JP2001048182A - Plastic bottle for beer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plastic beer bottle which as quite high oxygen barrier property and carbon dioxide gas barrier property catching oxygen passing through a resin layer by providing, on both surface layers, a structural resin layer or a gas barrier resin layer, and furthermore providing as an intermediate layer of the same an oxygen uptaking resin layer. SOLUTION: This relates to a multi layer plastic bottle which is made of three or more layers and two or more types of resin made of barrier resin and/or structural resin as a surface material, whose internal capacity is between 0.05 and 4 litters, the total thickness of whose body part is between 0.1 and 2 mm, and which has at least one layer including oxygen uptake resin as an intermediate layer. This oxygen uptake resin included in an oxygen uptaking resin layer is a copolymer combining polyolefin oligomer segment having carbon dioxide-carbon dioxide unsaturated bond in its main chain or ramification containing a transition-metal compound in a catalytic amount. When the bottle is stored for 180 days in the atmosphere between 4 deg.C and 25 deg.C closed airtight filled with beer, the amount of oxygen penetrated into the bottle is 1 ppm or less relative to beer wt.%.

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 requires oxidation-resistant contents and requires no escape of carbon dioxide gas from the container wall. The present invention relates to a multi-layered thermoplastic beer bottle having excellent impact resistance, recyclability, and gas barrier properties, and a method for producing the same.

[0002]

2. Description of the Related Art Beer has been popular in Europe since ancient times as a beverage for people, and in recent years has been consumed in large quantities as alcoholic beverages for common people worldwide. In recent years, beer has been brewed in large quantities in factories, filled in small containers, transported to consuming areas, stored, and sold. Such beer not only requires retention of aroma during transportation and storage, but also is easily oxidizable and contains carbon dioxide gas. Was used.

[0003] Aluminum cans have the advantages of being lightweight, being excellent in recyclability, gas barrier properties, impact resistance, light-shielding properties, and being beautiful, and having an easily oxidizable or non-oxidizable content. It is considered to be a very ideal material for packaging materials, and recently, its use has been increasing to occupy the mainstream as a container for beer. On the other hand, raw materials are expensive, manufacturing equipment such as aluminum can manufacturing equipment, contents filling equipment, etc. requires large, high-performance equipment, and requires a very large investment amount,
It can only deal with small varieties and mass production.
In addition, aluminum requires corrosion treatment, the product price is high, it is difficult to increase the size of the container, and the visibility of the contents in the food market is one of the major product concepts. Is mainly used for small containers of 1 liter or less that cannot be resealed.

[0004] Glass bottles that have been used in the largest quantities in the past have excellent recyclability, gas barrier properties, corrosion resistance, and resealability, can be used in a wide variety of small-quantity production, and are relatively inexpensive to produce. Although there are advantages that can be achieved, it has the serious disadvantage that the product weight is heavy and the impact resistance is extremely weak compared to aluminum cans and plastic bottles, and the market is gradually replacing aluminum cans etc. Although it seems that measures such as thinning the wall of the bottle to reduce its weight are being taken as a countermeasure, its effect is unclear because there is a limit.

[0005] Plastic containers are transparent and lightweight,
It is an excellent packaging material that has excellent impact resistance, corrosion resistance, low product price, small capital investment, and can be used for containers of high-mix low-volume production.
Glass bottles have no problem at all and have low gas barrier properties.They dislike oxidation in terms of quality, and contents that dislike escape of carbon dioxide gas.For example, as a container for beer, oxygen gas permeability, carbon dioxide gas permeability, etc. It has a serious drawback of low gas barrier properties. As a measure for improving the gas barrier properties of such a plastic container, a number of multilayer plastic bottles having improved gas barrier properties by laminating a gas barrier resin layer together with a structural material resin layer have been proposed.

[0006] Conventional multi-layer bottle manufacturing methods include saponification of a thermoplastic (structural material resin) and an ethylene-vinyl acetate copolymer (ethylene-vinyl alcohol copolymer; hereinafter referred to as "EVOH") and polyamide. A gas barrier resin such as polyvinylidene chloride and polyacrylonitrile is molded into a parison by multi-layer extrusion using the gas barrier resin as an intermediate layer, and a direct blow molding method for blow molding the same, after molding a plastic bottle, A method of applying a barrier resin such as EVOH to the surface (Japanese Patent Application Laid-Open No. 60-251027). When the barrier resin absorbs moisture, the gas barrier property is reduced. To prevent this, the surface of the barrier resin is coated with a hydrophobic resin. To cover a bottle with a shrinkable film covered with a resin (Japanese Patent Publication No. 62-7060) There are number of proposals such as JP), it is expected as a method of stretch-blow multilayer bottle even thinner can maintain the high strength of the product is the most expansive.

[0007] Containers such as beer that only need to have a shelf life of a relatively short time after filling are usually 20 ° C and relative humidity even if they do not have perfect gas barrier properties like aluminum cans and glass bottles. Oxygen gas permeability at 65% is ² cc / m ² · day · atm or less, CO 2
_{2 If the} gas permeability is less than 20 cc / m ² · day · atm, 4 ~ 25 ° C required for beer containers
And the amount of infiltration of oxygen is 1 ppm or less based on the weight of the content beer after storage for 300 days, and the amount of carbon dioxide gas escaped after storage for 180 days is 10
% Can be secured. Therefore, it is necessary to develop a low-cost multi-layer plastic bottle in which a gas barrier resin layer satisfying the above criteria is formed.

[0008]

According to the present invention, a structural material resin layer or a gas barrier resin layer is provided on both surface layers, and an oxygen-scavenging resin layer is provided on an intermediate layer between these layers. An object of the present invention is to provide a plastic beer bottle capable of capturing incoming oxygen and having extremely high oxygen barrier properties and carbon dioxide gas barrier properties.

