JP2001062975A - Plastic bottle for beer compatible with environment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a beer bottle of extremely high oxygen barrier properties and carbon dioxide gas barrier properties for trapping oxygen passed through a resin layer by providing a structural material resin layer or a gas barrier resin layer on both surface layers and also providing an oxygen trapping resin layer using a PET bottle recycle flakes generally as a low-molecular material PET on an intermediate layer. SOLUTION: A multilayer plastic bottle having the 0.05-4 liter content and the 0.1-2 mm total thickness of a bottle body section and containing a beverage PET bottle recycle material as an intermediate layer is constituted of two or more kinds of resins composed of a barrier resin or a structural material resin as a surface material and formed of three or more layers, and when a beer is filled, sealed and stored in atmosphere at 4-25 deg.C for 180 days, the infiltration amount of oxygen into the bottle is 1 ppm or less to the beer weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layered plastic bottle for beer which is not oxidized from the aspect of quality as a content and requires no escape of carbon dioxide gas from a container wall, and particularly to a beverage as an intermediate layer. The present invention relates to a multi-layer beer bottle made of a thermoplastic plastic which contains at least one oxygen-scavenging resin layer using a recycled material of a PET bottle, is inexpensive, lightweight, has excellent impact resistance, recyclability, and gas barrier properties, and a method for producing the same.

[0002]

2. Description of the Related Art The Containers and Packaging Recycling Law was enacted in June 1995.
The traditional autonomy is changing to something that should be strongly promoted as part of the national recycling system. The basic idea is to share the responsibilities of municipalities, consumers and businesses,
In other words, consumers are demanding "separate discharge", municipalities are "responsible for separate collection", and businesses are demanding "responsibility for recycling". PET bottles (second-class designated products) have been designated as specified containers, and since April 1997, separate collection and recycling according to the Container Recycling Law have become mandatory. Accordingly, the recovery rate of PET bottle resin was 2.
From 9% to 1997, 9.8% performance improvement was achieved. In 1998, the recovery rate is expected to increase sharply to 18%. This means that the recycling system has started working well.

[0003] As described above, when the collection of PET bottles goes on track, the next problem that emerges is that the collected P
The importance of ET bottle reuse and recycling business is important. Recycled PET resin is polyester itself and can be used and is suitable for all uses that can be used as polyester. Representative products of the three major fields of application of recycled PET resins are textiles, sheet products, and detergent bottles. At present, shirts, work clothes, uniforms,
Many used products such as socks are sold. Sheet products include cushioning materials, fruit packages, ink cans, and stationery. Detergent bottles are also used in large quantities, but recently boxes, cases and partitioning trays for various applications have been made. The current PET bottle consumption per capita is 1.3 kg, but it has been estimated that if recycling progresses, it will be necessary to use and consume 0.8 kg of recycled products per capita in the near future. This is a very big issue, and it is expected that not only the increase in fiber use, but also the development of new products such as sheet products and molded products, as well as the recycling of food containers, especially beverage bottles, will be indispensable.

[0004] From the above viewpoints, research and development of recycling are being actively promoted in Japan and overseas. To determine whether recycled plastic can be reused in food containers, you must ensure that the contaminants present in the recycled product are within the limits allowed by regulatory standards. For this reason, there are concepts of "functional barrier" and "threshold" as concepts for safe use in food containers in developed countries of Europe and the United States. Is the current situation. In addition, it is consistent with each country that a recycled product obtained by a chemical recycling process, so-called chemical recycling, is considered to be the same as an unused resin. Regarding the functional barrier, in the case of recycled plastic, if a structure that is not in direct contact with food is used with an unused plastic layer even if contaminants remain in it,
We believe that the transfer of contaminants to food can be prevented. For this purpose, when an unused plastic layer is used as a functional barrier, the recycled plastic layer intentionally contaminated with a substitute compound for contaminants is transferred into a food pseudo solvent through a barrier layer having a predetermined thickness. It is necessary to confirm by a dissolution test that the substance does not migrate.

[0005] In Japan, interest in bottle-to-bottle recycling is increasing. The “Recycled Plastic Hygiene Roundtable” was set up within the Polyolefin Hygiene Council and has been actively conducting research activities since 1993. The results were published in June 1996 in the report "Conditions for Reusing Plastic Recycled from Used Containers and Packaging for Food Containers and Packaging". Because of the difficulty in ensuring the sanitary safety of direct contact with food, a sandwich structure was proposed in which recycled plastic was used for the intermediate layer of a multilayer molded product and unused resin was used as a functional barrier layer. It has been put to practical use in several countries. If the recycled plastic inside contains harmful substances, it is important that the unused resin layer acts as a functional barrier layer to prevent harmful substances from penetrating and permeating and eluting. is suggesting.

In accordance with FDA guidelines,
We prepared test samples using model contaminants and developed a test method to confirm the elution of model contaminants from recycled plastic and the barrier function of unused resin. In Japan, an experiment was conducted with the first model contaminant, and no elution of the model contaminant from the recycled plastic through the functional barrier was observed. No migration was reported. Based on the above, it has been concluded that the self-regulation standards will be limited to three-layer containers and packaging with unused resin as the barrier layer for the time being. Based on the above, it has been concluded that the self-regulation standards will be limited to three-layer containers and packaging with unused resin as a barrier layer for the time being.

[0007] Active development of PET bottles for beer is being conducted under the initiative of Europe and the United States. Europe and the United States are more keen on bottles than Japan, and it is predicted that 75% of beer drinkers will buy plastic bottles of the same brand. Glass bottles are banned for watching sports and on the sandy beach due to scattering of glass, so they are first tested and sold in this area. Major beer makers, Anne Heuserbush (US), Miller (US), Bass (UK), Foster (Australia), etc. are also actively developing. The Japanese market has different consumer preferences,
Plasticization of beer bottles is expected to be more difficult than in Europe and the United States, but major beer makers are in the process of undertaking research and development underwater. Recycling has become a major theme even for PET bottles for beverages.
When it comes to T bottles, the sales volume is enormous, and the recycling problem cannot be avoided. Although such research has just begun, the development of plastic bottles for beer using recycled materials effectively is desired.

[0008]

According to the present invention, a structural resin or a gas-barrier resin layer is provided on both surface layers, and an intermediate layer between these layers is generally made of a low molecular weight PET.
An object of the present invention is to provide a beer bottle having an extremely high oxygen barrier property and a carbon dioxide gas barrier property, in which an oxygen-scavenging resin layer using T-bottle recycle flakes is provided so that oxygen passing through the resin layer can be trapped.

