived polyester and / or recycled polyester.

  Among polyesters, the polyester layer is preferably a polyethylene terephthalate layer containing polyethylene terephthalate, that is, polyethylene terephthalate derived from biomass and / or recycled polyethylene terephthalate.

  Moreover, the polyester layer may contain the above-mentioned other resin materials and additives as long as the properties of the present invention are not impaired.

  The thickness of the polyester layer is preferably 100 μm or more and 600 μm or less, and more preferably 150 μm or more and 500 μm or less.

<Others>
In one embodiment, a vapor deposition film may be formed on the inner surface of the multilayer container of the present invention. By providing the vapor deposition layer, the gas barrier property can be further improved.

  The vapor deposition film is preferably made of an inorganic oxide from the viewpoint of gas barrier properties and transparency. As such an inorganic oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, or the like can be used.

  As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

  Further, the film thickness of the deposited film is preferably about 0.005 μm to 0.4 μm, and specifically, the film thickness is preferably about 0.01 to 0.1 μm. By setting the thickness of the deposited film to 0.1 μm, and further to 0.4 μm or less, it is possible to prevent a problem that a crack or the like is likely to occur in the deposited film. On the other hand, by setting the thickness of the deposited film to 0.01 μm, further 0.005 μm or more, the gas barrier effect can be surely exhibited.

<Manufacturing method of multilayer container>
In one embodiment, the multilayer container of the present invention comprises a resin composition comprising polyethylene furanoate and, optionally, other resin materials and additives, biomass-derived polyester and / or recycled polyester, and optionally other resin. A step of producing a preform by co-injection molding a resin composition containing materials and additives;
And biaxial stretch blow molding of the preform.

<Co-injection molding process>
The preform used for manufacturing the multilayer container of the present invention can be manufactured by co-injection molding of two or more resin compositions. Injection molding of the resin composition can be performed by using a conventionally known apparatus.
The temperature during injection molding is preferably 260 ° C. or higher and 310 ° C. or lower, and more preferably 265 ° C. or higher and 300 ° C. or lower.

<Biaxial stretch blow molding>
In the multilayer container of the present invention, the preform is heated to a surface temperature of preferably 90 ° C. or higher and 130 ° C. or lower, more preferably 100 ° C. or higher and 120 ° C. or lower, followed by biaxial stretch blow molding in the mold. Can be obtained.
The preform may be heated by warm air or infrared rays, and can be performed using a conventionally known apparatus.
The biaxial stretch blow molding of the preform can also be performed by using a conventionally known apparatus, for example, LB01 (trade name) manufactured by KHS.
Thus, since the apparatus used for manufacturing the conventional container can be used as it is in the injection molding process of the resin composition, the preform heating process and the biaxial stretch blow process, the multilayer container of the present invention Therefore, it is not necessary to prepare a new molding equipment for manufacturing the steel.

<Other manufacturing methods>
In another embodiment, the preform used for the production of the multilayer container of the present invention can also be produced by compression molding (compression molding) of the resin composition in a mold.

<Application>
The contents filled in the multilayer container of the present invention are not particularly limited, and carbonated beverages such as natural foaming water (sparkling water), sakes such as sake and wine, tea, fruit juice beverages, sports drinks, various seasonings. Fees.
In particular, since the multilayer container of the present invention has high gas barrier properties, it can be suitably used as a carbonated beverage filling container.
In addition, since the multilayer container of the present invention has high heat resistance, it can withstand the filling of high-temperature contents and the heating after filling the contents, so it is suitable as a container for warming sales. Can be used.

  Hereinafter, although the present invention is explained based on an example, the present invention is not limited to these.

Example 1
<Manufacture of multilayer container A>
Co-injection molding was performed with a multilayer injection molding machine to obtain a multilayer preform A having a three-layer configuration of polyethylene terephthalate layer / polyethylene furanoate layer / polyethylene terephthalate layer. The content of biomass-derived polyethylene furanoate relative to the total amount of resin materials contained in the multilayer preform was 6% by mass.

  The preform obtained as described above was heated with a blow molding apparatus LB01 manufactured by KHS until the surface temperature became 107 ° C., and then biaxially stretched and blown in a mold to obtain the shape shown in FIG. Multilayer container A was obtained. The weight of the obtained container was 22 g, the total height was 132 mm, the trunk diameter was 66 mm, and the thickness of the container was 0.30 mm.

Example 2
A multilayer container B was obtained in the same manner as in Example 1 except that the mold used at the time of blow molding was changed and the shape of the resulting multilayer container was changed to the shape shown in FIG. The container thus obtained had a weight of 22 g, an overall height of 206 mm, a trunk diameter of 60 mm, and a container thickness of 0.27 mm. The biomass-derived polyethylene furanoate content relative to the total amount of the resin material contained in the multilayer container was 6% by mass, as in Example 1.

Comparative Example 1
A single-layer container C was obtained in the same manner as in Example 1 except that a single-layer container consisting of only a polyethylene terephthalate layer was prepared. Similar to the multilayer container A, the obtained container had a weight of 22 g, an overall height of 132 mm, a trunk diameter of 66 mm, and a container thickness of 0.30 mm.