[0009]

According to the present invention, there is provided [1] at least an oxygen-scavenging resin layer as an intermediate layer having a content of 0.05 to 4 liters and a total thickness of a bottle body of 0.1 to 2 mm. 2 or more kinds of resins comprising a barrier resin and / or a structural material resin as a surface material including one layer and 3
A multi-layer plastic bottle comprising at least one layer, wherein beer is filled and sealed, and when 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 the beer. A plastic bottle for beer, [2] The plastic bottle for beer according to [1], wherein the structural material resin is a resin whose copolymer is a copolymer or blend of 50% or more of polyethylene terephthalate, [3] Fill a beer plastic bottle with beer and seal it.
The plastic bottle for beer according to the above [1], wherein the amount of carbon dioxide escaping when stored in the atmosphere for 0 days is less than 10% as the carbon dioxide gas filling amount is reduced.

[4] A saponified ethylene-vinyl acetate copolymer whose surface material has a carbon dioxide gas barrier property (EVO
H), polymethaxylylenediamine adipate (MXD
6) The plastic bottle for beer according to the above [1], which is one of a polyester (PETI) resin in which 30% by mole or less of terephthalic acid in polyethylene terephthalate is substituted with isophthalic acid or polyethylene naphthalate (PEN). [5] At least one of the intermediate layers comprises a layer containing an oxygen-scavenging resin, which contains a catalytic amount of a transition metal compound and has a carbon-carbon unsaturated bond in its main chain or branch. The plastic bottle for beer according to the above [1], which is a (co) polymer having a polyolefin oligomer segment bonded thereto,
[6] A polyester-based, polyamide-based, polyolefin-based or vinyl-based (co) polymer in which the oxygen-scavenging resin is bonded to a polyolefin oligomer segment having a carbon-carbon unsaturated bond in the molecule (these (co) polymers). The coalescence is collectively referred to as the "main polymer segment.")
The plastic bottle for beer according to the above [1], which is

[7] The oxygen-scavenging resin contains 50 to 500 ppm of a transition metal compound as a metal atom, 1 to 15% by weight of a polyolefin oligomer segment having a carbon-carbon unsaturated bond, and 85 to 99% by weight of a main polymer. The plastic bottle for beer according to the above [1] or [7], comprising a segment, [8]
The plastic bottle for beer according to the above [6] or [7], wherein a photooxidation accelerator having a sensitizing effect on ultraviolet light and / or visible light is added to the oxygen-scavenging resin layer, [9] Oxygen-scavenging property The polyolefin oligomer segment in the resin contains any of polymerized units of butadiene, norbornene, dicyclopentadiene, and isoprene, and has a molecular weight of 1,000 to 10,000.
[7] to [9], which are oligomer segments of
A plastic bottle for beer according to any of the above,

[10] The above-mentioned [6], wherein the polyolefin oligomer segment having a carbon-carbon unsaturated bond in the oxygen-scavenging resin is an oxygen-scavenging resin bonded as a main chain of the main polymer segment or as a branched pendant. Or the plastic bottle for beer according to any one of [9] to [11], 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. [1] The plastic bottle for beer according to [1],
2] The beer plastic bottle according to any one of the above [1] to [11], which has a transparency of at least 70% as compared with the transparency of a single-layer polyester polymer plastic bottle having the same thickness.

[13] The multi-layer plastic bottle has a gas-barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas-barrier resin layer, a structural resin / a gas-barrier resin layer containing an oxygen-scavenging resin / a structural material from the innermost layer. The plastic bottle for beer according to the above [1], which has a configuration of a resin or a structural material resin layer / a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer / a structural material resin layer, and [14]. A multi-layer plastic bottle parison composed of a structure material resin or gas barrier resin layer forming both surface layers and two or more resins including at least one oxygen-scavenging resin layer as an intermediate layer and three or more layers is subjected to multi-layer injection. Developed a method for molding plastic bottles for beer, characterized by molding and molding by a stretch blow method To achieve the above object by Rukoto.

[0014]

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 meet this demand, a gas barrier resin is used as a surface material, and an intermediate layer has one oxygen scavenging resin layer as a whole. It is necessary to form a multilayer plastic bottle having a three-layer structure of a gas barrier resin and an oxygen-scavenging resin. The beer is filled and sealed in the plastic bottle, and when stored at room temperature for 180 days, the amount of oxygen that enters the bottle becomes 1 ppm or less with respect to the weight of the internal beer, and at room temperature, 18 ppm.
By adjusting the type and thickness of the gas barrier resin so that the escape amount of carbon dioxide gas passing through the bottle wall from the inside of the beer bottle in 0 days is less than 10% as measured as a decrease in the filling amount of carbon dioxide gas, Imparts properties. The oxygen-scavenging resin used as the intermediate layer is extremely effective in trapping oxygen permeating the gas-barrier resin layer and preventing entry into the inside of the bottle even when the oxygen-barrier property of the gas-barrier resin is insufficient. It is effective and can surely prevent unexpected defects of the gas barrier resin.

In particular, in a small container, the rigidity of the beer bottle is sufficient when the required minimum barrier property is achieved only with the gas barrier resin layer, but in a large beer bottle, the minimum barrier property is achieved. The stiffness of the bottle alone may be insufficient, and in such a case, the use of a gas barrier resin and a structural material resin which are expensive by laminating a structural material resin such as polyethylene terephthalate on the surface of the gas barrier resin. It is preferred to reduce the amount. The relationship between the thickness of each resin layer is
The thickness depends on the required gas barrier properties, but three layers,
In the case of five layers, the resin layer containing the oxygen-scavenging resin as the intermediate layer is 2 to 20% of the total thickness, preferably 5 to 20%.
The structural material resin layer, the gas barrier resin layer, and the resin layer containing the oxygen-scavenging resin in the case of 15%, and 5 layers are the structural material resin layer (25 to 40%) / gas barrier resin layer (5 to 20%).
/ Resin layer containing oxygen-scavenging resin (2 to 20%) / gas barrier resin layer (5 to 20%) / structural material resin layer (20 to 4%)
0%).

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.

