JP2003253131A - Oxygen-absorbent resin composition, and laminate and package made by using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition whose oxygen absorbency can be easily controlled and which has persistent oxygen absorbency, to obtain a laminate by combining the resin composition with various barrier layers and having oxygen barrier properties and oxygen absorbency, and a package made by using it. <P>SOLUTION: The oxygen-absorbent resin composition is obtained by blending 100 pts.wt. of a resin composition comprising 50-99 wt.% of a thermoplastic resin and 1-50 wt.% of an alicyclic unsaturated compound or its derivative, with 0.001-2 pts.wt. of a compound containing a transition metal and 0.001-2 pts.wt. of a photosensitizer. The laminate is provided with an oxygen-absorbent resin layer b made by using the composition. The package is made by using it. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having oxygen absorbing ability, a laminate using the same, and a package using the same, and more specifically, to a thermoplastic resin containing an alicyclic unsaturated compound. Alternatively, a derivative thereof, a transition metal compound, a resin composition having an oxygen absorbing ability obtained by blending a photosensitizer, and an oxygen barrier property and an oxygen absorbing ability obtained by combining the resin composition with a barrier layer The present invention relates to a laminate having the same and various packages using the same.

[0002]

2. Description of the Related Art In the field of packaging business for packaging various contents, the following contents can be broadly mentioned as keywords of "packaging" or "packaging". (1) "Display effect" such as giving purchase consciousness to consumers and presenting danger. (2) "Tolerance to contents" so that the packed body is not damaged by the filled contents themselves. (3) "Protection of contents" against external stimuli.

[0003] These keywords are further subdivided and developed into fine required quality. Among them, the protection of the contents from oxygen and moisture has been particularly attracting attention in terms of “protecting the contents”. Particularly in recent years, in various fields such as the food field, the industrial product field, and the medical / pharmaceutical field, the protection of the contents against oxygen and moisture has been emphasized. As the background, oxygen is decomposed and deteriorated by oxidation, and water is deteriorated due to moisture absorption or hydrolysis.

As described above, various methods have been studied in order to prevent alteration of the contents due to oxygen or water. One of them is to design a package using a material having an oxygen barrier property or a moisture barrier property. To give an example in terms of the oxygen barrier below, a laminate using a thermoplastic resin having excellent oxygen gas barrier properties such as an ethylene-vinyl alcohol copolymer, or a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, or alumina vapor deposition is polyester. Examples thereof include a laminate using a vapor deposition film obtained by providing it on a substrate or the like.

A package using these barrier base materials is
Due to its high oxygen barrier property, it is expanding into various applications. However, although these barrier base materials have high barrier properties, they allow a very small amount of oxygen to permeate. Further, when the contents are filled using these packages, the headspace gas is present in the upper part of the packages in most cases. Recently, it has been attempted to remove oxygen in the headspace by performing inert gas replacement from the viewpoint that the oxygen remaining in the headspace also deteriorates the contents, but still a small amount of oxygen remains. The situation remains.

As described above, in order to remove a small amount of oxygen passing through the barrier substrate or oxygen in the headspace gas inside the package, a resin having oxygen absorbing ability (oxygen absorbing resin) is developed. It's starting to happen. Typical types of these are as follows. (1) A type that uses an oxidative decomposition or an oxygen addition reaction of an unsaturated compound. (2) Oxygen coordination bond type using a transition metal complex. (3) Hydrogen peroxide conversion (reduction into other gas) using reduction / oxidation reaction with reducible compounds

Unlike the above-mentioned barrier resin, these oxygen absorbing resins consume (absorb) oxygen by utilizing phenomena such as oxidation and coordination, so that they are combined with the barrier substrate. As a result, it is possible to absorb a small amount of permeated oxygen, and it is also possible to remove a small amount of oxygen in the headspace, so that attention has been paid to the preservation of contents.

However, the problems of these oxygen absorbing resins are as follows. Among the oxygen absorbing resins of the above type (1), in the case of the decomposing type, problems such as generation of odor due to oxidative decomposition, deterioration of mechanical properties due to lower molecular weight of the polymer, and coloring are mentioned. In addition, in the case of the addition type, there may be mentioned one in which an oxygen absorption site by oxygen addition is introduced by transesterifying an ethylene-acrylic acid ester-based polymer, but since it is introduced in the form of copolymer in the polymer skeleton. Moreover, if the unit necessary for oxygen absorption is completely consumed, no further absorption effect can be expected. Further, since the transesterification reaction is used, it is difficult to quantitatively control the unit. Further, depending on the skeleton, oxygen reversibly coordinates oxygen in the type (2) of the above-mentioned type, so that it may be deoxygenated under certain conditions, but its oxygen absorption capacity is relatively low. Further, the oxygen absorbing resin of the type (3) above may generate a harmful gas such as hydrogen peroxide.

The appearance of oxygen-absorbing resins is a field that is expected in terms of the effect of preserving the contents of the package in the future, but as mentioned above, there are still many items to be improved as described above.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to consider the above-mentioned circumstances, and it is easy to control the oxygen absorption capacity and to have a resin composition having an oxygen absorption capacity with a continuous oxygen absorption capacity. The object is to obtain a laminate having an oxygen barrier property / oxygen absorbing property and a package using the same by forming a composite with an object and various barrier layers.