[0009]

Means for Solving the Problems The present invention relates to [1] a recycled material for PET bottles for beverages as an intermediate layer having a content of 0.05 to 4 liters and a total thickness of the bottle body of 0.1 to 2 mm. A multi-layer plastic bottle comprising at least one layer of an oxygen-scavenging resin layer using at least two layers of a barrier resin or a structural material resin as a surface material and a structure of three or more layers, wherein beer is filled. A plastic bottle for beer, wherein when sealed and stored in the atmosphere at 4 to 25 ° C. for 180 days, the amount of oxygen entering the bottle is 1 ppm or less with respect to the weight of beer,
[2] The plastic bottle for beer according to the above [1], wherein the structural material resin is a resin in which 50% or more of the resin is a copolymer or a blend composed of polyethylene terephthalate. The beer according to the above [1], wherein the escaped amount of carbon dioxide gas is less than 10 w% as the carbon dioxide gas filling amount is reduced when filled and sealed and stored in the atmosphere at 4 to 25 ° C. for 180 days. Plastic bottles,

[4] The plastic bottle for beer according to the above [1], wherein the surface material is any one of EVOH, MXD6, PETI or PEN having a carbon dioxide gas barrier property, [5] the oxygen-scavenging resin layer comprises The plastic bottle for beer according to [1], which is a polyethylene terephthalate-based oxygen-scavenging resin using a recycled PET bottle for beverage (IV value, 0.3 to 0.8),
[6] At least one of the intermediate layers is composed of a layer containing a polyethylene terephthalate-based oxygen-scavenging resin using a recycled material, and the polyethylene-terephthalate-based polymer segment constituting the main part of the oxygen-scavenging resin and a small part thereof [7] The plastic bottle for beer according to the above [1], which comprises a constituent olefin oligomer segment and further contains a catalytic amount of a transition metal compound.
The plastic bottle for beer according to [1], wherein the oxygen-scavenging resin is a polyethylene terephthalate (co) polymer in which an olefin oligomer segment having a carbon-carbon unsaturated bond in a molecule is bonded,

[8] The polyethylene terephthalate-based oxygen-scavenging resin comprises an olefin oligomer segment having a molecular weight of 1,000 to 10,000 and a polyethylene terephthalate segment having a molecular weight of 99.5 to 85 w%, which corresponds to 0.5 to 15 w%. The copolymer contains 50 to 500 pp of a transition metal compound which promotes oxidation.
The plastic bottle for beer according to the above [1] or [7], which is a resin composition containing m. [10] The plastic bottle for beer according to the above [7] or [8], which contains an agent.
The plastic bottle for beer according to the above [1], wherein the olefin oligomer segment in the oxygen-scavenging resin is an oligomer of butadiene, norbornene, dicyclopentadiene, and isoprene.

[11] The above-mentioned [7], wherein the olefin oligomer segment having a carbon-carbon unsaturated bond in the oxygen-scavenging resin is an oxygen-scavenging resin bonded as a main chain of a main polymer segment or as a branched pendant. [10] The plastic bottle for beer according to any one of [10] to [12], wherein at least one layer other than the innermost layer of the multilayer plastic bottle is blended with an ultraviolet absorbing material and / or an ultraviolet shielding material. ] The plastic bottle for beer according to [13].
The plastic bottle for beer according to any one of [1] to [12], which has a transparency of at least 70% as compared with the transparency of a plastic bottle of a single-layer polyester polymer having the same thickness, and [14] a multilayer plastic. The bottle has a gas barrier resin layer / a resin layer containing an oxygen scavenging resin / a gas barrier resin layer or a structural material resin layer / a gas barrier resin layer / a resin layer containing an oxygen scavenging resin / a gas barrier resin layer / structure from the innermost layer. The above problem was solved by developing a plastic bottle for beer according to the above [1] having a constitution of a material resin layer.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The plastic bottle for beer of the present invention is intended for a small beer bottle having an inner volume of about 0.05 to 4 liters. Generally, in such a container, as the internal volume decreases, the surface area of the container (so-called specific surface area) relative to the internal volume of the container increases, and in such a small container, the gas barrier is determined only by the thickness of the bottle wall. In order to improve the performance, the smaller the bottle, the higher the gas barrier property needs to be.Therefore, a bottle with a thicker wall is required. . Therefore, there is a need for a plastic bottle that satisfies both the rigidity required for a beer bottle and the gas barrier property required for the bottle, is lightweight, has low cost, and is easily manufactured. In order to respond to the above demands and the problem of recycling responsibility, a gas barrier resin or a structural material resin is used as a surface material, and as an intermediate layer, one layer of an oxygen-scavenging resin layer using a recycled material of a PET bottle for beverages is used. A multilayer plastic bottle having at least a three-layer structure or a five-layer structure of an oxygen-scavenging resin using a structural material resin for the surface layer and a gas-barrier resin and a recycled PET bottle for beverages inside. Is considered as one solution.

When the plastic bottle is filled and sealed with beer and stored at room temperature for 180 days, the amount of oxygen entering the bottle keeps 1 ppm or less with respect to the weight of the internal beer, and at room temperature for 180 days. The type and thickness of the gas barrier resin are adjusted so that the escape amount of the carbon dioxide gas permeating the bottle wall from the inside of the beer bottle is less than 10% when measured as a decrease in the carbon dioxide gas filling amount, thereby providing gas barrier properties. . Incidentally, the oxygen-scavenging resin using the recycled material of the PET bottle for beverages used as the intermediate layer of the beer bottle of the present invention can pass through the gas-barrier resin layer even when the oxygen-barrier property of the gas-barrier resin is insufficient. This is extremely effective for capturing incoming oxygen to prevent intrusion into the inside of the bottle, and ensures that unexpected defects in the gas barrier resin layer are compensated.