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. As such a gas barrier resin, EVOH is the most suitable resin in view of the balance between performance and cost.
Can be mentioned. For example, if the ethylene content is 20
Ethylene of up to 60 mol%, in particular 25 to 50 mol%
Saponified copolymers obtained by saponifying a vinyl acetate copolymer so that the degree of saponification is 96 mol% or more, particularly 99 mol% or more can be mentioned. This EVOH is
It should have a molecular weight sufficient to form a film and is generally at least 0.01 dl / g, especially at least 0.05 dl / g, measured at 30 ° C. in a mixed solvent of phenol: water at a weight ratio of 85:15. It is preferable to have a viscosity of

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 such as nylon 6, nylon 66, nylon 6-66 copolymer, nylon 6,10, nylon 11, nylon 1
2. Aliphatic polyamides such as nylon 13 and polymethacrylicylene adipamide (hereinafter referred to as MXD6).
And other aromatic polyamides. 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. It is desirably at least 1, especially at least 1.5. 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.

It is necessary that at least one of the intermediate layers contains an oxygen-scavenging resin. This may be an intermediate layer of the oxygen-scavenging resin alone or may be diluted with another resin, for example, a resin compatible with the oxygen-scavenging 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. As the dilution ratio, the oxygen-scavenging resin can be blended at least 5% by weight, preferably 20% or more.

The oxygen-scavenging resin in the present invention means a polyester, polyamide, polyolefin or vinyl polymer having a polyolefin oligomer segment having a carbon-carbon unsaturated bond in the molecule. Examples of the polyester polymer include PET,
(Co) polycondensates of alkylene glycols such as PBT and PEN with aromatic dibasic acids, polycarbonate polymers of carbonic acid obtained by polycondensation reaction of bisphenol with phosgene and dihydric phenols, dibasic acids and dibasic acids Examples include polyarylate, which is a polycondensate of a phenol. Examples of the polyamide-based polymer include aliphatic polyamides such as nylon 6, nylon 66, and nylon 12, and aromatic polyamides such as polyxylylenediamine adipamide (MXD6).

In order to introduce a polyolefin oligomer segment having a carbon-carbon unsaturated bond into such a polycondensate, for example, an oligomer of a polybutadiene derivative having a hydroxyl group, a carboxyl group or an amino group at both ends is converted into a divalent glycol, Copolycondensate instead of a part of dibasic acid, diamine, etc. to bond a polyolefin oligomer segment in the main chain. Alternatively, several methods are conceivable for introducing an olefin oligomer segment having a carbon-carbon unsaturated bond in a pendant manner with respect to the polymer main chain. One of them is that, when synthesizing a polymer, for example, an oligomer of a butadiene derivative having two hydroxyl groups, carboxyl groups or amino groups at one end is copolymerized by substituting a part of divalent glycol, dibasic acid, diamine or the like. Method, or other methods such as glycols, dibasic acids,
A functional group is introduced into the main chain of the polycondensate by substituting a part of a diamine or the like with a polyvalent compound having three or more functional groups in a molecule, and at least one functional group reactive with the functional group is added to the polycondensate. The polyolefin oligomers having other functional groups and having a carbon-carbon unsaturated bond may be reacted to bond the polyolefin oligomer segments in a pendant manner without entering the main chain. For example, in PET, a hydroxyl group is added to the polyester main chain by substituting a part of ethylene glycol with an equimolar glycerin, and a carboxyl group, a carboxylic anhydride group reactive with the hydroxyl group,
It can be obtained by reacting a polyolefin oligomer into which an epoxy group, an isocyanate group or the like has been introduced. Further, in PET or the like, a polyolefin oligomer segment having two hydroxyl groups introduced at one end is referred to as 2
It can be obtained by co-condensing instead of a monovalent glycol. When having such a pendant-type polyolefin oligomer segment, even if the oxygen-scavenging resin captures oxygen, only the branch is cut and the main chain is not cut, and the performance deterioration as a polyester copolymer is small. There are features. Further, a polyester or polyamide may be reacted with a polyolefin oligomer having two functional groups at one end, and a transesterification reaction or a transamidation reaction may be performed.
Many reactions such as transesterification or transamidation reaction by reacting a divalent carboxylic acid, alcohol or amine to introduce a functional group and then introducing a carbon-carbon unsaturated bond olefin oligomer segment to the functional group Can be used.

In the case of polyolefin polymers such as polyethylene and polypropylene, a functional group is introduced by grafting an unsaturated carboxylic acid such as acrylic acid or maleic anhydride to the polymer, and the functional group has reactivity. A polyolefin oligomer having at least one functional group and having a carbon-carbon unsaturated bond is reacted to introduce a polyolefin oligomer segment in a pendant form, or the polymer itself has a functional group such as an ethylene-acrylic acid copolymer. Similarly, there is a method of introducing a polyolefin oligomer segment using a polymer having In a polystyrene or a polyvinyl polymer such as polymethyl methacrylate, a reactive functional group such as glycidyl methacrylate is introduced at the time of polymerization to introduce an olefin oligomer segment or a styrene-butadiene block having transparency. It may have an olefin oligomer segment in the molecule, such as a copolymer or an ABS resin. Further, in a vinyl polymer having a functional group itself, such as EVOH and a vinyl copolymer having (meth) acrylic acid as one component, a polyolefin oligomer segment is introduced in the same manner as the polyolefin polymer. be able to. In addition, the polymer itself may be transparent and have a polyolefin oligomer segment in the molecule, such as a transparent grade butadiene-styrene copolymer.

As the oxygen-scavenging resin, oxygen is trapped in a polyolefin oligomer segment having a carbon-carbon unsaturated bond active to oxygen. At this time, α-activated by the carbon-carbon unsaturated bond is activated. 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 a polyolefin oligomer segment in the main chain undergoes main chain cleavage. On the other hand, a polymer in which a polyolefin oligomer segment is bonded in a pendant form is only a problem of cleavage of the pendant olefin oligomer segment.
Scavenging oxygen will not be affected at all.
When only physical properties are considered, a pendant-bound oxygen-scavenging resin is preferred.

As the polyolefin oligomer to be introduced, a bond having a carbon-carbon unsaturated bond and a carbon having hydrogen at the α-position in the oligomer molecule [allyl bond = (— CH ＝ CH—CHR—), R is a hydrogen atom,
And a lower alkyl group. ] 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, a polyolefin oligomer segment containing an isoprene segment has high oxygen scavenging activity. The molecular weight of this polyolefin oligomer segment depends on whether the oxygen-scavenging resin requires transparency or is opaque, the type of the main constituent compound of the oxygen-scavenging resin, introduction into the main chain, or introduction 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 1000 to 1000.
About 0 can be used.