[0011]

The present invention has been conceived to overcome the above-mentioned problems. The invention according to claim 1 is based on 50 to 99 wt% of a thermoplastic resin and has an alicyclic structure. To 100 parts by weight of a resin composition containing 1 to 50 wt% of a saturated compound or its derivative, 0.001 to 2 parts by weight of a compound containing a transition metal and 0.001 to 1 part of a photosensitizer are added.
An oxygen-absorbing resin composition, characterized in that it is blended in an amount of 2 parts by weight.

According to a second aspect of the present invention, in the oxygen-absorbing resin composition according to the first aspect, the unsaturation calculated from the iodine value or bromine number of the alicyclic unsaturated compound or its derivative. The amount of binding is 0.1 mol /
100 g (alicyclic unsaturated compound or its derivative)
It is an oxygen absorbing resin composition characterized by the above.

According to a third aspect of the present invention, in the oxygen-absorbing resin composition according to the first or second aspect, the alicyclic unsaturated compound is a polymer or derivative of a cyclic diene compound. It is a characteristic oxygen absorbing resin composition.

The invention according to claim 4 of the present invention is the oxygen-absorbing resin composition according to any one of claims 1 to 3, wherein the compound containing a transition metal is cobalt, manganese, iron or nickel. , An aromatic carboxylic acid salt selected from one or more kinds of copper, a transition metal compound salt such as a saturated or unsaturated carboxylic acid salt, or various transition metal complexes such as acetylacetonato, ethylenediaminetetraacetic acid, salen, porphyrin and phthalocyanine An oxygen-absorbing resin composition comprising one or more compounds selected.

According to a fifth aspect of the present invention, in the oxygen-absorbing resin composition according to any one of the first to fourth aspects, the photosensitizer is a benzophenone type, an acetophenone type, or an azide. It is an oxygen-absorbing resin composition characterized by being selected from at least one kind of a series compound.

The invention according to claim 6 of the present invention is the oxygen-absorbing resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin is polyethylene or an ethylene-α-olefin copolymer. , Polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene random copolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, ethylene-propylene-polybutene-1 copolymer ,
Representative of polyolefin resins such as ethylene-cyclic olefin copolymers, ethylene-α, β unsaturated carboxylic acids or esterified products thereof, ionically crosslinked products thereof, ethylene-vinyl acetate copolymers or partially saponified products or fully saponified products thereof An oxygen-absorbing resin composition, which is a simple substance of an ethylene copolymer, a polyester resin, a polyamide resin, a polyacrylonitrile resin, or a graft-modified polyolefin resin such as an acid anhydride, or a mixture of one or more thereof. Is.

The invention according to claim 7 of the present invention is a laminate characterized in that the oxygen-absorbing resin composition according to any one of claims 1 to 6 is laminated and provided.

The invention according to claim 8 of the present invention is characterized in that, in the laminate according to claim 7, the oxygen-absorbing resin composition layer is laminated in a thickness range of 5 to 200 μm. It is a laminated body.

According to a ninth aspect of the present invention, in the laminated body according to the seventh or eighth aspect, the oxygen permeability is 50.
cm ³ [25 μm (thickness) / 1 m ² (area) / 24 h
(Hour) /1.01325×10 ⁵ Pa (pressure)] or less, at least one barrier layer selected from a thermoplastic resin layer, a metal foil layer, a metal vapor deposition thermoplastic polymer layer, and an inorganic compound vapor deposition thermoplastic polymer layer. It is a laminated body characterized by laminating the above.

According to a tenth aspect of the present invention, in the laminate according to the ninth aspect, the barrier layer is a polyester resin layer, a polyamide resin layer, a polyacrylonitrile layer, a polyvinyl alcohol layer, an ethylene-vinyl alcohol copolymer. Polymer layer, thermoplastic resin layer selected from polyvinylidene chloride layer, metal foil layer such as aluminum foil, at least one kind of various thermoplastic resin layers provided with aluminum vapor deposition layer, silica vapor deposition layer, or alumina vapor deposition layer It is a laminated body characterized by being processed.

The invention according to claim 11 of the present invention is a packaging body characterized by being formed from the laminated body according to any one of claims 6 to 10.

The invention according to claim 12 of the present invention is the package according to claim 11, wherein the package is formed as a soft package.

The invention according to claim 13 of the present invention is the package according to claim 11, which is formed as a bottle container.

The invention according to claim 14 of the present invention is the package according to claim 11, which is formed as a tray container or a cup container.

The invention according to a fifteenth aspect of the present invention is the package according to the eleventh aspect, which is formed as a lid material for a container.

The sixteenth aspect of the present invention is the package according to the eleventh aspect, which is formed as a cap or an inner cap of the container.

The invention according to claim 17 of the present invention is the package according to claim 11, which is formed as a composite paper container.

The invention according to claim 18 of the present invention is a package formed by combining any two or more of the packages according to claims 12 to 17 above. .

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The oxygen-absorbing resin composition of the present invention has a transition ratio of 100 parts by weight of a resin composition containing 50 to 99 wt% of a thermoplastic resin and 1 to 50 wt% of an alicyclic unsaturated compound or a derivative thereof. Compound containing metal is 0.0
It is a resin composition having an oxygen-absorbing ability, which is obtained by blending 01 to 2 parts by weight and a photosensitizer in an amount of 0.001 to 2 parts by weight.

