JP6024495B2 - Oxygen absorbing PTP package - Google Patents

Description

  The present invention relates to an oxygen-absorbing PTP package excellent in oxygen barrier performance and oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  In the field of packaging pharmaceuticals and foods, PTP (press-through package) packages (also referred to as blister packages) are widely used for packaging drugs such as tablets and capsules, granular foods, and the like. PTP packaging is, for example, forming a pocket part to store the object to be stored by pressure forming, vacuum forming, etc., using a plastic sheet such as polyvinyl chloride resin or polypropylene resin as the bottom material, After storing the object to be stored, for example, a package in a form in which a foil or film of a material that can be easily torn by hand or easily opened like aluminum foil is laminated and sealed as a lid. In the PTP package, a transparent plastic sheet is used as the bottom material, so that the object to be stored stored in the pocket can be confirmed directly with the naked eye before opening. Further, when opening, the object to be preserved can be easily taken out by pushing the object to be preserved with a finger from the pocket portion side and breaking the lid material.

  However, when the object to be stored is sealed after being stored in the PTP package, if this is performed in the air, air is taken in and enclosed in the package when stored. Naturally, a certain amount of oxygen is taken in along with this. As a result, the object to be preserved is affected by the mixed oxygen. Although the degree of influence varies depending on the chemical properties of the material to be preserved, the medicinal properties of the drug and the flavor and color of the food are gradually lost after sealing. The longer the storage period or distribution period after sealing, the more the quality is impaired due to the influence of oxygen. Therefore, the presence of even a small amount of oxygen cannot be ignored.

  On the other hand, for the purpose of preserving for a long period of time, oxygen removal of various products that are easily altered or deteriorated due to the influence of oxygen, such as food, beverages, pharmaceuticals, and cosmetics, is performed to remove oxygen in the package. An oxygen absorbent is used.

  As the oxygen absorbent, an oxygen absorbent containing iron powder as a main reaction agent is generally used from the viewpoint of oxygen absorption capacity, ease of handling, and safety. However, since this iron-based oxygen absorbent is sensitive to a metal detector, it has been difficult to use the metal detector for foreign object inspection. Furthermore, since iron is required for the oxidation reaction of the iron powder, the effect of oxygen absorption could only be expressed if the material to be stored is a high moisture system.

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). However, this is also sensitive to metal detectors, so metal detectors cannot be used for foreign object inspection, only high-moisture materials are effective, and internal visibility is insufficient due to opacity problems. There is a problem.

  In view of the above circumstances, an oxygen absorbent using an organic substance as a reaction main agent is desired. As an oxygen absorbent containing an organic substance as a main reaction agent, an oxygen absorbent containing ascorbic acid as a main agent is known (see Patent Document 2).

  On the other hand, an oxygen-absorbing resin composition comprising a resin and a transition metal catalyst is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst as an oxidizable organic component is known (see Patent Document 3). Furthermore, Patent Document 3 also exemplifies an oxygen absorbent, a packaging material, and a multilayer laminated film for packaging obtained by molding this resin composition.

  As an oxygen-absorbing resin composition that does not require moisture for oxygen absorption, an oxygen-absorbing resin composition comprising a resin having a carbon-carbon unsaturated bond and a transition metal catalyst is known (see Patent Document 4). .

  Furthermore, as a composition for collecting oxygen, a composition comprising a polymer containing a substituted cyclohexene functional group or a low molecular weight substance to which the cyclohexene functional group is bonded and a transition metal is known (see Patent Document 5). .

Japanese Patent Laid-Open No. 9-234832 JP-A-51-136845 JP 2001-252560 A Japanese Patent Laid-Open No. 05-115776 Special table 2003-521552 gazette

  However, the oxygen absorbent of Patent Document 2 has a problem that oxygen absorption performance is low in the first place, and only a high-moisture material is effective and is relatively expensive.

  Moreover, since the resin composition of patent document 3 expresses an oxygen absorption function by containing a transition metal catalyst and oxidizing a xylylene group-containing polyamide resin, the polymer chain due to oxidative degradation of the resin after oxygen absorption. There is a problem that cutting occurs and the strength of the packaging container itself is reduced. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  Furthermore, the oxygen-absorbing resin composition of Patent Document 4 generates a low molecular weight organic compound that becomes an odor component by breaking the polymer chain accompanying the oxidation of the resin in the same manner as described above, and generates odor after oxygen absorption. There's a problem.