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. The transition metal compound and the photo-oxidation accelerator are described in detail in JP-A-5-194949. Other methods of activating the oxygen-scavenging properties of the oxygen-scavenging resin include irradiation with radiation such as electron beams, γ-rays, and X-rays, ultrasonic waves for imparting α-hydrogen abstraction energy, high-frequency waves, heat (high The application of energy from the outside such as temperature) is also effective, and the combination thereof can shorten the induction period and increase the oxygen capture rate and oxygen capture rate. Such an oxygen-scavenging resin is
The resin may be used alone, or may be diluted with another resin to reduce the cost. The type of resin to be diluted is preferably a polyester resin such as PET if it is a polyester-based oxygen-scavenging resin, and the same type of resin such as nylon 6 or nylon 66 is highly compatible if it is a polyamide-based oxygen-scavenging resin, It is preferable because the resin layer is likely to be transparent. In this case, the blending amount of the oxygen-scavenging resin is related to the thickness of the oxygen-scavenging resin layer, but the oxygen-scavenging resin concentration is at least 5%, preferably 2%.
Those containing 0% or more can be used.

The polycondensation-type oxygen-scavenging polymer of the present invention has a high possibility that the polycondensation-type oxygen-scavenging polymer is also a transparent polymer when the main-chain polycondensation-type linear polymer is transparent. When the oxygen-scavenging resin is used, the molding processability is substantially the same as that of the polycondensation-type linear polymer, unlike the resin blended with the reduced iron-based deoxidizer. In particular, a reduced iron-based oxygen scavenger has a humidity dependency and cannot exhibit its activity without humidity, but has a characteristic that it can effectively deoxidize even in a dry state without humidity. In the case of a resin having a small oxygen permeability of the polycondensation-based linear polymer itself serving as the base material, the amount of oxygen permeating through the polycondensation-type oxygen-scavenging polymer layer is extremely small, so that the amount dissolved in the polymer is also small. Because the dissolved oxygen is completely trapped in the polymer layer, the performance as a gas barrier resin is stronger than the apparent oxygen trapping polymer. Among them, it was found that, for example, in MXD6 having a low oxygen permeability, the gas barrier property was remarkably improved so that the oxygen permeability could not be detected (although the oxygen scavenging property was slightly recognized). 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, so that the oxygen-scavenging resin layer further functions as a gas-barrier resin layer. 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 also expensive, and as a structural material resin is inadequate in physical properties compared to PET etc.,
When the oxygen-scavenging resin also has a gas barrier function, it is effective to use a structural material resin instead of the gas barrier resin layer.

The plastic bottle according to the present invention has a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer, and a structural material resin layer / an intermediate layer containing an oxygen-scavenging resin layer having a gas barrier function. / Structure of structural material resin layer or structural material resin layer / gas barrier resin layer /
A bottle parison comprising a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer / a structural material resin layer 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 polyester-based oxygen-scavenging resin) 1) Block copolymer [Polyester-based oxygen-scavenging resin-(PE-)] Twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (TEM37BS, 3
7 mmφ, L / D = 45) to produce an oxygen-scavenging resin. 96 parts by weight of PET (manufactured by Nippon Unipet Co., Ltd., Unipet RT543, intrinsic viscosity IV = 0.75) were introduced from a hopper. The melting temperature of the resin was set at 280 ° C., and 200 ppm of cobalt stearate, based on the total amount of PET and the hydroxyl group-containing butadiene oligomer at 4 parts by weight, was added to 4 parts by weight of a liquid butadiene oligomer having hydroxyl groups at both ends (RHT45 manufactured by Elphatochem Co., Ltd.). The mixture was introduced into an extruder using a liquid injector, melt-kneaded for a residence time of about 5 minutes, and transesterified. Then, unreacted substances and low molecular substances were removed from a vacuum vent. This was extruded and the molten strand was quenched in water to form 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.
For 4 hours, and it was confirmed that the water content was 0.005 parts by weight or less, and was used for subsequent molding.

[Polyester-based oxygen-scavenging resin- (P
E-)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
37BS, 37 mmφ, L / D = 45) was used to produce an oxygen-scavenging resin. PETN8 (manufactured by Nippon Unipet Co., Ltd., Unipet NS553, Ultimate Mucin IV = 0.
82) was introduced through a hopper at 92 parts by weight. The melting temperature of the resin was set at 260 ° C., and a hydroxyl-butadiene oligomer at both ends (RLM20, manufactured by Elphachem Chem, Mw = 12)
30) 200 parts by weight of cobalt stearate is added to 8 parts by weight of the liquid material, based on the total amount of PET and butadiene oligomer.
The mixture containing pm was introduced into the extruder using a liquid injector, and was melt-kneaded for a residence time of about 5 minutes, and transesterified. Then, unreacted substances and low-molecular substances were removed from the vacuum vent. Next, the molten strand was quenched in water to form 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.

[Polyester-based oxygen-scavenging resin- (P
E-)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
(37 BS, 37 mmφ, L / D = 45) was used to prepare an oxygen-scavenging resin. PETN8 (manufactured by Nippon Unipet Co., Ltd., Unipet NS553, intrinsic viscosity IV = 0.
82) 88 parts by weight were introduced from the hopper. The melting temperature of the resin is set to 260 ° C., and the hydroxyl group at both ends is an octadiene oligomer (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 ppm of cobalt stearate and 200 ppm of benzophenone based on the total amount of PET and octadiene oligomer in parts by weight was introduced into the extruder using a liquid injector, and the mixture was melt-kneaded for about 5 minutes and transesterified. Unreacted substances and low molecular substances were removed from the vacuum vent. Next, 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.