As the thermoplastic resin which is the main component of the resin composition, a polyolefin resin or an ethylene copolymer can be mentioned. For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, α-olefins are butene-1, hexene-1, octene-1, 4,
An ethylene-α-olefin copolymer such as methylpentene-1, a polyα-olefin such as polypropylene, polybutene-1, poly-4-methylpentene-1, an α-olefin-ethylene copolymer such as random polypropylene or block polypropylene, or It is also possible to use a copolymer of two or more α-olefins, such as an ethylene-propylene-butene copolymer, a butene-propylene copolymer, a propylene-butene-hexene copolymer.

Also, a polyolefin resin such as an ethylene-cyclic olefin copolymer can be used. As the ethylene-based copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl ester, ethylene- (meth) acrylic acid ethyl ester, ethylene- (meth) acrylic acid n-butyl ester, ethylene -I-butyl (meth) acrylate, t-butyl ethylene- (meth) acrylate, various ion-crosslinked products of ethylene- (meth) acrylic acid, ethylene- (meth) acrylic acid- (meth) acrylic acid ester ternary Ethylene-α, β unsaturated carboxylic acids such as copolymers or esterified products thereof, or ion-crosslinked products thereof, ethylene-vinyl acetate copolymers or partially saponified products thereof, ethylene-α,
Examples include β-unsaturated carboxylic acid ester-maleic anhydride terpolymers and ethylene- (meth) acrylic acid glycidyl ester copolymers.

Further, there may be mentioned a maleic anhydride, a vinyl or (meth) acryloxysilane compound, a polyolefin resin having a reactive functional group such as glycidyl ester of (meth) acrylic acid graft-reacted.

If necessary, various components may be copolymerized, and various components such as those copolymerized with carbon monoxide and those copolymerized with an allyl compound can be selected. These polyolefins or ethylene copolymers can be used alone or as a mixture of one or more of them.

As an essential component to be blended with these thermoplastic resins, an alicyclic unsaturated compound or its derivative can be mentioned. Linear unsaturated compounds such as butadiene rubber,
Isoprene rubber, butadiene-isoprene copolymer rubber, styrene-butadiene block copolymer, styrene-isoprene copolymer, etc., form a hydroperoxide by radicals generated by the photosensitizer described below, the main chain Cause the cleavage of.

Therefore, it is preferable to use an alicyclic unsaturated compound. Examples of these include a linear diene compound, a cyclic diene compound, or a derivative thereof, for example, a polymer of a cyclic diene compound formed by a diene reaction using butadiene, cyclopentadiene, or furan as a starting material or a derivative thereof. . Examples thereof include dicyclopentadiene-based polymers and norbornene-based polymers. Further, these materials may be polymers obtained by random copolymerization or alternating copolymerization with ethylene, and various functional groups may be introduced into the skeleton if necessary.

The unsaturated bond site contained in these compounds affects the oxygen absorption capacity. The quantitative index of the unsaturated bond site can be determined by iodine value and bromine value. Iodine, bromine, etc. undergo an addition reaction with unsaturated bond, and 1 molecule (1 mol) per 1 mol of unsaturated bond
Is added.

The amount of unsaturated bond in the polymer calculated from the above values is preferably 0.1 mol / 100 g (alicyclic unsaturated compound or its derivative) or more. The amount of unsaturated bond sites is related to oxygen absorption capacity,
If it is less than 0.1 mol / 100 g (alicyclic unsaturated compound or its derivative), the oxygen absorption capacity is insufficient. There is no upper limit for the amount of unsaturated bonds, but 0.3-1 mol /
If it is 100 g (alicyclic unsaturated compound or its derivative), it has a sufficient oxygen absorption capacity.

The amount of the alicyclic unsaturated compound or its derivative compounded in the thermoplastic resin is 50 to 50% by weight.
The alicyclic unsaturated compound or its derivative is 1 to 50 wt% with respect to 99 wt%. If it is less than 1 wt%, the oxygen absorption capacity is poor, and if it exceeds 50 wt%, it causes a problem in molding processability. It is preferably 5 to 40 wt%, more preferably 10 to 30 wt%.

As an additive to be added to this resin composition,
First, a compound containing a transition metal can be mentioned. The compound containing the transition metal functions as a catalyst for the oxygen absorption mechanism. As these transition metals, the periodic law 3A to 7A,
The elements of Group 8 and 1B are mentioned, and among them, one or more compounds selected from cobalt, manganese, iron, nickel and copper are particularly preferable.

Examples of the compounds composed of these transition metals include salts of transition metal compounds such as aromatic carboxylic acid salts, saturated or unsaturated carboxylic acid salts, and various kinds of acetylacetonato, ethylenediaminetetraacetic acid, salen, porphyrin, phthalocyanine and the like. Transition metal complexes may be mentioned. Particularly, saturated or unsaturated fatty acid salts of these transition metals having 10 to 20 carbon atoms are preferable, and various transition metal salts such as stearate, linoleate, and linolenate or derivatives thereof are preferable in terms of handling and cost. . The blending amount is 0.001 to 2 parts by weight of these transition metal compounds with respect to 100 parts by weight of the resin composition. If the amount is less than this amount, the oxygen absorption capacity associated with oxidation decreases. The amount added may be more than this, but since the saturation limit is reached, the required amount is 2
Parts by weight.