  On the other hand, the composition of Patent Document 5 requires the use of a special material containing a cyclohexene functional group, and there is still a problem that this material is relatively odorous.

  The present invention has been made in view of the above problems, and its purpose is to suppress the generation of odor after oxygen absorption without using a material sensitive to a metal detector, and has excellent oxygen absorption performance. An object of the present invention is to provide an oxygen-absorbing PTP package using a novel oxygen-absorbing multilayer body as a bottom material of an oxygen-absorbing PTP package. Another object of the present invention is to provide an oxygen-absorbing multilayer body having excellent oxygen-absorbing performance under a wide range of humidity conditions from low humidity to high humidity, using oxygen-absorbing multilayer body as the bottom material of the oxygen-absorbing PTP package. The object is to provide an absorbent PTP package.

  As a result of studying the oxygen-absorbing PTP package, the present inventors solved the above problem by using an oxygen-absorbing resin composition comprising a copolymerized polyolefin compound having a predetermined tetralin ring and a transition metal catalyst. As a result, the present invention has been completed.

That is, the present invention provides the following <1> to <5>.
<1> A sealant layer containing a thermoplastic resin, an oxygen absorbing layer composed of an oxygen absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a gas barrier layer containing a gas barrier material were laminated in this order. An oxygen-absorbing bottom material formed by molding an oxygen-absorbing multilayer body comprising at least three layers;
An inner layer containing a thermoplastic resin and a gas barrier layer containing a gas barrier substance, laminated in this order, and a gas barrier lid material comprising at least two layers,
An oxygen-absorbing PTP package in which the sealant layer in the oxygen-absorbing bottom material and the inner layer in the gas barrier lid material are joined,
The copolymer polyolefin compound is a structural unit represented by the following general formula (1);

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of: structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group , Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and It is at least one selected from the group consisting of imide groups, and these may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , R ₈ , R ₉ , R ₁₀ or R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is 0 to 4. Each represents an integer, and at least one hydrogen atom is bonded to the benzylic position of the tetralin ring, where X is — (C═O) O—, — (C═O) NH—, —O (C═O). A divalent group selected from the group consisting of-, -NH (C = O)-and-(CHR) s-, wherein s represents an integer of 0 to 12. Y is-(CHR) t-. T represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
An oxygen-absorbing PTP package, which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing PTP package according to <1>, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.
<3> The oxygen-absorbing PTP package according to <1> or <2>, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymer polyolefin compound. .
<4> The content ratio of the structural unit (a) to the content ratio of the structural unit (b) contained in the copolymerized polyolefin compound is 1/99 to 99/1 in terms of molar ratio. The oxygen-absorbing PTP package according to any one of <3>.
<5> Structural units in which the structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of: wherein the structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing PTP package according to any one of <1> to <4>, which is at least one structural unit selected from the group consisting of:

  According to the present invention, an oxygen-absorbing PTP package using an oxygen-absorbing multilayer body having excellent oxygen-absorbing performance under a wide range of humidity conditions from low humidity to high humidity can be realized. In addition, the oxygen-absorbing PTP package has good internal visibility, and after the oxygen absorption, the strength of the copolymerized polyolefin compound due to oxidation is extremely small, and the strength of the oxygen-absorbing layer is maintained even in long-term use. Therefore, an oxygen-absorbing PTP package that hardly causes delamination can also be realized, and an object to be stored can be suitably stored.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

[Oxygen-absorbing multilayer]
The oxygen-absorbing multilayer body of this embodiment includes a sealant layer (layer C) containing a thermoplastic resin, at least one ethylene selected from the group consisting of structural units represented by the general formula (1), or a substitution A substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural unit (a) which is an ethylene structural unit and the structural unit represented by the general formula (2) or (3). An oxygen-absorbing layer (layer) comprising an oxygen-absorbing resin composition containing a copolymerized polyolefin compound containing the structural unit (b) (hereinafter also simply referred to as “tetralin ring-containing copolymerized polyolefin compound”) and a transition metal catalyst. A) and at least three gas barrier layers (layer D) containing a gas barrier substance are laminated in this order. Moreover, the oxygen-absorbing multilayer body of the present embodiment may have a layer other than these three layers at an arbitrary position as necessary.