2) Graft copolymer [Polyester-based oxygen-scavenging resin- (PE-)] Coaxial twin-screw extruder (TEM37BS, 3) manufactured by Toshiba Machine Co., Ltd.
7 mmφ, L / D = 45) to produce an oxygen-scavenging resin. A solution obtained by adding 1 part by weight of glycerin to 99 parts by weight of PETN8 (Unipet NS553, manufactured by Nippon Unipet Co., Ltd., intrinsic viscosity IV = 0.82) was added to 265 parts.
The mixture was kneaded at a temperature of 100 ° C. to obtain modified PET pellets.

Next, 96 parts by weight of the modified PET were introduced from a hopper. Set the melting temperature of the resin to 265 ° C,
One-terminal epoxy-group butadiene oligomer (One-terminal epoxy-group butadiene oligomer was obtained by subjecting butadiene to ordinary anionic living polymerization and using shrimp chlorohydrin for termination reaction. This time, a molecular weight of 5,000 was prepared.) A mixture of 200 ppm of cobalt stearate with respect to the total amount of the modified PET and the one-terminal epoxy group butadiene oligomer in 4 parts by weight of the liquid material was introduced into the extruder using a liquid injector, and the residence time was about 5 minutes. The reaction was performed by melt-kneading, and unreacted substances and low-molecular substances were removed from the vacuum vent, and 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. Further, the pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours, dried at 150 ° C. for 4 hours, and confirmed to have a water content of 0.005 parts by weight or less. Used for

[Polyester-based oxygen-scavenging resin- <P
E-)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
(37 BS, 37 mmφ, L / D = 45) was used to prepare an oxygen-scavenging street fat. PENT8 copolymer (Nippon Unipet Co., Ltd., Unipet NS663, intrinsic viscosity IV
= 0.72) A mixture of 99 parts by weight and 1 part by weight of glycerin was melt-kneaded at 280 ° C to obtain modified PEN pellets. This modified PEN was used in the following reactions.

The above-mentioned modified PEN was introduced from a 96 parts by weight hopper. The melting temperature of the resin was set at 280 ° C., and a one-terminal epoxy-group butadiene oligomer (butadiene was subjected to ordinary anionic living polymerization, and epichlorohydrin was used for termination reaction to obtain a one-terminal epoxy-group butadiene oligomer. A mixture prepared by mixing 200 parts by weight of cobalt stearate with 4 parts by weight of the liquid material, based on the total amount of the modified PEN and the one-terminal epoxy group butadiene oligomer, was introduced into the extruder using a liquid injector. Then, the mixture was melt-kneaded for a residence time of about 5 minutes to carry out a reaction. After removing the unreacted products 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, after the pellets were sufficiently crystallized in a vacuum dryer at a temperature of 120 ° C. for 2 hours,
After drying at 150 ° C. for 4 hours, it was confirmed that the water content was 0.005 parts by weight or less, and used for the following molding.

[Polyester-based oxygen-scavenging resin- (P
E-)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
37BS, 37 mmφ, L / D = 45) was used to produce an oxygen-scavenging resin. PET (Nihon Unipet Co., Ltd.)
Made, Unipet RT543, intrinsic viscosity IV = 0.75)
A mixture of 99 parts by weight and 1 part by weight of glycerin was melt-kneaded at 280 ° C. to obtain a modified PET pellet. This modified PET was used in the following reactions.

96 parts by weight of this modified PET was introduced from a hopper. The melting temperature of the resin was set at 280 ° C., and a one-terminal epoxy-group butadiene oligomer (butadiene was subjected to ordinary anionic living polymerization, and epichlorohydrin was used for termination reaction to obtain a one-terminal epoxy-group butadiene oligomer. In this case, the molecular weight was 10,000. A butadiene oligomer obtained by mixing 200 parts by weight of the modified PET and the one-terminal epoxy-group butadiene oligomer with 4 parts by weight of the modified PET and the butadiene oligomer introduced into the extruder was introduced into the extruder. P
The ET is preferably introduced from the second supply port after melting, but may be dry-blended with the modified PET and introduced from a hopper, and then melt-kneaded for a residence time of about 5 minutes,
After removing the 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. The pellets are further dried in a vacuum dryer at a temperature of 120.
After sufficiently crystallizing at 2 ° C. for 2 hours, it was 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 the subsequent molding.

[Polyester-based oxygen-scavenging resin (P
E-)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
(37 BS, 37 mmφ, L / D = 45) was used to prepare an oxygen-scavenging resin. PETN8 (manufactured by Nippon Unipet Co., Ltd., Unipet NS553, intrinsic viscosity IV = 0.
82) 92 parts by weight were introduced from the hopper. The temperature of the resin was set at 265 ° 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 hydroxyl groups at one end. A butadiene oligomer having a molecular weight of 5000 was prepared.) A mixture of 200 parts by weight of cobalt stearate based on the total amount of PENT8 and a butadiene oligomer having a hydroxyl group at one end was mixed with 8 parts by weight of a liquid material. Using a liquid injector, 8 parts by weight are introduced into the extruder, 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 rapidly cooled in water. Cut 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.

[Polyester-based oxygen-scavenging resin (P
E-1)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM
(37 BS, 37 mmφ, L / D = 45) was used to prepare an oxygen-scavenging resin. PENT8 (Nihon Unipet Co., Ltd., Unipet NS663, intrinsic viscosity IV = 0.
72) 92 parts by weight were introduced from the hopper. The temperature of the resin is set at 280 ° C., butadiene oligomer having two hydroxyl groups at one end (butadiene is subjected to ordinary anionic living polymerization, epichlorohydrin is used for termination reaction, and further hydrolysis is carried out. A butadiene oligomer having two is obtained. This time, a butadiene oligomer having a molecular weight of 5,000 was prepared.) 200 parts by weight of a liquid material was mixed with 200 ppm of cobalt stearate based on the total amount of the above-mentioned PENT8 and one-terminal hydroxyl group butadiene oligomer. The melted 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.
Cut 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 and then dried and sooted at 150 ° C. for 4 hours to obtain a water content of 0.0,0.
After confirming that it was not more than 05 parts by weight, it was used for subsequent molding.