The following essential components include photosensitizers selected from at least one of benzophenone compounds, acetophenone compounds, and azide compounds.

These can be easily decomposed by an active energy ray such as UV or EB to form various radicals. It is possible to cause an oxygen addition reaction with various radicals thus obtained as a starting point. Preferably, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, alkylated benzophenone, 3,
Benzophenone compounds such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone are preferred. The addition amount of these is 0.001 to 2 parts by weight of the photosensitizer with respect to 100 parts by weight of the resin composition. If the amount is less than this amount, the oxygen absorption capacity will decrease. The upper limit is the same as that described in the section of the transition metal compound.

The compound containing a transition metal and the photosensitizer described above can exhibit the function as oxygen absorption if at least one of them is blended or both are not blended. However, the combination of these amplifies the oxygen absorption cycle and is also reflected in the oxygen absorption rate. In this sense, it is preferable to add both of them in terms of function.

Although not an essential component, it is preferable to add a hindered phenol or phosphorus antioxidant to these resin compositions. These compounds trap radicals generated by irradiation with UV or EB, and thus have a function of hindering oxygen absorption ability. However, a compound having an unsaturated bond may be easily decomposed by heating at the time of molding, which may cause deterioration of processability. In that sense, they may be appropriately blended for the purpose of imparting processability stability and for the purpose of controlling the oxygen absorption ability.

If desired, various additives other than the above, such as flame retardants, slip agents, antiblocking agents, etc., may be added.

The advantage of the resin composition having oxygen absorbing ability of the present invention is that the oxygen absorbing site is made of an alicyclic unsaturated compound, and oxygen absorption is expressed by an additive in the resin composition. Therefore, the oxygen absorption capacity can be easily controlled by the amount of addition.

As a method for producing these resin compositions having oxygen absorbing ability, various predetermined compounding amounts set according to the molding method of the final product and the required oxygen absorbing ability are used to prepare a ribbon mixer, a tumbler mixer, and a Henschel. A kneader such as a single-screw extruder or an extruder such as a twin-screw extruder, or a Banbury mixer, which is dry-blended using a mixer or the like, or which is blended in a predetermined amount with each feeder installed in the kneader in advance. Depending on the thermoplastic resin used as the base, a melting point or higher but 280 ° C. or lower, preferably 260 ° C. or lower, more preferably 240
It can be obtained by kneading at a temperature of ℃ or below.

The resin composition having oxygen absorbing ability of the present invention can be formed into a laminate by various molding methods such as extrusion lamination molding, extrusion cast molding, inflation molding, injection molding and direct blow molding. In addition, for films (inflation etc.) obtained by the above-mentioned molding method, it is possible to obtain a laminate by dry lamination, wet lamination, or non-solvent lamination in a later step, and stretch the preform obtained by injection molding. Although it is possible to form a multi-layer stretch blow bottle by blow molding, it is not limited to these molding methods.

The simple substance of the resin composition having oxygen absorbing ability of the present invention has oxygen absorbing ability, but since the thermoplastic resin constituting the resin composition is a material having high oxygen permeability, it is referred to as oxygen transmitting and absorbing. There is a problem that concertation occurs and oxygen permeation becomes large. Also in the sense of overcoming such problems, at least one layer using the resin composition,
Oxygen permeability 50 cm ³ [25 μm (thickness) / 1 m ² (area) / 24 h (hour) /1.01325×10 ⁵ Pa
(Pressure)] It is preferable to provide the following barrier layer.

Examples of these materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide 6 and polyamide 6-polyamide 6
6 copolymer, polyamide resin such as aromatic polyamide,
Polyacrylonitrile resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, thermoplastic resin layer selected from polyvinylidene chloride resin, metal foil layer such as aluminum foil, aluminum, silica, PVD deposition method such as alumina, Alternatively, a vapor deposition thermoplastic resin layer obtained by a CVD vapor deposition method using an organosilane such as hexamethylene disiloxane, an acetylene gas, or another carbon gas source can be used. Furthermore, these vapor deposition layers, especially P
In VD deposition, in order to improve its gas barrier property,
A polyvinyl alcohol / silane compound-based overcoat layer may be provided. In addition, various primer layers for improving the adhesion between the vapor deposition layer and the thermoplastic resin layer may be provided.

By using these barrier layers, not only the resin composition layer having oxygen absorbing ability completely absorbs the oxygen gas slightly permeated through these barrier layers,
Since the amount of permeated oxygen gas consumed is small, it becomes possible to absorb the oxygen gas in the head space of the package.