Particularly, in a small container, the rigidity of the beer bottle is sufficient only by the thickness of the gas-barrier resin layer which secures a necessary minimum gas-barrier property, but in a relatively large beer bottle, the minimum barrier property is sufficient. It is possible that rigidity as a bottle may be insufficient just by achieving the thickness, and in such a case, a gas barrier resin with high cost can be obtained by laminating a structural resin such as polyethylene terephthalate on the surface of the gas barrier resin. It is preferable to reduce the amount of the structural material resin used. The relationship between the thickness of each resin layer is determined by the required gas barrier properties, but in the case of three or five layers, the oxygen scavenging property using recycled PET bottle beverage material as the intermediate layer The resin layer containing the resin is 2 to 70% of the total thickness, preferably 5 to 70%.
The structural material resin layer, the gas barrier resin layer and the resin layer containing the oxygen-scavenging resin in the case of 5 layers are: structural material resin layer (5 to 45%) / gas barrier resin layer (5 to 20% )
/ Resin layer containing oxygen scavenging resin (5-70%) / gas barrier resin layer (5-20%) / structural material resin layer (5-45%)
%).

The gas barrier resin used in the present invention is not particularly limited as long as it has a high gas barrier property against oxygen and carbon dioxide and can be thermoformed. EVO is the most suitable resin as such a gas barrier resin in view of the balance between performance and cost.
H can be mentioned. For example, if the ethylene content is 2
An ethylene-vinyl acetate copolymer having 0 to 60 mol%, particularly 25 to 50 mol%, has a saponification degree of 96 mol% or more,
In particular, a saponified copolymer obtained by saponifying it to be 99 mol% or more can be mentioned. This EVOH
Should have a molecular weight sufficient to form a film and are generally at least 0.01 dl / g, especially 0.05 dl / g, as measured at 30 ° C. in a mixed solvent of phenol: water at a weight ratio of 85:15. It preferably has a viscosity of at least g.

Other examples of the gas-barrier resin having the above-mentioned properties include polyvinylidene chloride, polyacrylonitrile, and the number of amide groups per 100 carbon atoms is 5 to 5;
Polyamides and polyester copolymers in the range of 0, especially 6 to 20 can be used. For example, polyamides include nylon 6, nylon 66, nylon 6-66 copolymer, polymethacrylicylene adipamide (hereinafter referred to as MXD).
6 ". ), Nylon 6,10, nylon 11, nylon 12, nylon 13, and the like. Examples of the polyester copolymer include a modified polyester copolymer in which 30 mol% or less of terephthalic acid used in PET, PBT and PEN is substituted with isophthalic acid. These gas barrier resins also preferably have a molecular weight sufficient to form a film. In the case of polyamide, the relative viscosity (η _rel ) measured at a concentration of 1.0 dl / g in concentrated sulfuric acid at a temperature of 30 ° C. is 1. One or more, especially 1.
It is desirable that the number be 5 or more. In the present invention, among the above gas barrier resins, MXD6 and an isophthalic acid-modified polyester copolymer are preferable from the viewpoint of the oxygen barrier property and the carbon dioxide gas barrier property.

In the present invention, a polyester resin is used as a structural resin used when strength is insufficient. 80% by weight or more of the polyester resin is PET, PB
It is composed of a polymer of T or PEN, a copolymer mainly composed of T or PEN, or a mixture of polymers having these segments. Of these, PET is considered to be the most suitable material because it is transparent when stretch blown, has high rigidity and is inexpensive. PBT has heat resistance and high rigidity, but is more expensive and opaque than PET. Although PEN is transparent, has high rigidity and excellent heat resistance, it is considered that it can be used only in special cases because it has the highest cost. PET is the best in terms of cost and performance balance.

In the beer bottle of the present invention, it is necessary that at least one of the intermediate layers contains an oxygen-scavenging resin made of recycled PET bottles for beverages. This may be an intermediate layer of the oxygen-scavenging resin alone using the recycled material for the beverage PET bottle, or may be compatible with the recycled material for the beverage PET bottle, other resins, for example, the oxygen-scavenging resin. It may be used after being diluted with a resin. By diluting with another resin, there is also an advantage that the physical properties of the intermediate layer can be physically improved when selecting a combination of resins to be diluted. As a resin compatible with the oxygen-scavenging resin, a resin of the same type as the oxygen-scavenging resin is preferable. The dilution ratio is at least 5 for the oxygen-scavenging resin.
It can be blended so as to have a concentration of at least 20% by weight, preferably at least 20%.

The oxygen-scavenging resin using a recycled PET bottle for a beverage in the present invention refers to a polyester-based recycled PET beverage bottle having an olefin oligomer segment having a carbon-carbon unsaturated bond in the molecule. Means a polymer. Polyethylene terephthalate recovered from PET bottles for beverages is mostly used as the recycled polymer. However, some of the polyester polymers are made from alkylene glycols such as PBT and PEN and aromatic dibasic acids. A polycondensate, a polycarbonate polymer composed of carbonic acid and a dihydric phenol obtained by a polycondensation reaction of bisphenol and phosgene, and a polyarylate which is a polycondensate of a dibasic acid and a dihydric phenol may be included. In addition, some polyamide polymers, for example, nylon 6, nylon 66, nylon 1
2 or the like, and polyxylylenediamine adipamide (MXD6) in some cases. .

In order to introduce an olefin oligomer segment having a carbon-carbon unsaturated bond into the polycondensate used as a recycled material for such a PET bottle for beverages,
For example, the recovered PET bottle recycled material is subjected to a transesterification reaction of an olefin oligomer having a hydroxyl group or a carboxyl group at both ends and having a carbon-carbon unsaturated bond, and an olefin oligomer segment is introduced into the PET main chain to thereby reduce oxygen content. It can be a trapping resin. Separately, an olefin oligomer having two hydroxyl groups or carboxyl groups at one end and having a carbon-carbon unsaturated bond may be transesterified into recycled PET bottle material, or glycerin, trimellitic acid , 3 in a molecule such as trimesic acid
A polyvalent compound having at least one functional group is introduced into the main chain of PET by a transesterification reaction, which has at least one other functional group reactive with the functional group, and An olefin oligomer having a carbon-carbon unsaturated bond may be reacted to bond olefin oligomer segments pendant without entering the main chain.

For example, a required amount of glycerin is subjected to a transesterification reaction with a recycled material of a PET bottle to add a hydroxyl group to a polyester main chain, and a carboxyl group, a carboxylic anhydride group, an epoxy group, and the like which are reactive with the hydroxyl group. An oxygen-scavenging resin can be obtained by reacting an olefin oligomer having a carbon-carbon unsaturated bond into which an isocyanate group or the like has been introduced. Also PET
In such a case, an oxygen scavenging resin can be obtained by directly transesterifying an olefin oligomer having two hydroxyl groups introduced at one end. The resin having such a pendant type olefin oligomer segment has little performance degradation as a polyester copolymer because the main chain is not cut but only the branch is cut even when the oxygen-scavenging resin captures oxygen. There are features.