(Production of polyamide-based oxygen-scavenging resin) 1) Block copolymer [Polyamide-based oxygen-scavenging resin- (PA-)] Coaxial twin-screw extruder (TEM37BS, 37) manufactured by Toshiba Machine Co., Ltd.
mmφ, L / D = 45) to produce an oxygen-scavenging resin. Nylon MXD6 (Mitsubishi Gas Chemical Co., Ltd., M
88 parts by weight of X nylon 6007, relative viscosity 2.7) were introduced from a hopper. The melting temperature of the resin is set at 280 ° C, and the carboxyl group at the both ends is a norbornene oligomer (Norbornene is used to perform normal metathesis polymerization to synthesize a norbornene oligomer, and the carboxyl ester group at both ends is converted to a carboxyl group. This time, the molecular weight is 2,000.) In 12 parts by weight of the liquid material, 200 ppm of cobalt stearate based on the total of MXD6 and the oligomer at the carboxyl group at both ends is added.
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. The pellets are further dried in a vacuum dryer at a temperature of 80 ° C. for 6 hours,
It was confirmed that the water content was 0.05 parts by weight or less. MXD6 nylon copolymer 50 produced as described above during molding
A dry blend of 50 parts by weight of MX Nylon 6007 and 50 parts by weight was used.

[Polyamide-based oxygen-scavenging resin- (PA
−)] Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM3
7BS, 37 mmφ, L / D = 45) was used to produce an oxygen-scavenging resin. 96 parts by weight of PA6 (manufactured by Mitsubishi Chemical Corporation, Novamid 1020, relative viscosity 3.4) was introduced from a hopper. The melting temperature of the resin was set to about 260 ° C., and a dicyclopentadiene oligomer having amino groups at both terminals (a dicyclopentadiene oligomer was synthesized by the above-described metathesis polymerization, and both terminal groups were substituted with carboxyl groups was used. Molecular weight: 1000) A mixture of 4 parts by weight of liquid material and 200 ppm of cobalt stearate based on the total amount of PA6 and both terminal aminolidicyclopentadiene oligomers 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. The pellets are further dried in a vacuum dryer at a temperature of 80 ° C. for 6 hours.
After drying for a time, it was confirmed that the water content was not more than 0.05 part by weight, and it was used for the subsequent molding.

2) Graft copolymer [Polyamide-based oxygen-scavenging resin- (PA-)] Co-directional two-wheel extruder (TEM37BS, 37) manufactured by Toshiba Machine Co., Ltd.
mmφ, L / D = 45) to produce an oxygen-scavenging resin. Nylon MXD6 (Mitsubishi Gas Chemical Co., Ltd., M
X nylon 6007, relative viscosity 2.7) 99 parts by weight,
One part by weight of alkylenetriamine was added to
The mixture was melt-kneaded at 80 ° C. to obtain a modified MXD6 pellet. This modified MXD6 was used in the following reactions.

The above-mentioned modified MXD6 was introduced from a 92 parts by weight hopper. The melting temperature of the resin was set at 280 ° C., and a one-terminal epoxy-group butadiene oligomer (butadiene was subjected to ordinary anionic living polymerization, and epichlorohydrin was used for termination reaction to obtain a one-terminal epoxy-group butadiene oligomer. A mixture prepared by mixing 200 parts by weight of MXD6 and cobalt stearate with respect to the total amount of MXD6 and one-terminal epoxy group butadiene oligomer in 8 parts by weight of the liquid was introduced into the extruder using a liquid injector. Then, the mixture was melt-kneaded for a residence time of about 5 minutes to remove unreacted substances and low-molecular substances from the vacuum vent, and then quenched the molten strand in water to obtain pellets. Until a pellet was obtained from the molten strand, the embedding was performed under a nitrogen atmosphere. Further, the pellets were dried in a vacuum dryer at a temperature of 80 ° C. for 6 hours, and confirmed to have a water content of 0.05 parts by weight or less, and used for subsequent molding.

[Polyamide-based oxygen-scavenging resin (PA)
1)] Toshiba Isoki Co., Ltd. co-axial twin screw extruder (TEM3
7BS, 37 mmφ, L / D = 45) to prepare an oxygen-scavenging resin. 96 parts by weight of PA6 (Mitsubishi Chemical Corporation Novamid 1020, relative viscosity 3.4) was introduced from a hopper. The temperature of the resin was set to 260 ° C, butadiene oligomer having two carboxyl groups at one end (butadiene was subjected to ordinary anionic living polymerization, maleic acid dimethyl ester was used for termination reaction, and further hydrolyzed to one end A butadiene oligomer having two carboxyl groups was obtained in this example. A butadiene oligomer having a molecular weight of 5,000 was prepared this time. A mixture of 200 ppm of cobalt oxide was introduced into the extruder using a liquid injector, and the residence time was about 5 hours.
After melt kneading for one minute, unreacted substances and low molecular substances were removed from the vacuum vent, and the molten strand was quenched in water and cut to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were dried in a vacuum drier at a temperature of 80 ° C. for 6 hours, and confirmed to have a water content of 0.05 part by weight or less, and used for subsequent molding.

(Production of EVOH-based acid-scavenging resin) [EVOH-based oxygen-scavenging resin-(EV-)] A co-axial twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (TEM37BS, 37m)
mφ, L / D = 45) to prepare an oxygen-scavenging resin. 96 parts by weight of an ethylene-vinyl alcohol copolymer resin (manufactured by Kuraray Co., Ltd., EP-E105, ethylene content 44 mol%, MI 35.5, melting point 165 ° C.) was fed from a hopper. The melting temperature of the resin was set at 185 ° C., and a one-terminal epoxy-group butadiene oligomer (butadiene was subjected to ordinary anionic living polymerization, and epichlorohydrin was used for the termination reaction to obtain a one-terminal epoxy-group butadiene oligomer. 5000 parts were prepared.) Cobalt stearate was added to 4 parts by weight of the liquid material with respect to the total amount of the ethylene-vinyl alcohol resin and the one-terminal epoxy group butadiene oligomer.
The mixture obtained by mixing 0 ppm was introduced into the extruder using a liquid injector, and was melt-kneaded for a residence time of about 5 minutes.
After removing the low molecular weight material 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 dried in a vacuum dryer at a temperature of 60 ° C. for 6 hours, and confirmed that the water content was 0.05 parts by weight or less,
It was used for subsequent molding.