An example of the laminate is described below. The symbols described in the example of the laminate are described below. A: Polyolefin resin, B: Acid anhydride graft modified polyolefin resin C: Ethylene-vinyl alcohol copolymer D: Alumina vapor deposition polyester film, E: Aluminum foil F: Ethylene- (meth) acrylic acid copolymer G: Polyvinyl alcohol -Based overcoat layer, H: Urethane-based adhesive I: Polyester film configuration example-1: A / B / C / B / oxygen absorbing resin composition ... Molding method: extrusion molding, injection molding, blow molding, etc .... Use: sheet , Bottles, cups, trays, etc. Configuration example-2: D / G / H / A / oxygen absorbing resin composition ... Molding method: extrusion lamination, dry lamination, etc .... Use: Soft packaging, lid material configuration example-3: I / H / E / F / oxygen absorbing resin composition ... Molding method: extrusion lamination, etc .... Use: Inner cap, etc. Configuration example-4: Paper / A / D / G / H / A / Iodine adsorption resin composition ... molding: extrusion lamination, etc. ... Applications: composite paper containers etc.

The above-mentioned constitutional example is a case in which the oxygen absorbing resin composition layer is the innermost layer, but by incorporating an alicyclic unsaturated compound or its derivative, visco-adhesiveness is exhibited, and therefore, for example, In extrusion lamination, there is a possibility that the release roll property (relative to roll release property) may deteriorate.
In such a case, the oxygen absorbing resin composition of the present invention may be used as an intermediate layer, and a polyolefin resin or the like may be provided in the innermost layer as shown in FIG.

As described above, the laminated body obtained in various constitutions can be expanded as it is to a packaging body for various uses. These examples are not limited to the contents described above,
It is possible to develop into various packaging forms. Further, by combining these packaging forms, it becomes possible to form a packaging body that absorbs oxygen.

[0055]

EXAMPLES Examples of the present invention will be shown below, but the invention is not limited thereto.

[Preparation of Resin Composition Having Oxygen Absorption Capacity:
Materials] The following materials were used. <Thermoplastic resin> -A-1: Low-density polyethylene resin (MI = 5.1) -A-2: Homopolypropylene resin (MI = 4) -A-3: Maleic anhydride graft-modified polypropylene resin (MI = 5) ) A-4: Polyethylene terephthalate resin (IV =
0.85 dl / g) <Alicyclic unsaturated compound> -B-1: Dicyclopentadiene polymer (iodine value:
180 g / 100 g ... 0.71 mol / 100 g) B-2: norbornene-based polymer (bromine number: 55 g / 1
00g ... 0.34mol / 100g) <Processability stabilizer> -Phosphorus-based antioxidant-Hindered phenol-based antioxidant <Transition metal compound> -Cobalt stearate <Photosensitizer> -Benzophenone

[Preparation of Resin Composition Having Oxygen Absorption Capability:
Manufacture] The above-mentioned thermoplastic resin and alicyclic unsaturated compound dry-blended to have the formulation shown in the following examples, 100 parts by weight of the above-mentioned thermoplastic resin and 2 parts by weight of a transition metal compound, 100 parts by weight of the above-mentioned thermoplastic resin and 2 parts by weight of the photosensitizer, and if necessary, the above-mentioned thermoplastic resin and the processability stabilizer, were each added in a twin-screw extruder (φ = 3).
0 mm, screw size: L / D = 49, L: length,
D: Diameter, discharge rate 9 kg / h (hour), temperature 1
Mix at 80 ℃, 50 rpm of the extrusion screw,
After each compound was obtained, these compounds were dry-blended to prepare a resin composition having oxygen absorbing ability, and stored in an aluminum package (completely replaced with an inert gas).

[Preparation of Evaluation Sample: Material] <Resin Composition Having Oxygen Absorption Capability> -Resin composition having oxygen absorption capacity according to the compounding ratio of the following examples <Barrier base material> -Alumina-deposited polyester base material (polyvinyl) Alcohol / silane coupling agent-based overcoat layer: 12 μm thick <Intermediate layer> ・ Low density polyethylene (inflation film: 40 μm thick)
m) ・ Random polypropylene resin (cast film: thickness 40μm)

[Preparation of Evaluation Sample: Production] A laminated film obtained by laminating the above-mentioned alumina vapor-deposited polyester film substrate as a barrier substrate and an olefin film as an intermediate layer by a urethane adhesive by a dry laminating method. As a base material, on the surface of the base material, a resin composition having a thickness of 25 μm having the above-mentioned oxygen absorption ability, a low-density polyethylene resin with MI = 35 (thickness 15 μm)
= 23 random polypropylene resin (thickness 15μm)
2 kinds of two-layer coextruder (φ = 65 mm, screw size: L / D = 23, L: length, D: diameter) at a temperature of 2
A film is formed under the conditions of 40 ° C and a processing speed of 50 m / min.
The following laminate was formed. <Laminate 1> (Outside) Alumina-deposited polyester film layer (thickness 12 μm) / adhesive layer / low density polyethylene layer (thickness 40 μm) / resin composition layer having oxygen absorbing ability (thickness 25 μm) / low Density polyethylene layer (thickness 1
5 μm) (Inner) <Laminate 2> (Outer) Alumina-deposited polyester film layer (12 μm) / Adhesive layer / Random polypropylene layer (40 μm thickness) / Oxygen-absorbing resin composition layer (25 μm thickness) / Random polypropylene layer (15μm thickness) (inside)

[Preparation of evaluation sample: sample adjustment and
And evaluation method] From the inside of the above-mentioned laminated body, a high pressure mercury lamp
2000 mJ / cm²To irradiate
Cut the sample into 200 mm x 100 mm and seal
Seal the two sides with an impulse sealing machine with a width of 10 mm
It was After that, on a vacuum seal machine with a seal width of 10 mm
After creating a more vacuum package, from the package corner,
General air (oxygen concentration 21%) and adjusted gas (N₂: 9
9%, O₂25% of 1%) was injected. At the injection site
The corner part is a 10mm impulse seal
A seal was applied to prevent gas leakage. Surface area is 1
4000 mm ²Is. After that, use an oximeter to
Then, 10 ml of the gas was injected and the oxygen absorption capacity was confirmed.