  The oxygen-absorbing multilayer body of the present embodiment absorbs oxygen in the container and permeates or penetrates the container wall surface from outside the container by using the layer C as an inside for a part or all of the sealing packaging container. In the case where a small amount of oxygen is used, the permeated or invaded oxygen is also absorbed, and alteration of the stored content item (stored object) due to oxygen can be prevented.

[Sealant layer (layer C)]
The sealant layer (layer C) of the oxygen-absorbing multilayer body of this embodiment contains a thermoplastic resin. In addition to the role as a sealant, this layer C allows oxygen in the container to permeate to the oxygen absorbing layer and at the same time isolates the oxygen absorbing layer (layer A) from the contents (stored material) (layer A and stored product). (Inhibiting physical contact with objects). Here, the oxygen permeability of the layer C is 300 mL / (m ² · day · atm) or more when measured with a film having a thickness of 20 μm at 23 ° C. and a relative humidity of 60%. It is preferably 400 mL / (m ² · day · atm) or more, and more preferably 500 mL / (m ² · day · atm) or more. When the oxygen permeability is equal to or higher than the above preferable value, the rate of absorbing the oxygen in the layer A can be further increased as compared with the case where the oxygen permeability is not so.

  As the thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body of this embodiment, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, and metallocene catalyst are used. Polyethylenes such as polyethylene; polystyrene; polymethylpentene; polypropylenes such as propylene homopolymers, propylene-ethylene block copolymers, and propylene-ethylene random copolymers; co-polymers made from olefins such as norbornene and ethylene And cycloolefin copolymer (COC) that is a copolymer of tetracyclododecene and olefin such as ethylene as raw materials, and cycloolefin polymer (COP) that is a polymer obtained by ring-opening polymerization of norbornene and hydrogenation Heat sealability A PET, A-PET, PETG, polyester such as PBT, amorphous nylon, and the like. These can be used alone or in combination. These thermoplastic resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid, if necessary. A copolymer, ethylene-methyl methacrylate copolymer, or thermoplastic elastomer may be added. The thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body of the present embodiment has a melt mass flow rate (hereinafter referred to as “MFR”) of 1 at 200 ° C. in consideration of the moldability and workability of the multilayer body. It is preferable to use ˜35 g / 10 minutes or MFR of 2 to 45 g / 10 minutes at 240 ° C. In the present specification, unless otherwise specified, MFR means a value when measured under the condition of a load of 2160 g at a specific temperature using an apparatus conforming to JIS K7210. Expressed with the measured temperature in units of “10 minutes”.

  Further, the layer C of the oxygen-absorbing multilayer body of the present embodiment may contain various additives known in the art in addition to the thermoplastic resin. Examples of such optional components include desiccants, coloring pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, plasticizers, stabilizers, additives such as lubricants, calcium carbonate, clay, mica, Examples thereof include fillers such as silica, deodorants and the like, but are not particularly limited thereto. In particular, it is preferable to add an antioxidant to the layer C from the viewpoint of recycling and reworking offcuts generated during production.

  The content ratio of the thermoplastic resin in the layer C can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably based on the total amount of the layer C. Is 90 to 100% by mass. In addition, the thermoplastic resin used for the layer C of the present embodiment preferably contains 50 to 100% by mass of the thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound, more preferably 70 to 100 mass%, More preferably, it is 90-100 mass%.

[Oxygen absorbing layer (layer A)]
The oxygen absorbing layer (A) of the oxygen-absorbing multilayer body of the present embodiment is a structural unit that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1). And (a) and a structural unit (b) that is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3) And an oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound in layer A is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass with respect to the total amount of layer A. That's it. When the content ratio of the tetralin ring-containing copolymer polyolefin compound is equal to or more than the preferable value, the oxygen absorption performance can be further improved as compared to the case where the content is not so.

<Tetralin ring-containing copolymer polyolefin compound>
The tetralin ring-containing copolymer polyolefin compound of this embodiment is a structural unit (a) that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1), And a structural unit (b) which is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3).