(Production of polyolefin-based oxygen-scavenging resin) [Polyolefin-based oxygen-scavenging resin-(PO-)]
Toshiba Machine Co., Ltd. co-rotating twin screw extruder (TEM37BS,
37 mmφ, L / D = 45) to produce an oxygen-scavenging resin. Maleic anhydride modified polypropylene resin (ER-320P, manufactured by Nippon Polyolefin Co., Ltd.) 9
6 parts by weight were introduced from the hopper. The melting temperature of the resin is 1
Butadiene oligomer having one hydroxyl group at one end (butadiene is subjected to ordinary anionic living polymerization and ethylene oxide is used for termination reaction to obtain a butadiene oligomer having two hydroxyl groups at one end. This time, a product having a molecular weight of 5000 was prepared.) A liquid injection machine was prepared by mixing 200 parts by weight of cobalt stearate with respect to the total of maleic anhydride-modified polypropylene resin and one terminal hydroxyl group butadiene oligomer in 4 parts by weight of the liquid material. The mixture was introduced into an extruder and 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. The pellets were dried in a vacuum drier at a temperature of 60 ° C. for 6 hours, and confirmed to have a water content of 0.05 part by weight or less, and used for subsequent molding.

(Production of polystyrene-based oxygen-scavenging resin) [Polystyrene-based oxygen-scavenging resin-(PS-)] Coaxial twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (TEM37BS, 3
7 mmφ, L / D = 45) to produce an oxygen-scavenging resin. 85 parts by weight of a styrene-glycidyl methacrylate copolymer (manufactured by Arakawa Chemical Industries, Ltd., GMA-8, GMA content = 5% by weight) were introduced from a hopper. The melting temperature of the resin is set at 200 ° C, butadiene oligomer having one hydroxyl group at one end (butadiene is subjected to ordinary anionic living polymerization, and ethylene oxide is used for termination reaction. A butadiene oligomer having a molecular weight of 10,000 was prepared.) A mixture of 15 parts by weight of cobalt stearate and 200 ppm based on the total amount of the styrene-glycidyl methacrylate copolymer was introduced into the extruder. (It is preferable that the PS is introduced from the second supply port after melting, which is different from the hopper of the PS, but may be dry-blended with the PS and introduced from the hopper), and the residence time is about 5 hours.
Melted and kneaded for 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. The pellets were dried in a vacuum drier at a temperature of 60 ° C. for 6 hours, and confirmed to have a water content of 0.05 part by weight or less, and used for subsequent molding.

(Barrier resin) [PETI- (PI-)] Isophthalic acid / terephthalic acid: 5 mol% / 95 mol% and a copolymer obtained by reacting the same with ethylene glycol in an equimolar amount, IV = 0.80 [PETI- (PI-)] B-010 (manufactured by Mitsui Chemicals, Inc.) / PET is melt-blended at a ratio of 1/4.

[MXD6] MX Nylon 6007, manufactured by Mitsui Gas Chemical Co., Ltd .: relative viscosity = 2.7, melt index = 2 g / 10 minutes (measuring temperature = 260 ° C., load = 2160 g) [EVOH] Kuraray Co., Ltd. EVAL EP-E105: ethylene copolymer ratio = 44 mol%, melting point = 165 ° C., melt index = 5.5 g / 10 min, (measuring temperature = 260 ° C.,
Load = 2160g)

(Structural material resin) [Polyethylene terephthalate resin] Unipet RT543: intrinsic viscosity (IV = 0.75) manufactured by Nippon Unipet Co., Ltd. [PETN8] Unipet NS553: extreme viscosity manufactured by Nippon Unipet Co., Ltd. Viscosity (IV = 0.82), PEN / PET = 8 mol% /
92 mol% [PENT8] Unipet NS663 manufactured by Nippon Unipet Co., Ltd .: Intrinsic viscosity (IV = 0.72), PEN / PET = 92 mol%
/ 8 mol% [PET / PENT8: 50/50 w% melt blend (B-)] Unipet RT543 / Unipet NS663 [PET / U-110 = 30: 1 (B-)] U-110 (Mitsubishi Chemical Corporation) ), Novapex U-11
0, UV shielding material)

(Examples 1 to 15) 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. As shown in Table 1, a multilayer preform (weight: 31 g, height: 110 mm, diameter: 25 mm) in which the intermediate layer was made of PE (polyethylene naphthalate-based oxygen-scavenging resin) and both surfaces of which were formed of PET layers was obtained. 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 with compressed air to obtain a capacity of 350.
ml, average thickness of bottle body 560 μm (outside PET /
(PE- / PET inside: about 245 μm / about 70 μm / about 245 μm), and a bottle sample having a height of 180 mm was obtained. In the same manner as in Example 2 and thereafter, bottle samples (both having a capacity of 500 ml) were produced under the conditions shown in Table 1.
Table 1 shows the mixing ratio of the raw material system of the oxygen-scavenging resin, Table 2 shows the configuration of the bottle sample and the production conditions thereof, and Table 3 shows the gas barrier properties and relative transparency of the bottle sample.

(Comparative Examples 1 to 3) A multilayer injection molding machine (Nissei ASB-50HT) was used at a cylinder 1 (for outer layer resin) temperature and a cylinder 2 (for intermediate layer resin) temperature of 280 ° C. and a mold temperature of 30 ° C. The procedure was performed in the same manner as in Example 1 to obtain a multilayer preform (weight: 31 g, height: 110 mm, diameter: 25 mm) composed of MXD6 nylon as an intermediate layer and PET layers on both sides as shown in Table 1. Next, 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 the bottle body of 500 μm (outside PET). / MXD6 / PET inside:
About 225 μm / about 50 μm / about 225 μm), height 20
A 0 mm bottle sample was obtained. Similarly, bottle samples were manufactured under the conditions shown in Table 1 after Comparative Example 2. Table 2 shows the configuration of the bottle sample and the manufacturing conditions thereof, and Table 3 shows the gas barrier properties and relative transparency of the bottle sample.