Example 1 70 wt% of A-1 as a thermoplastic resin and 30 w of B-1 as an alicyclic unsaturated compound.
With respect to 100 parts by weight of the resin composition mixed with t%, 0.1 parts by weight of a transition metal compound and a photosensitizer, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant as a processability stabilizer, 0.05 parts by weight and 0.025 parts, respectively
The compound, which was adjusted to be parts by weight, was dry blended as described above to prepare a resin composition having an oxygen absorbing ability. Next, the prepared resin composition having oxygen absorption ability was formed into a film on the low-density polyethylene layer surface of a laminated film substrate composed of an alumina-deposited polyester film layer / adhesive layer / low-density polyethylene layer with an extruder. A laminate of the present invention was obtained. The results are shown in Table 1 and FIG.

Example 2 A resin composition having oxygen absorbing ability was prepared by dry blending in the same manner as in Example 1 except that 70 wt% of A-2 was blended as the thermoplastic resin. A film was formed in the same manner as in Example 1 above to obtain a laminate of the present invention.

<Example 3> B as an alicyclic unsaturated compound
-2 was blended in the same manner as in Example 1 except that 30 wt% was blended, and a dry blend was performed to prepare a resin composition having an oxygen absorbing ability, and a film was formed in the same manner as in Example 1 above. A laminate of the present invention was obtained.

Example 4 85 wt% of A-1 as a thermoplastic resin and 15 w of B-1 as an alicyclic unsaturated compound.
The same procedure as in Example 1 was carried out except that t% was blended, and dry blending was carried out to prepare a resin composition having an oxygen absorbing ability, and a film was formed in the same manner as in Example 1 above. A laminated body was obtained.

<Embodiment 5> Using the laminate having the structure shown in the above Embodiment 1, a lid material for a container (surface area: 20,000 m)
m ² ) was created. The container at that time was a three-kind five-layer barrier container made of polyethylene, an ethylene vinyl alcohol copolymer, and an acid anhydride graft-modified polyethylene. After filling the container with the contents, the container was sealed with the above-mentioned lid material, and the head space gas amount in the upper part of the container (adjusted gas: N ₂ : 9
9%, O ₂ : 1%) was adjusted to 25 ml, and the temporal change in oxygen concentration was similar to the result shown in Example 1 (Table 1 and FIG. 1).

<Example 6> The laminate having the structure shown in Example 4 was cut into a circle, and the insert-molded insert was used to form an oxygen-absorbing inner cap (surface area: about 700 mm ² ). The container used at that time was a polyethylene terephthalate bottle having an internal capacity of 500 ml in which a silica film was formed by CVD deposition using hexamethylene disiloxane. UV irradiation is performed in the state of the cap before filling the sample, and after filling the bottle with the powder sample, the adjusted gas (N ₂ : 99%,
O ₂ : 1%) was substituted for capping. The headspace gas amount was 10 ml. Since the effective area is small, but the filling gas amount is small, the oxygen absorption site could at least sufficiently absorb oxygen.

Example 7 70 parts by weight of A-3 as a thermoplastic resin and 30 parts by weight of B-1 as an alicyclic unsaturated compound were mixed with 100 parts by weight of a resin composition.
0.1 parts by weight of the transition metal compound and the photosensitizer, and 0.05 parts by weight and 0.05 parts by weight of a phosphorus-based antioxidant and a hindered phenol-based antioxidant as processability stabilizers, respectively.
025 parts by weight were compounded and dry blended as in Example 1 above to prepare a polypropylene resin composition having an oxygen absorption capacity. Next, the polypropylene-based resin composition having the above-described oxygen absorption ability is formed into a film on a barrier substrate with an extruder, and a polypropylene resin layer (outermost layer) / A-3 simple substance adhesive layer / ethylene-vinyl alcohol is used. A film was formed on the polypropylene resin layer surface of a laminated film substrate of 5 layers of 4 types consisting of copolymer layer / polypropylene resin composition / polypropylene resin layer (innermost layer) to obtain a laminate of the present invention. Then, using the above-mentioned laminated body, a tray container having the same laminated constitution as in the above-mentioned Example 5 was prepared by vacuum forming. Next, a lid member was prepared using the same laminated body as in Example 2, the container was filled with the contents, and then the container was sealed with the lid member,
The head space gas amount (adjusted gas: N ₂ : 99%, O ₂ : 1%) in the upper part of the tray container was adjusted to 25 ml in the same manner as in Example 5 above, and the contents were stored. Since the effective area occupied by the resin possessed was large, the ability to absorb oxygen was improved as compared with Example 5.