Comparative Example 2
A single-layer container D was obtained in the same manner as in Example 2 except that a single-layer container consisting of only a polyethylene terephthalate layer was prepared. Similar to the multilayer container B, the weight of the obtained container was 22 g, the total height was 206 mm, the trunk diameter was 60 mm, and the thickness of the container was 0.27 mm.

<Gas barrier property evaluation>
(Oxygen permeability measurement)
In accordance with JIS K 7126 (isobaric method), the oxygen permeability of the containers obtained in Examples and Comparative Examples was measured using an oxygen gas permeability measuring device (manufactured by MOCON, trade name: OX-TRAN). , 23 ° C., humidity 40% RH. The measurement results are summarized in Table 1.

  As is clear from Table 1, it can be seen that the multilayer container obtained in the examples has excellent gas barrier properties as compared with the container obtained in the comparative example, which is a conventionally used container. Moreover, the container of an Example and the container of a comparative example can be manufactured using the same apparatus, and the resin composition used for manufacture of the container of this invention has high moldability. Recognize.

(Evaluation of carbon dioxide barrier properties)
The container having the shape shown in FIG. 1 obtained in Example 2 and Comparative Example 2 was filled with capped water of 3.4 gas volume using a carbonator Pilot Plant BPP-1 manufactured by Bixle, and capped. .
Under conditions of 22 ° C. and 40% RH, GV in the container after standing for 6 weeks and 12 weeks was measured using DGV-1 (trade name) manufactured by Bixle. The measurement results are summarized in Table 2.

<Evaluation of whitening resistance under high temperature environment>
The container having the shape shown in FIG. 2 obtained in Example 1 was filled with normal temperature water so that a head space of 25 mm was formed from the top surface, and capped. This was stored in Kanwarmer (Nippon Heater Equipment Co., Ltd., trade name: TW75-C3) so that the liquid temperature was 70 ° C. The containers after 7 days and 17 days were visually observed and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 3.
Further, as Comparative Example 3, a multilayer container having a three-layer configuration of polyethylene terephthalate layer / metaxylene adipamide + cobalt stearate / polyethylene terephthalate layer was used.
(Evaluation criteria)
○: No whitening of the container was observed.
Δ: Whitening of the container was observed.
X: Many whitening of the container was seen.

<Whitening resistance test under high humidity>
The container having the shape shown in FIG. 2 obtained in Example 1 and the container of Comparative Example 3 were allowed to stand for 2 weeks in an environment of 40 ° C. and 90% RH, and then the appearance of the container was visually observed. Evaluation was performed according to the following evaluation criteria. The evaluation results are summarized in Table 4.
(Evaluation criteria)
○: No whitening of the container was observed.
X: Whitening of the container was observed.

<Dimensional stability test>
A container was produced in the same manner as in Example 1 (Example 3). The weight of the container was 22 g, the total height including the cap was 134.42 mm, and the bottom depth was 17.38 mm.
Moreover, the container was produced like the comparative example 1 (comparative example 4). The weight of the container was 22 g, the total height including the cap was 134.35 mm, and the bottom depth was 16.93 mm.
The container was filled with normal temperature water so that a head space of 25 mm from the top surface was formed, and capped. This was stored so that the liquid temperature would be 70 ° C. in Kanwarmer (trade name: TW75-C3, manufactured by Nippon Heater Equipment Co., Ltd.).
The dimensional changes of the containers after storage for 1 week and after storage for 2 weeks were measured and summarized in Table 5.
In addition, the dimensional change of the total height is Digimatic Height Gauge Code No. manufactured by Mitutoyo. According to 192-663, the dimensional change of the bottom depth was measured by a depth gauge Model ID-C1012XBD manufactured by Mitutoyo.

10: Multilayer container 20: Polyethylene furanoate layer 30: Polyester layer

Claims (7)

A multilayer container comprising at least a layer comprising polyethylene furanoate,
The multi-layer container, wherein the polyethylene furanoate is a polycondensate of polyethylene glycol derived from biomass and furan carboxylic acid derived from biomass.   2. The multilayer container according to claim 1, wherein the polyethylene furanoate is contained in an amount of 2% by mass or more and 10% by mass or less based on the total amount of the resin material contained in the multilayer container.   The multilayer container according to claim 1, wherein the multilayer container includes three or more layers and includes a layer containing the polyethylene furanoate as an intermediate layer.   The multilayer container as described in any one of Claims 1-3 provided with the layer containing biomass origin polyester and / or recycled polyester. The multi-layer container according to any one of claims 1 to 4, wherein the full capacity is 280 ml, and the oxygen permeability is 0.025 cc / m ² · day or less. The multi-layer container according to any one of claims 1 to 4, wherein the full capacity is 350 ml, and the oxygen permeability is 0.035 cc / m ² · day or less. Co-injecting a resin composition containing polyethylene furanoate and a resin composition containing biomass-derived polyester and / or recycled polyester to produce a multilayer preform;
The biaxial stretch blow molding of the preform;
A method for producing a multilayer container, comprising:

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