As the oxygen-scavenging resin layer, the degree of utilization of the recycled material is reduced, but a newly synthesized oxygen-scavenging resin compatible with the recycled material of the PET bottle, for example, a carbon-carbon compound in the main chain or the branch. A resin obtained by blending a PET bottle recycled material with a polyester-based, polyamide-based, polyolefin-based, or polyvinyl-based oxygen-scavenging resin into which an olefin oligomer segment having an unsaturated bond is introduced can also be used. . Newly synthesized oxygen-scavenging resin or PET
When the recycled material of the PET bottle is blended with the oxygen-scavenging resin obtained by modifying the recycled material of the bottle, the amount of the compound is determined by the amount of the olefin oligomer having an effective carbon-carbon unsaturated bond in the oxygen-scavenging resin. , But usually at least 5% as an oxygen-scavenging resin.
%, Preferably at least 20% by weight. If the content is less than 5% by weight, the oxygen scavenging amount is small, and if there is no barrier resin, the oxygen scavenging property is lost in a short time and oxygen is permeated. Of course, the oxygen-scavenging resin layer may be 100% oxygen-scavenging resin.

As the oxygen-scavenging resin, oxygen is scavenged in an olefin oligomer segment having a carbon-carbon unsaturated bond active for oxygen. The reaction is initiated by hydrogen abstraction of the carbon at the position, and eventually the carbon chain is cleaved from this part. Therefore, a polymer having an olefin oligomer segment in the main chain undergoes main chain cleavage. On the other hand, in a polymer in which olefin oligomer segments are bonded in a pendant form, the problem is only the cleavage of the pendant olefin oligomer segments, and the main chain having a large effect on physical properties is not affected at all even if oxygen is trapped. become. When only physical properties are considered, a pendant-bound oxygen-scavenging resin is preferred.

The olefin oligomer to be introduced includes a carbon-carbon unsaturated bond and its α
Bond having a carbon having a hydrogen at the -position [allyl bond =
(—CH ＝ CH—CHR—), wherein R represents a hydrogen atom, a lower alkyl group, or the like. ] Is preferable. Such a bond is obtained when polymerizing or copolymerizing a conjugated diene such as isoprene, butadiene, norbornene, dicyclopentadiene or a non-conjugated diene. Among them, an olefin oligomer segment containing an isoprene segment has high oxygen scavenging activity. The molecular weight of this olefin oligomer segment depends on whether the oxygen-scavenging resin requires transparency or may be opaque, the type of the main constituent compound of the oxygen-scavenging resin, introduced into the main chain, or introduced in a pendant form. The appropriate value may vary depending on the form of introduction such as squid, the type of compound constituting the oligomer, the average number of oligomer segments introduced into one molecule of the oxygen-scavenging resin, and the number of carbon-carbon unsaturated bonds in the oligomer. Although the molecular weight may be small when the number of the introduced oligomer segments is large, the molecular weight tends to be large when the number of the introduced oligomer segments is small, and generally less than about 5 in one molecule of the oxygen-scavenging resin. When transparency is required, if it is a butadiene oligomer, the oligomer molecular weight is about 1,000 to 10,000. It can be used ones.

Since such an oxygen-scavenging resin has low reactivity with oxygen as it is, it is necessary to add a catalytic amount of a transition metal compound to the resin in order to preferably increase the reactivity with oxygen. . Suitable metal compounds include manganese, cobalt, nickel, copper, rhodium, ruthenium, and the like, most preferably cobalt. Preferred counterions for this metal include, but are not limited to, chloride, acetate, sterate, palmitate, 2-ethylhexanoate, neodecanoate, naphthenate and the like. . Particularly preferred are cobalt 2-ethylhexanoate and cobalt neodecanoate. Alternatively, the transition metal compound may be an ionomer, which are well known in the art. The amount of the transition metal compound is 0.001% by weight of the oxygen-scavenging resin as the metal.
To 1%, preferably 0.01 to 0.3%
It is. Below the lower limit, the effect of promoting the reaction is not recognized, and even if it exceeds 1%, the effect is saturated and does not increase the reaction rate with oxygen, but merely increases the cost.

In the case where an antioxidant is added to the oxygen-scavenging resin layer, it is preferable to add a photooxidation accelerator (sensitizer) in addition to the transition metal compound of the copolymer. Benzophenone,
o-methoxybenzophenone, acetophenone, o-methoxyacetophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanophenone, α-
Phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, and the like can be used, but are not limited thereto.

This photo-oxidation accelerator enhances the oxygen scavenging rate of the oxygen-scavenging resin by exposure to light.
It varies depending on the type of oxygen-scavenging resin, wavelength and intensity of light, and the like. If the transparency of the resin is low, it is necessary to increase the amount of the photo-oxidation accelerator used. Usually, it is about 0.01 to 10% by weight, preferably about 0.1 to 1% by weight, based on the whole resin composition. The transition metal compound and the photo-oxidation accelerator are described in detail in JP-A-5-194949. In the case of beer bottles, it is required to shield ultraviolet rays from the viewpoint of preservation of aroma of beer,
It is preferable that at least one layer of the multilayer plastic bottle is blended with an ultraviolet ray shielding property, an ultraviolet ray absorbent and the like.

As can be seen from the above description, it is possible to provide a gas barrier resin layer as an intermediate layer or to impart a gas barrier property to the oxygen-scavenging resin. It is also possible to have a function, and in such a case, it is also possible to use a structural material resin layer instead of the gas barrier resin layers on both surface layers. Oxygen scavenging resin is expensive, and PE
By using the recycled material of the T bottle, it becomes possible to make the price very low. In addition, there is a concern about the toxicity of the recycled material of the PET bottle (for example, when an agrochemical or the like is put in an empty PET bottle), but it has been confirmed that there is no problem because it is used for the intermediate layer. However, it is necessary to clarify the collection route of PET bottles and use recycled materials free of toxic substances.