Example 8 70 wt% of A-4 as a thermoplastic resin and 30 w of B-1 as an alicyclic unsaturated compound.
With respect to 100 parts by weight of the resin composition mixed with t%, 0.1 parts by weight of the transition metal compound and the photosensitizer, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant as processability stabilizers, 0.05 parts by weight and 0.025 parts, respectively
Dry blending was carried out in the same manner as in Example 1 in such a blending ratio that the amount would be parts by weight to prepare a polyethylene terephthalate (PET) -based resin composition having oxygen absorbing ability. A book comprising a polyethylene terephthalate resin layer (outermost layer) / PET resin composition layer (intermediate layer) / polyethylene terephthalate resin layer (innermost layer) using the PET resin composition having the above oxygen absorption ability The laminate of the invention was formed, and a PET-based multi-layer preform using this laminate was prepared. Next, the PET-based multi-layer preform obtained was stretch blow-molded to obtain the same internal capacity as in Example 6 of 500.
A ml PET bottle was made. At that time, the oxygen absorbing layer of the intermediate layer (innermost layer) (resin composition layer having oxygen absorbing ability)
The thickness was adjusted to be 15 μm to 20 μm at the thinnest. Next, the PET bottle and an oxygen absorbing inner cap (surface area of about 700) prepared by insert injection molding in Example 6 above.
(mm ² ), UV irradiation is performed to fill the bottle with the powder sample, and then the above-mentioned adjusted gas (N ₂ : 99%, O ₂ : 1%).
And capped. The headspace gas amount was 10 ml. As a result of performing the same evaluation as in Example 6 above, it was possible to sufficiently absorb oxygen due to the effects of the oxygen absorption bottle and the inner cap.

The evaluation results of Examples 1 to 4 are shown in Tables 1 and 2 below.

[0070]

[Table 1]

[0071]

[Table 2]

Tables 1 and 2 show that the filled oxygen gas concentration is 2
Example 1 in the case of 1% and filling oxygen gas concentration 1%
4 shows changes in oxygen absorption capacity of Sample No. 4 over time.

[0073]

INDUSTRIAL APPLICABILITY The resin composition having oxygen absorbing ability of the present invention, and the laminate and package using the same are made of the thermoplastic resin 5.
0.001 to 2 parts by weight of a compound containing a transition metal based on 100 parts by weight of a resin composition containing 1 to 50% by weight of an alicyclic unsaturated compound or its derivative with respect to 0 to 99% by weight, and a photosensitizer By blending so as to be 0.001 to 2 parts by weight, oxygen having a good oxygen absorption capacity, and the absorption capacity can be easily controlled by the addition amount of the alicyclic unsaturated compound. It is possible to provide a resin composition having an absorption capacity.

The resin composition having an oxygen absorbing ability in the present invention has an oxygen addition type oxygen absorbing mechanism,
It is possible to avoid discoloration of color tone such as browning, deterioration of strength physical properties, and odor due to decomposition.

In particular, the resin composition having an oxygen absorbing ability according to the second embodiment of the present invention is a mixture of a polypropylene resin with a transition metal compound and a photoinitiator. Although there is concern about the effects of oxidative decomposition, it is possible to obtain results that do not lead to a large decrease in physical properties, and it was confirmed that the combined use of a decomposition type slightly improves oxygen absorption capacity. Was done.

The laminate using the resin composition having oxygen absorbing ability in the present invention has a good oxygen barrier property as a material such as polyester resin, polyamide resin, polyacrylonitrile, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, By combining with a thermoplastic resin layer selected from polyvinylidene chloride, a metal foil layer such as an aluminum foil, various thermoplastic resin layers provided with an aluminum vapor deposition layer, a silica vapor deposition layer or an alumina vapor deposition layer, oxygen permeation is extremely low, Moreover, it is possible to remove the headspace oxygen inside the package.

The resin composition having oxygen absorbing ability and the laminate using the same in the present invention can be easily applied to various packages, and the resin composition having oxygen absorbing ability is
Basically, it functions by the decomposition of the base polymer, polyolefin or ethylene copolymer, so that the function decreases with the consumption of oxygen absorption sites, like the oxygen absorption polymers of unsaturated bond site oxidation type. Therefore, it can be applied to an oxygen-absorbing package for a long period of time.

[Brief description of drawings]

FIG. 1 is a laminated sectional view illustrating an example of development of a laminated body using a resin composition having an oxygen absorbing ability in the present invention.

FIG. 2 is a graph showing changes over time in oxygen absorption capacity at a packed oxygen gas concentration of 21% in a package formed of a laminate using the resin composition having oxygen absorption capacity shown in the examples of the present invention.

FIG. 3 is a graph showing the time course of the oxygen absorption capacity at a packed oxygen gas concentration of 1% in a package formed of a laminate using the resin composition having the oxygen absorption capacity shown in the examples of the present invention.