  The structural unit (a) represented by the general formula (1) is preferably at least one selected from the group consisting of structural units represented by the above formulas (4) and (5). The structural unit (b) represented by the general formula (2) is preferably at least one selected from the group consisting of structural units represented by the above formulas (6) and (7). Here, “containing a structural unit” means that the compound has one or more of the structural unit. Such a structural unit is preferably contained as a repeating unit in the tetralin ring-containing copolymer polyolefin compound. The tetralin ring-containing copolymer polyolefin compound may be either a random copolymer of the structural unit (a) and the structural unit (b) or a block copolymer of the structural unit (a) and the structural unit (b). . Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

  Further, the tetralin ring-containing copolymer polyolefin compound may contain other structural units other than the structural unit (a) and the structural unit (b), and the structural unit (a), the structural unit (b), and the other structural units. Any of a random copolymer with a structural unit and the block copolymer of the said structural unit (a), a structural unit (b), and another structural unit may be sufficient. Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

In the structural units represented by the general formulas (1) to (3), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ (Denoted as “R _{1 to} R ₁₁ ”, the same applies hereinafter) (first monovalent substituent, second monovalent substituent, and third monovalent substitution) As the group, a halogen atom (for example, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably having a carbon number of 1 to 15, more preferably a straight chain, branched or cyclic having 1 to 6 carbon atoms) Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group), alkenyl group (preferably having carbon number) 2 to 10, more preferably a straight chain having 2 to 6 carbon atoms , Branched or cyclic alkenyl groups such as vinyl and allyl groups, alkynyl groups (preferably alkynyl groups having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms such as ethynyl groups and propargyl groups). ), An aryl group (preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 12 carbon atoms, Preferably, a monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound having 2 to 6 carbon atoms, such as a 1-pyrazolyl group 1-imidazolyl group, 2-furyl group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably having 1 to 10 carbon atoms, Preferably, it is a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, such as a methoxy group or an ethoxy group, and an aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 carbon atoms). An aryloxy group having ˜8, for example, a phenoxy group, an acyl group (including a formyl group, preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, preferably 7 carbon atoms. To 12, more preferably an arylcarbonyl group having 7 to 9 carbon atoms, such as an acetyl group, a pivaloyl group or a benzoyl group, an amino group (preferably having a carbon number of 1 to 10, more preferably 1 to 6 carbon atoms). Alkylamino group, preferably 6-12 carbon atoms, more preferably an anilino group having 6-8 carbon atoms, preferably 1-12 carbon atoms, more preferably 2-6 carbon atoms. Heterocyclic amino group, for example, amino group, methylamino group, anilino group), mercapto group, alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, for example, methylthio group) , Ethylthio group), arylthio group (preferably having 6 to 12 carbon atoms, more preferably arylthio group having 6 to 8 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having 2 to 10 carbon atoms, More preferably, the heterocyclic thio group having 1 to 6 carbon atoms, such as a 2-benzothiazolylthio group, or an imide group (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms). Examples thereof include, but are not particularly limited to, N-succinimide group and N-phthalimide group).

In the case where the substituents _R 1 _{to R 11} of the above monovalent have a hydrogen atom, with the hydrogen atoms substituent T (wherein the substituents T is a substituent _R 1 _{to R 11} of the above monovalent It may be further substituted with the same meaning as described. Specific examples thereof include an alkyl group substituted with a hydroxy group (eg, hydroxyethyl group), an alkyl group substituted with an alkoxy group (eg, methoxyethyl group), and an alkyl group substituted with an aryl group (eg, benzyl). Group), an alkyl group substituted with a primary or secondary amino group (eg, aminoethyl group), an aryl group substituted with an alkyl group (eg, p-tolyl group), an aryl substituted with an alkyl group Examples thereof include, but are not particularly limited to, an oxy group (for example, 2-methylphenoxy group) and the like. When the monovalent substituents R _{1 to} R ₁₁ have a monovalent substituent T, the number of carbons described above does not include the number of carbons of the substituent T. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. Further, if the substituents R ₁ to R ₁₁ of the above monovalent has a substituent T, the substituent T can be a plurality.

In the structural unit represented by the general formula (2) or (3), X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH. The divalent group selected from the group which consists of (C = O)-and-(CHR) s- is shown, and s shows the integer of 0-12. Y is-(CHR) t-, and t represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom (—H), a methyl group (—CH ₃ ), and an -ethyl group (C ₂ H ₅ ).

  The tetralin ring-containing copolymer polyolefin compound of the present embodiment can be obtained by copolymerizing a vinyl compound (I) having a tetralin ring and another vinyl compound (II).