(Evaluation method) Examples 1 to 14, Comparative examples 1
The gas barrier property of the bottle sample manufactured in 3 was measured by the following method. Table 2 shows the results. 1) Oxygen permeability The oxygen permeability is OX-TRAN2 / 20M manufactured by Mocon.
L-measured. The measurement conditions are 23 ° C. and 65% RH for both the inner and outer surfaces. 2) Oxygen intrusion Ingol equipped with a soft package sampzong device
Using a polarographic oxygen sensor IL 307 manufactured by dlinstruments Inc., the period until the oxygen content in the head space completely replaced with carbon dioxide gas reached 1 ppm by oxygen entering from the atmosphere was measured. Storage condition: temperature 23 ° C: relative humidity 100% inside the bottle, 65% outside

3) 500 ml of carbonated water of gas volume 3 was added to a bottle sample of 500 ml of carbon dioxide gas loss (350 ml only in Example 1) (Example 1).
Only 350 ml). The change over time of the weight was measured, and the number of days required for the loss of carbon dioxide gas to reach 10% was determined. Storage conditions: temperature 23 ° C: relative humidity 100% RH inside the bottle, 65% R outside
H 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 40
The light transmittance from 0 nm to 700 nm is measured by U (manufactured by Shimadzu Corporation).
It measured using V-160. Specific transparency to PET (%) = [(Integration of light transmittance at 400 to 700 nm of bottles of Examples and Comparative Examples) / (Monolayer P
400-700 nm light transmittance integration of ET bottle)] ×
100

[0058]

[Table 1]

* 1: PE = polyester, PA = polyamide, EV = EVOH, PO = polyolefin * 2: PBD = polybutadiene * 3: POD = polyoctadiene * 4: PNB = polynorbornene * 5: PDCPD = Polydicyclopentadiene

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

The plastic bottle of the present invention has a structure material resin or a gas barrier resin layer provided on both surface layers, and further has an oxygen scavenging resin layer provided on an intermediate layer between these layers so that oxygen passing through the resin layer is provided. The present invention provides a beer bottle having an extremely high oxygen barrier property and a carbon dioxide gas capable of trapping oxygen, and also capturing oxygen in the head space of the bottle to completely prevent oxidation of beer as a content.

 ──────────────────────────────────────────────────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 F-term (Showa Aluminum Can Co., Ltd.) 3E062 AA09 AB02 AC08 JA01 JA07 JA08 JB11 JC07 JD01 4F100 AH08A AH08H AK01A AK01B AK01C AK03A AK03J AK28A AK41B AK41C AK41K AK42A AK42B AK42C AK46A AK46B AK46C AK69B AK69C AK80A AL01A BA03 BA06 BA07 BA10B BA10C CA07A CA23A CA30A DA01 GB16 GB23 JD01B JD01C JD02 JD03 JD14A JN01 YY00 YY00A 4F208 AA03L AA04 AA10J AA12L AA19 AA24 AA26 AA29 AH55 LA01 LA05 LB01 LG28

Claims (14)

[Claims] Claims: 1. An intermediate layer having an inner volume of 0.05 to 4 liters and a total thickness of a bottle body of 0.1 to 2 mm, comprising at least one oxygen-scavenging resin layer, and a barrier resin as a surface material. And / or 2 composed of structural resin
A multi-layer plastic bottle composed of at least three kinds of resins and three or more layers. When the beer is filled and sealed and stored in the atmosphere at 4 to 25 ° C. for 180 days, the amount of oxygen entering the bottle is reduced. A plastic bottle for beer having a weight of 1 ppm or less. 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 is less than 10% as a decrease in the amount of carbon dioxide. 2. The plastic bottle for beer according to claim 1, which is reduced. 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. An intermediate layer comprising at least one layer containing an oxygen-scavenging resin, wherein said oxygen-scavenging resin contains a catalytic amount of a transition metal compound, and has a carbon atom in its main chain or branch.
The plastic bottle for beer according to claim 1, which is a (co) polymer having a polyolefin oligomer segment having a carbon unsaturated bond bonded thereto. 6. An oxygen-scavenging resin comprising a polyester-based, polyamide-based, polyolefin-based or vinyl-based (co) polymer having a polyolefin oligomer segment having a carbon-carbon unsaturated bond in the molecule bonded thereto (these (co) ) Polymers are collectively referred to as “main polymer segments”
That. 3. The plastic bottle for beer according to claim 1, wherein 7. An oxygen-scavenging resin having a metal atom of 50
Containing 1 to 500 ppm of a transition metal compound
The plastic bottle for beer according to claim 1 or 6, comprising 5% by weight of a polyolefin oligomer segment having a carbon-carbon unsaturated bond and 85 to 99% by weight of a main polymer segment. 8. The plastic bottle for beer according to claim 6, wherein a photo-oxidation accelerator having a sensitizing effect on ultraviolet light and / or visible light is added to the oxygen-scavenging resin layer. 9. The polyolefin oligomer segment in the oxygen-scavenging resin contains a polymerized unit of butadiene, norbornene, dicyclopentadiene and isoprene, and has a molecular weight of 1,000 to 10,000.
The plastic bottle for beer according to any one of claims 6 to 8, which is an oligomer segment of: 10. The polyolefin oligomer segment having a carbon-carbon unsaturated bond in the oxygen-scavenging resin,
The beer plastic bottle according to any one of claims 6 to 9, which is an oxygen-scavenging resin bonded as a main chain of a main polymer segment or as a pendant in a branched shape. 11. The plastic bottle for beer 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. 12. 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 11, which has transparency. 13. A multi-layer plastic bottle, wherein a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer, a structural material resin / a gas barrier resin layer containing an oxygen-scavenging resin / a structural material resin from the innermost layer. 2. The beer plastic bottle according to claim 1, having a structure of a structural material resin layer / a gas barrier resin layer / a resin layer containing an oxygen-scavenging resin / a gas barrier resin layer / a structural material resin layer. 3. 14. A multilayer plastic bottle comprising two or more resins including a structural resin or a gas barrier resin layer forming both surface layers and at least one oxygen-scavenging resin layer as an intermediate layer, and three or more layers. A method for molding a plastic bottle for beer, comprising molding a parison by multilayer injection, and molding the same by a stretch blow method.