[Detailed description of symbols]

a: thermoplastic resin layer (innermost layer) b ... Resin composition layer having oxygen absorption ability c ... Polyolefin layer (intermediate layer) d ... Adhesive layer e ... Polyvinyl alcohol coating layer f ... Alumina vapor deposition layer g ... Polyester film layer (outermost layer)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 101/00 C08L 45:00 45:00) F term (reference) 3E067 BA03A BA10A BA12A BA14A BA17A BB01A BB12A BB14A BB15A BB16A BB22A BB25A CA04 CA06 EA34 EE25 EE31 EE33 GB11 GB13 GD10 3E086 AB01 AD01 AD04 AD05 AD06 AD23 BA04 BA13 BA14 BA15 BB05 CA01 CA11 CA28 4F100 AA01D AA19 AB01C AB02A AB14A AB15A AB16A AB17A AB33B AH01A AH02A AH03A AH08A AH10A AK01A AK02A AK03A AK04A AK06 AK07A AK09A AK21B AK21C AK21D AK27A AK27B AK27C AK27D AK41A AK41B AK41C AK41D AK46A AK46B AK46C AK46D AK62A AK64A AK68A AK69B AK69C AK69D AK70A AK71A AL02A AL03A AL05A BA02 BA03 BA04 BA07 BA10A BA10B BA10C BA10D CA30 EH66C EH66D GB16 GB18 JB16A JD02 JD02B JD02C JD02D JD14 JD14A YY00A 4J002 AA011 BB031 BB051 BB061 BB071 BB081 BB121 BB151 BB171 BB221 BB 231 BG101 BK002 BN051 BP021 CE002 CF001 CL001 EE037 EE046 EG006 EG076 EN116 EQ037 EU006 FD206 FD207 GF00 GG02

Claims (18)

[Claims] 1. A cycloaliphatic unsaturated compound or its derivative is contained in an amount of 1 to 50 wt% with respect to 50 to 99 wt% of a thermoplastic resin.
With respect to 100 parts by weight of the blended resin composition, 0.001 to 2 parts by weight of the compound containing a transition metal and 0.00 of the photosensitizer are used.
An oxygen-absorbing resin composition, which is blended in an amount of 1 to 2 parts by weight. 2. The amount of unsaturated bond calculated from the iodine value or bromine number of the alicyclic unsaturated compound or its derivative is 0.1 mol / 100 g (alicyclic unsaturated compound or its derivative) or more. The oxygen-absorbing resin composition according to claim 1, which is present. 3. The oxygen-absorbing resin composition according to claim 1 or 2, wherein the alicyclic unsaturated compound is a polymer or derivative of a cyclic diene compound. 4. The compound containing a transition metal is cobalt,
Aromatic carboxylic acid salts selected from one or more kinds of manganese, iron, nickel, copper, transition metal compound salts such as saturated or unsaturated carboxylic acid salts, or acetylacetonate,
The oxygen absorbing resin composition according to any one of claims 1 to 3, which is one or more compounds selected from various transition metal complexes such as ethylenediaminetetraacetic acid, salen, porphyrin, and phthalocyanine. 5. The photosensitizer is selected from at least one selected from the group consisting of benzophenone-based compounds, acetophenone-based compounds, azido-based compounds, and benzoin-based compounds. The oxygen absorbing resin composition of. 6. The thermoplastic resin is polyethylene, ethylene-α-olefin copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-
Propylene random copolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, ethylene-propylene-polybutene-1 copolymer,
Representative of polyolefin resins such as ethylene-cyclic olefin copolymers, ethylene-α, β unsaturated carboxylic acids or esterified products thereof, ionically crosslinked products thereof, ethylene-vinyl acetate copolymers or partially saponified products or fully saponified products thereof 6. An ethylene-based copolymer, a polyester resin, a polyamide resin, a polyacrylonitrile resin, or a graft-modified polyolefin resin such as an acid anhydride, which is a single substance or a mixture of one or more types thereof. An oxygen-absorbing resin composition according to any one of items. 7. A laminate comprising the oxygen-absorbing resin composition according to any one of claims 1 to 6 laminated. 8. The oxygen-absorbing resin composition layer has a thickness of 5 to 5.
The laminated body according to claim 7, which is laminated in a range of 200 μm. 9. An oxygen permeability of 50 cm ³ [25 μm (thickness) / 1 m ² (area) / 24 h (hour) /1.0132
5 × 10 ⁵ Pa (pressure) or less, at least 1 barrier layer selected from a thermoplastic resin layer, a metal foil layer, a metal vapor deposition thermoplastic polymer layer, and an inorganic compound vapor deposition thermoplastic polymer layer.
The laminated body according to claim 7 or 8, wherein one or more kinds are laminated. 10. The barrier layer is a polyester resin layer,
Polyamide resin layer, polyacrylonitrile layer, polyvinyl alcohol layer, ethylene-vinyl alcohol copolymer layer, thermoplastic resin layer selected from polyvinylidene chloride layer, metal foil layer such as aluminum foil, aluminum vapor deposition layer, silica vapor deposition layer or alumina The laminate according to claim 9, wherein the laminate is selected from at least one kind of various thermoplastic resin layers provided with a vapor deposition layer. 11. A packaging body, which is formed from the laminated body according to any one of claims 6 to 10. 12. The package according to claim 11, which is formed as a soft package. 13. The package according to claim 11, which is formed as a bottle container. 14. The package according to claim 11, which is formed as a tray container or a cup container. 15. The package according to claim 11, which is formed as a lid material for a container. 16. The package according to claim 11, which is formed as a cap or an inner cap of a container. 17. The package according to claim 11, which is formed as a composite paper container. 18. A package formed by combining any two or more of the packages according to claim 12 to 17.