As vinyl compound (I) which has a tetralin ring used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by the following general formula (8) or (9) is mentioned, for example. The vinyl compound (I) having a tetralin ring can be used singly or in combination of two or more.

(Wherein R _{5 to} R ₇ each independently represents a hydrogen atom or a second monovalent substituent, and R _{8 to} R ₁₁ each independently represents a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a _{substituent, and} when R _8, R _{9, R 10} or _{R 11} there are a plurality, the plurality of _{R 8,} R _{9, R 10} or _{R 11} are each M is 0 to 3, n is 0 to 7, p is 0 to 6, q is an integer of 0 to 4, and at least one is present at the benzyl position of the tetralin ring. Hydrogen atoms are bonded, X is — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — (CHR) a divalent group selected from the group consisting of s-, wherein s represents an integer of 0 to 12. Y represents-(CHR) t-, t represents an integer of 0 to 12, R represents -H, it shows a -CH _3, and _-C 2 _H species monovalent selected from the group consisting of _5.)

As vinyl compound (II) used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by following General formula (10) is mentioned, for example. Vinyl compound (II) can be used individually by 1 type or in combination of 2 or more types.

(Wherein R _{1 to} R ₄ each independently represent a hydrogen atom or a first monovalent substituent, and the first monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, or an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic ring It is at least one selected from the group consisting of a thio group and an imide group, and these may further have a substituent.)

  Examples of the vinyl compound represented by the general formula (10) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene Ethylene or α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohex Cycloolefins such as cene and cyclooctene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; butadiene, isoprene, Conjugated dienes such as 2,3-dimethylbutadiene, pentadiene, hexadiene; styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4 -Styrenes such as dodecylstyrene, 2-ethyl-4-benzylstyrene, 2,4,6-trimethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl ( (Meth) acrylate, n-butyl (meth) Acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, (meth) acrylic acid, crotonic acid , Cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, (meth) acrylonitrile, α-chloroacrylonitrile, ethacryl Ronitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, (meth) acrylamide, α-chloro (meth) acrylamide, ethacrylamide, N-methyl (meth) acrylamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-nitroethyl (meth) acrylate, 3-nitropropyl (meth) acrylate and the like can be mentioned. These can be used alone or in combination of two or more. In addition, (meth) acrylate means an acrylate and its corresponding methacrylate, and (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid.

The tetralin ring-containing copolymer polyolefin compound of this embodiment is a substituent having at least one naphthalene ring selected from the group consisting of the structural unit (a) and a structural unit represented by the following general formula (11). It can also be obtained by reacting a copolymerized polyolefin compound containing a structural unit (c) that is a substituted ethylene structural unit containing hydrogen with hydrogen.

(Wherein R _{5 to} R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ and R ₉ each independently represent a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a substituent, and when R ₈ or R ₉ there are a plurality, the plurality of R ₈ or R ₉ is optionally being the same or different .m 0 to 3, n represents an integer of 0 to 4, and X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O )-And-(CHR) s- represents a divalent group selected from the group consisting of-and s represents an integer of 0 to 12. Y is-(CHR) t-, where t is 0-12. R represents a monovalent chemical species selected from the group consisting of —H, —CH ₃ , and —C ₂ H _5. )

  As another production method of the tetralin ring-containing copolymer polyolefin compound of the present embodiment, there is a method of reacting a polyolefin (III) having a reactive functional group in the side chain with a compound (IV) having a tetralin ring. It is done.

  Examples of the polyolefin (III) having a reactive functional group in the side chain include unsaturated carboxylic acid polymers such as poly (meth) acrylic acid; unsaturated carboxylic acid ester polymers such as poly (meth) acrylic acid methyl Polyvinyl acetate and polyvinyl acetate derivatives such as polyvinyl acetate; ethylene-unsaturated carboxylic acid copolymer; ethylene-unsaturated carboxylic acid ester copolymer; ethylene-vinyl alcohol copolymer; maleic anhydride-modified polyethylene, maleic anhydride Examples include maleic anhydride-modified polyolefin such as acid-modified polypropylene. These can be used alone or in combination of two or more.