The plastic bottle according to the present invention has a gas barrier resin layer (which may be a structural resin layer) / a resin layer containing an oxygen-scavenging resin using a recycled PET bottle / gas barrier resin layer. (Or resin layer of structural material) or bottle composed of structural resin layer / gas barrier resin layer / resin layer containing oxygen scavenging resin using recycled PET bottle material / gas barrier resin layer / structural material resin layer A parison is formed by injection molding, and this is formed into a multilayer plastic bottle by stretch blow. The plastic bottle is usually transparent, and it is easy to ensure that the transparency is at least 70% or more as compared with a PET bottle of the same thickness. If it is desired to make this opaque for some reason, it can be easily made opaque by adding a filler such as a pigment or an inorganic oxide. For the gas barrier resin and the structural material resin in the present invention, beer toxicity, antioxidants, coloring agents, plasticizers, fillers, and other additives as necessary as long as they do not affect taste or aroma Can be used.

[0031]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. [Production of Oxygen-scavenging Resin] The following oxygen-scavenging resin is produced by a co-axial twin screw extruder (TEM3 manufactured by Toshiba Machine Co., Ltd.).
7BS, 37 mmφ, L / D = 45) to prepare an oxygen-scavenging resin.

(Production of polyethylene terephthalate-based oxygen-scavenging resin) 1) Block copolymer Polyester-based oxygen-scavenging resin-A (PE-A) As a base polymer, polyethylene terephthalate flakes obtained by pulverizing a beverage PET bottle (intrinsic viscosity IV =
0.65) was introduced from a 96 parts by weight hopper. The melting temperature of the resin was set at 280 ° C., and both ends of the hydroxyl group butadiene oligomer (RTF45 manufactured by Elphatochem, Mw = 2
800) Cobalt stearate is added to 4 parts by weight of the liquid material, and 200 p with respect to the total amount of the base polymer and the oligomer.
pm is introduced into the extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, unreacted substances and low molecular substances are removed from the vacuum vent, and the molten strand is quenched in water. Then, a pellet was obtained. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, and then dried at 150 ° C. for 4 hours to obtain a water content of 0.1%.
After confirming that the content was 005 parts by weight or less, it was used for subsequent molding.

B. Polyester oxygen scavenging resin-B
(PE-B) Polyethylene terephthalate flakes (intrinsic viscosity IV = 0.65) obtained by pulverizing PET for beverage were introduced from a 92 parts by weight hopper. The melting temperature of the resin is set at 280 ° C,
A mixture of 8 parts by weight of a liquid butadiene oligomer having hydroxyl groups at both ends (RLM20 manufactured by Elphatochem Co., Ltd., Mw = 1230) and 200 ppm of cobalt stearate based on the total amount of the base polymer and the oligomer is extruded using a liquid injector. The mixture was melt-kneaded for a residence time of about 5 minutes to remove unreacted substances and low molecular weight substances from a vacuum vent. Then, the molten strand was quenched in water to obtain pellets.
The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours.
After drying for an hour, it was confirmed that the water content was not more than 0.005 parts by weight, and used for subsequent molding.

C. Polyester-based oxygen-scavenging resin -C
(PE-C) Polyethylene terephthalate flakes (intrinsic viscosity IV = 0.65) obtained by pulverizing PET for beverage were introduced from a hopper by 88 parts by weight. The melting temperature of the resin is set at 280 ° C,
Hydroxyl octadiene oligomer at both ends (an octadiene oligomer is synthesized from octadiene by metathesis polymerization, and both ends are substituted with hydroxyl groups by hydrolysis.
Mw = 2000) A mixture of 200 parts by weight of cobalt stearate and 200 ppm of benzophenone based on the total amount of the base polymer and the oligomer in 12 parts by weight of the liquid was introduced into an extruder using a liquid injector, and the residence time was measured. After melt kneading for about 5 minutes, unreacted substances and low molecular substances were removed from the vacuum vent, and the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets are sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, then dried at 150 ° C. for 4 hours, and confirmed to have a moisture content of 0.005 parts by weight or less, and used for subsequent molding. did.

D. Polyester-based oxygen-scavenging resin-D
(PE-D) Polyethylene terephthalate flakes (intrinsic viscosity IV = 0.55) obtained by pulverizing PET for beverages were introduced from a 96 parts by weight hopper. The melting temperature of the resin is set at 280 ° C,
Both-end hydroxyl group norbornene oligomer (a norbornene oligomer is synthesized from norbornene by metathesis polymerization, and both ends are substituted with hydroxyl groups by hydrolysis.
(Mw = 5000) Cobalt stearate is added to 4 parts by weight of the liquid material based on the total amount of the base polymer and the oligomer.
The mixture containing 00 ppm was introduced into an extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, and unreacted substances and low-molecular substances were removed from a vacuum vent. Then, the molten strand was quenched in water. Then, a pellet was obtained. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were sufficiently crystallized at a temperature of 120 ° C. for 2 hours in a vacuum dryer, and then dried at 150 ° C. for 4 hours.
After confirming that the water content was 0.005 parts by weight or less, it was used for subsequent molding.

E. Polyester-based oxygen-scavenging resin-E
(PE-E) 92 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.55) obtained by pulverizing PET for beverage were introduced from a hopper. The melting temperature of the resin is set at 280 ° C,
Both ends hydroxyl group dicyclopentadiene oligomer (a dicyclopentadiene oligomer synthesized from dicyclopentadiene by metathesis polymerization, and both ends are substituted with hydroxyl groups by hydrolysis. Mw = 10000) Basically, cobalt stearate is used in 8 parts by weight. Polybutadiene mixed with 200 ppm based on the total amount of the polymer and the oligomer is introduced into an extruder (P different from the PET hopper).
ET is preferably introduced from the second supply port after melting, but may be dry-blended with PET and introduced from a hopper, and then melt-kneaded for a residence time of about 5 minutes to obtain unreacted substances and low molecular weight substances. After the material was removed from the vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were sufficiently crystallized at a temperature of 120 ° C. for 2 hours in a vacuum dryer, and then dried at 150 ° C. for 4 hours.
After confirming that the water content was 0.005 parts by weight or less, it was used for subsequent molding.

F. Polyester-based oxygen-scavenging resin-F
(PE-F) Polyethylene terephthalate flakes (intrinsic viscosity IV = 0.40) obtained by pulverizing PET for beverages were introduced from a 96 parts by weight hopper. The melting temperature of the resin is set at 280 ° C,
Both terminal carboxyl group butadiene oligomer (normal anionic living polymerization was carried out using butadiene.
In order to obtain a carboxyl group at both ends, a bifunctional initiator which generates two anionic terminals is used as the initiator. Further, carbon dioxide gas was used in the termination reaction. This time the molecular weight is 380
0. 4) Cobalt stearate is added to 4 parts by weight of the liquid based on the total amount of the base polymer and the oligomer.
ppm was introduced into the extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, unreacted substances and low molecular substances were removed from the vacuum vent, and the molten strand was quenched in water. Then, a pellet was obtained. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets are sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, then dried at 150 ° C. for 4 hours, and confirmed to have a moisture content of 0.005 parts by weight or less, and used for subsequent molding. did.

2) Graft copolymer Polyester-based oxygen-scavenging resin-G (PE-G) 96 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.65) obtained by pulverizing PET for beverage were introduced from a hopper. The melting temperature of the resin is set at 280 ° C,
Butadiene oligomer having two hydroxyl groups at one end (butadiene was subjected to ordinary anionic living polymerization, epichlorohydrin was used for termination reaction, and further hydrolyzed to obtain a butadiene oligomer having two hydroxyl groups at one end. This time, the one with a molecular weight of 5000 was created.)
A mixture obtained by mixing 200 parts by weight of cobalt stearate with respect to the total amount of the base polymer and the oligomer to 4 parts by weight of the liquid material was introduced into an extruder using a liquid injection machine, and the mixture was melt-kneaded for a residence time of about 5 minutes. After removing unreacted substances and low molecular substances from the vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets are sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, then dried at 150 ° C. for 4 hours, and confirmed to have a moisture content of 0.005 parts by weight or less, and used for subsequent molding. did.

H. Polyester-based oxygen-scavenging resin-H
(PE-H) 92 parts by weight of crushed polyethylene terephthalate flakes (intrinsic viscosity IV = 0.65) of PET for beverage were introduced from a hopper. The melting temperature of the resin was set at 280 ° C., butadiene oligomer having two hydroxyl groups at one end (butadiene was subjected to ordinary anionic living polymerization, epichlorohydrin was used for termination reaction, and further hydrolyzed to give 2 ends at one end. A butadiene oligomer having two hydroxyl groups was obtained.This time, a butadiene oligomer having a molecular weight of 5000 was prepared.) A liquid obtained by mixing 200 parts by weight of cobalt stearate with 8 parts by weight of a liquid material based on the total amount of the base polymer and the oligomer was obtained. The mixture was introduced into an extruder using an injection machine and melt-kneaded for a residence time of about 5 minutes. After removing unreacted substances and low molecular substances from a vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets are sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, then dried at 150 ° C. for 4 hours, and confirmed to have a moisture content of 0.005 parts by weight or less, and used for subsequent molding. did.

I. Polyester oxygen scavenging resin-I
(PE-I) 88 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.65) obtained by pulverizing PET for beverage were introduced from a hopper. The melting temperature of the resin is set at 280 ° C,
A norbornene oligomer having two hydroxyl groups at one end (a norbornene oligomer was synthesized by the above-described metathesis polymerization and modified to have two hydroxyl groups at one end; a molecular weight of 10,000 was prepared this time).
A butadiene oligomer obtained by mixing 200 parts by weight of cobalt stearate with respect to the total amount of the base polymer and the oligomer to 2 parts by weight is introduced into the extruder (PET different from the PET hopper is introduced from the second supply port after melting. It is preferable to dry blend with PET and introduce from a hopper), and melt-knead for a residence time of about 5 minutes to remove unreacted substances and low molecular substances from a vacuum vent. It was quenched in water to obtain pellets.
The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours.
After drying for an hour, it was confirmed that the water content was not more than 0.005 parts by weight, and used for subsequent molding.

J. Polyester-based oxygen-scavenging resin -J
(PE-J) 96 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.55) obtained by pulverizing PET for beverage were introduced from a hopper. The melting temperature of the resin is set at 280 ° C,
Butadiene oligomer having two carboxyl groups at one end (butadiene is subjected to ordinary anionic living polymerization, dimethyl ester of maleic acid is used for termination reaction, and further hydrolysis is performed to form two carboxyl groups at one end. A butadiene oligomer having a molecular weight of 2,000 was prepared this time.) A liquid injector was prepared by mixing 4 parts by weight of a liquid substance with cobalt stearate at 200 ppm based on the total amount of the base polymer and the oligomer. The mixture was melt-kneaded for a residence time of about 5 minutes to remove unreacted substances and low-molecular-weight substances from a vacuum vent, and the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours.
After drying at 4 ° C. for 4 hours, it was confirmed that the water content was not more than 0.005 parts by weight, and used for subsequent molding.

K. Polyester-based oxygen-scavenging resin -K
(PE-K) A mixture of 99 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.55) obtained by pulverizing PET for beverage and 1 part by weight of glycerin was melt-kneaded at 280 ° C. to obtain a modified PET pellet. Obtained. Then this modified PE
T92 parts by weight were introduced from a hopper. The melting temperature of the resin is set at 280 ° C., butadiene oligomer having one epoxy group at one end (butadiene is subjected to ordinary anionic living polymerization, epichlorohydrin is used for termination reaction, butadiene having an epoxy group at one end) This time, an oligomer having a molecular weight of 3000 was prepared.) Cobalt stearate was added to 8 parts by weight of the liquid material at 200 ppm based on the total amount of the base polymer and the oligomer.
The mixture was introduced into an extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, unreacted substances and low-molecular substances were removed from a vacuum vent, and the molten strand was quenched in water. To obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellet was sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, and then dried at 150 ° C. for 4 hours to obtain a water content of 0.0
After confirming that it was not more than 05 parts by weight, it was used for subsequent molding.

L. Polyester-based oxygen-scavenging resin-L
(PE-L) A mixture of 99 parts by weight of polyethylene terephthalate flakes (intrinsic viscosity IV = 0.40) obtained by pulverizing PET for beverage and 1 part by weight of glycerin was melt-kneaded at 280 ° C. to obtain a modified PET pellet. Obtained. This modified PET was used in the following reactions. 96 parts by weight of the above modified PET was introduced from a hopper. The melting temperature of the resin is set to 280 ° C, butadiene oligomer having one epoxy group at one end (butadiene is subjected to ordinary anionic living polymerization, and epichlorohydrin is used for termination reaction, so that one epoxy A butadiene oligomer having a group was obtained.This time, a product having a molecular weight of 5000 was prepared.) Cobalt stearate was added to 4 parts by weight of a liquid material at 200 ppm based on the total amount of the base polymer and the PO oligomer.
The mixture was introduced into an extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, unreacted substances and low-molecular substances were removed from a vacuum vent, and the molten strand was quenched in water. To obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellet was sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, and then dried at 150 ° C. for 4 hours to obtain a water content of 0.0
After confirming that it was not more than 05 parts by weight, it was used for subsequent molding.

M. Polyester-based oxygen-scavenging resin -M
(PE-M) Polyethylene terephthalate (Nihon Unipet Co., Ltd.)
Made, Unipet RT543, intrinsic viscosity IV = 0.75)
92 parts by weight were introduced from the hopper. The melting temperature of the resin was set to 280 ° C., and cobalt stearate was mixed with 8 parts by weight of a liquid butadiene oligomer having hydroxyl groups at both ends (RHT45, manufactured by Elphatochem Co., Ltd., Mw = 2800) at 200 ppm based on the total amount of the base polymer and the oligomer. The mixture was introduced into an extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, unreacted substances and low-molecular substances were removed from a vacuum vent, and the molten strand was quenched in water.
A pellet was obtained. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets are sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, then dried at 150 ° C. for 4 hours, and confirmed to have a moisture content of 0.005 parts by weight or less, and used for subsequent molding. did.

N. Polyester-based oxygen-scavenging resin -N
(PE-N) Polyethylene terephthalate (Nihon Unipet Co., Ltd.)
Made, Unipet RT543, intrinsic viscosity IV = 0.75)
92 parts by weight were introduced from the hopper. The melting temperature of the resin was set at 280 ° C., butadiene oligomer having two hydroxyl groups at one end (butadiene was subjected to ordinary anionic living polymerization, epichlorohydrin was used for termination reaction, and further hydrolyzed to give 2 ends at one end. A butadiene oligomer having two hydroxyl groups was obtained.This time, a butadiene oligomer having a molecular weight of 5000 was prepared.) A liquid obtained by mixing 200 parts by weight of cobalt stearate with 8 parts by weight of a liquid material based on the total amount of the base polymer and the oligomer was obtained. The mixture was introduced into an extruder using an injection machine and melt-kneaded for a residence time of about 5 minutes. After removing unreacted substances and low molecular substances from a vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were sufficiently crystallized at a temperature of 120 ° C. for 2 hours in a vacuum dryer, and then dried at 150 ° C. for 4 hours.
After confirming that the water content was 0.005 parts by weight or less, it was used for subsequent molding. Details of the oxygen-scavenging resin are shown in Table 1.

[0046]

[Table 1]

(Barrier Resin) [PETI- (PI-)] Isophthalic acid / terephthalic acid: a copolymer obtained by reacting 5 mol% / 95 mol% with an equimolar amount of ethylene glycol. IV = 0.80 [PETI- (PI-)] B-010 (manufactured by Mitsui Chemicals, Inc.): Melt blended PET at a ratio of 1: 4. [PENT8] Nippon Unipet Co., Ltd., Unipet NS663: intrinsic viscosity (IV = 0.72), PEN / PET = 92 mol%
/ 8 mol% [PEN] Nippon Unipet Co., Ltd., Unipet NS763: intrinsic viscosity (IV = 0.70), PEN homopolymer (structural resin) [PET] Nippon Unipet Co., Ltd., Unipet RT5
43: intrinsic viscosity (IV = 0.75)

(Examples 1 to 12) In a multilayer injection molding machine (Nissei ASB-50HT), the temperature of the cylinder 1 (for the outer layer resin) and the temperature of the cylinder 2 (for the intermediate layer resin) were 280 ° C. and the mold temperature was 30 ° C. , The intermediate layer is PE-A
(Polyethylene terephthalate-based oxygen-scavenging resin as a recycled material for PET bottles), and a multilayer preform (weight: 31 g, height: 110 mm, diameter: 25 mm) having PET layers on both sides thereof were obtained. Next, the multilayer preform is subjected to Kr
Using an upp stretch blow molding machine, 100
℃, stretch blow-molded using compressed air, capacity 350ml, average thickness 560μm (outside PET
/ PE-A / PET inside: 245 μm / 70 μm / 24
5 μm) and a bottle sample having a height of 180 mm was obtained. Table 2 shows the bottle capacities and molding conditions of Examples 2 to 12.

(Comparative Examples 1 and 2) The temperature of the cylinder 1 (for the outer layer resin) and the temperature of the cylinder 2 (for the intermediate layer resin) were 280 ° C. and the mold temperature was 30 ° C. using a multilayer injection molding machine (Nissei ASB-50HT). A multilayer preform (weight: 31) in which the intermediate layer is composed of PE-M and both surfaces of which are composed of PET layers.
g, height 110 mm, diameter 25 mm). Then, the multilayer preform was adjusted to a temperature of 100 ° C. using a stretch blow molding machine manufactured by Krupp and stretch blow-molded using compressed air to have a capacity of 500 ml and an average wall thickness of 500 μm (outside PET / MXD6 / PET). Inside: 22
5 μm / 50 μm / 225 μm) and a 200-mm-high bottle sample. Table 2 shows the bottle capacity and molding conditions of Comparative Example 2.

[0050]

[Table 2]

(Evaluation method) 1) Oxygen permeability The oxygen permeability was OX-TRAN2 / 20M manufactured by Mocon.
Measured by L. The measurement condition is 75% inner surface at 23 ° C.
RH, outer surface is 50% RH. 2) Carbon Dioxide Gas Loss 500 ml of carbonated water of gas volume 3 was put into a 500 ml bottle sample. The change over time of the weight was measured, and the retention of carbon dioxide was determined. Storage conditions: temperature 23 ° C / relative humidity 100 inside the bottle
%, Outside 65% 3) Oxygen penetration Ingol with soft package sampling device
d The headspace oxygen content was measured using a polarographic oxygen sensor model IL 307 manufactured by Instruments. Storage conditions: temperature 23 ° C / relative humidity 100 inside the bottle
%, Outside 65% Measured in a carbonated water filled container equivalent to 2) above.

4) Relative transparency to PET Single-layer PE having the same shape as the bottle used in Examples and Comparative Examples
A T bottle was molded and its transparency was compared. Sampling should be performed from the same layer thickness as much as possible, and a wavelength of 400 nm
The light transmittance up to 00 nm was measured. Relative transparency (%) with respect to PET = {[integration of light transmittance of 400 to 700 nm of Example and Comparative Example bottles]} [integral of light transmittance of 400 to 700 nm of single-layer PET bottle]} × 100. Table 3 shows the measurement results of the plastic bottles obtained in Examples 1 to 12 and Comparative Examples 1 and 2.

[0053]

[Table 3]

[0054]

According to the present invention, a PET resin recycling flake, which is generally a PET having a low molecular weight, is provided on both surface layers provided with a structural material resin or a gas barrier resin layer. Beer with extremely high oxygen barrier properties and carbon dioxide gas barrier properties despite the use of recycled PET bottles, provided with an oxygen-scavenging resin layer containing a recycled material and capable of capturing oxygen passing through the resin layer. We were able to provide a bottle.
For this reason, it is extremely excellent as a multi-layer plastic bottle for beer, which does not dislike oxidation from the aspect of quality as a content and requires that carbon dioxide gas does not escape from the container wall. It is a plastic bottle suitable for recycling PET bottles, which is currently a problem due to the use of recycled materials. The plastic bottle of the present invention is a multilayer bottle for beer of a thermoplastic plastic which is inexpensive, lightweight, impact resistant, recyclable, and excellent in gas barrier properties. It can be implemented.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirotaka Tagoshi 1-1-1 Onodai, Midori-ku, Chiba-shi, Chiba Showa Denko KK (72) Inventor Tomohiko Miyauchi 1-13 Shiba-Daimon, Minato-ku, Tokyo No. 9 Showa Denko K.K. (72) Inventor Kensuke Onishi 3-6-5 Iidabashi, Chiyoda-ku, Tokyo Showa Aluminum Can Co., Ltd. F-term (reference) 3E033 BA13 BA14 BA17 BA18 BA19 BA21 BB01 BB04 BB08 CA03 CA16 CA18 CA20 GA02 4F100 AA17A AA17H AH02H AH08H AK01B AK01C AK01D AK01E AK03A AK29A AK29K AK41A AK42A AK42B AK42C AK42J AK47B AK47C AK69B AK69C AL01A AL01B AL01C AL02 AL05A AL05B AL05C BA03 BA04 BA05 BA06 BA10B BA10C BA10D BA10E BA13 CA07 CA09A CA30A DA01 GB16 GB23 JA07A JD02 JD02B JD02C JD03 JD09 JD14A JK10 JL03 JL08A JL08H JL16A JN01 YY00 YY00A YY00B YY00C

Claims (14)

[Claims] 1. A bottle having a content of 0.05 to 4 liters and a total thickness of a bottle body of 0.1 to 2 mm and using a polyester resin for a beverage as an intermediate layer (hereinafter referred to as “P”).
"ET bottle". A) a multi-layer plastic bottle comprising at least one layer of an oxygen-scavenging resin layer using a recycled material of (3), two or more resins composed of a barrier resin or a structural resin as a surface material, and three or more layers, Fill and seal beer, 18 at 4-25 ° C
A beer plastic bottle in which the amount of oxygen entering the bottle is 1 ppm or less with respect to the beer weight when stored in the atmosphere for 0 days. 2. The plastic bottle for beer according to claim 1, wherein the structural material resin is a resin that is a copolymer or a blend of polyethylene terephthalate at least 50% of which is used. 3. When the beer is filled and sealed in a plastic bottle for beer and stored in the atmosphere at 4 to 25 ° C. for 180 days, the escape amount of carbon dioxide gas decreases by less than 10 w% as the carbon dioxide gas filling amount decreases. The plastic bottle for beer according to claim 1, which is: 4. A terephthalic acid in a saponified product of ethylene-vinyl acetate copolymer (EVOH), polymethaxylylenediamine adipate (MXD6), and polyethylene terephthalate whose surface material has a carbon dioxide gas barrier property.
Mol% or less of a polyester (P
ETI) resin or polyethylene naphthalate (PE
The plastic bottle for beer according to claim 1, which is any one of N). 5. The beer according to claim 1, wherein the oxygen-scavenging resin layer is a polyethylene terephthalate-based oxygen-scavenging resin using a recycled PET bottle for beverage (IV value, 0.3 to 0.8). For plastic bottles. 6. At least one of the intermediate layers is composed of a layer containing a polyethylene terephthalate-based oxygen-scavenging resin using a recycled material, wherein the oxygen-scavenging resin and a polyethylene terephthalate-based polymer segment constituting a main part are small. The plastic bottle for beer according to claim 1, comprising an olefin oligomer segment constituting a part, and further comprising a catalytic amount of a transition metal compound. 7. The plastic bottle for beer according to claim 1, wherein the oxygen-scavenging resin is a polyethylene terephthalate (co) polymer having an olefin oligomer segment having a carbon-carbon unsaturated bond in the molecule. 8. The polyethylene terephthalate-based oxygen-scavenging resin has a molecular weight of 10 to 15% by weight.
The resin composition comprising an olefin oligomer segment of 00 to 10000 and a polyethylene terephthalate segment of 99.5 w% to 85 w%, and the copolymer is a resin composition containing 50 to 500 ppm of a transition metal compound which promotes oxidation. 7. The plastic bottle for beer according to 7. 9. The plastic bottle for beer according to claim 7, wherein a photo-oxidation accelerator having a sensitizing effect on ultraviolet light and / or visible light is added to the oxygen-scavenging resin layer. 10. The plastic bottle for beer according to claim 1, wherein the olefin oligomer segment in the oxygen-scavenging resin is an oligomer of butadiene, norbornene, dicyclopentadiene and isoprene. 11. The oxygen-scavenging resin in which the olefin oligomer segment having a carbon-carbon unsaturated bond in the oxygen-scavenging resin is bonded as a main chain of a main polymer segment or as a branched pendant. The plastic bottle for beer according to any one of the above. 12. The beer plastic bottle according to claim 1, wherein at least one layer other than the innermost layer of the multilayer plastic bottle contains a UV-absorbing substance and / or a UV-shielding substance. 13. At least 70% of the transparency of a single-layer polyester polymer plastic bottle of the same thickness.
The plastic bottle for beer according to any one of claims 1 to 12, which has transparency. 14. A multilayer plastic bottle, wherein the innermost layer includes a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer or a structural material resin layer / a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin. The plastic bottle for beer according to claim 1, which has a configuration of / gas barrier resin layer / structural material resin layer.