  As the compound (IV) having a tetralin ring, a compound having a functional group that easily binds to the polyolefin (III) having a reactive functional group in the side chain is preferable, and an alcohol compound, an amine compound, a carboxyl having a tetralin ring is preferable. Examples thereof include acid compounds, acid anhydride compounds, and epoxide compounds. These can be used alone or in combination of two or more.

  In particular, a tetralin ring as the compound (IV) having the tetralin ring is added to a solution obtained by dissolving a polyolefin having an ester group in the side chain as a polyolefin (III) having a reactive functional group in the side chain in an organic solvent. A method of adding an alcohol compound having a transesterification catalyst and a transesterification reaction is preferable.

  The transesterification reaction can be performed by a known method. The reaction temperature and reaction time are not particularly limited as long as transesterification is possible, but the reaction temperature is preferably 50 to 300 ° C. and the reaction time is preferably 10 minutes to 24 hours. The organic solvent used for the transesterification reaction can be used without particular limitation as long as it is an organic solvent capable of dissolving the polymer. Examples of such an organic solvent include benzene, toluene, xylene, decalin and the like.

  As another method of transesterification, for example, a polyolefin (III) having a reactive functional group in the side chain as a polyolefin (III) having an ester group in the side chain and a tetralin ring as the compound (IV) having the tetralin ring are used. Examples thereof include a method of melt-kneading the alcohol compound having and the transesterification catalyst with a single screw extruder, a twin screw extruder, a kneader, or the like.

  As the transesterification catalyst used in the transesterification reaction, a known substance can be used. For example, sodium tert-butoxide, sodium propoxide, sodium ethoxide, sodium hydroxide, tetraisopropyl titanate, tetrabutyl titanate , Titanium oxide, titanium chloride, zirconium chloride, hafnium chloride, tin chloride, and metallocene complex catalysts of titanium, zirconium, and tin. These can be used alone or in combination of two.

  The content ratio ((a) / (b)) of the structural unit (a) to the content ratio of the structural unit (b) contained in the tetralin ring-containing copolymer polyolefin compound of the present embodiment is 1/99 in molar ratio. To 99/1, more preferably 1/19 to 19/1, and particularly preferably 1/9 to 9/1.

  The MFR (measured in accordance with JIS K7210 at 190 ° C. and a load of 2.16 kg) of the tetralin ring-containing copolymer polyolefin compound of the present embodiment is not particularly limited. ˜500 g / 10 min is preferable, and 0.2 to 100 g / 10 min is more preferable.

  Preferable specific examples of the structural unit (a) include, but are not limited to, the structural unit represented by the above formula (4) or (5).

Preferred specific examples of the structural unit (b) include structural units represented by the above formula (6) or (7) and structural units represented by the following formula (12) or (13). It is not limited.

The molecular weight of the tetralin ring-containing copolymer polyolefin compound can be appropriately set in consideration of desired performance and handling properties, and is not particularly limited. In general, the weight average molecular weight (Mw) is preferably 1.0 × 10 ^{3 to} 8.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁵ . Similarly, the number average molecular weight (Mn) is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ , and more preferably 5.0 × 10 ^{3 to} 1.0 × 10 ⁵ . In addition, all the molecular weights here mean the value of polystyrene conversion. In addition, said tetralin ring containing copolymer polyolefin compound can be used individually by 1 type or in combination of 2 or more types.

  All of the tetralin ring-containing copolymer polyolefin compounds described above have hydrogen at the benzylic position of the tetralin ring, and when used in combination with the transition metal catalyst described in detail later, the hydrogen at the benzylic position is extracted, which is excellent. Expresses oxygen absorption ability.

  Moreover, the oxygen-absorbing resin composition of the present embodiment is one in which odor generation after oxygen absorption is remarkably suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the above-described tetralin ring-containing copolymer polyolefin compound, hydrogen at the benzylic position of the tetralin ring is first extracted to generate a radical, and then the carbon at the benzylic position is oxidized by the reaction between the radical and oxygen, Group or ketone group is considered to be formed. Therefore, in the oxygen-absorbing resin composition of the present embodiment, the molecular chain of the oxygen-absorbing main agent is not broken by the oxidation reaction as in the prior art, the structure of the tetralin ring-containing copolymer polyolefin compound is maintained, and the odor is reduced. This is presumably because the low molecular weight organic compound that is the cause is difficult to be formed after oxygen absorption.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing resin composition of the present embodiment is appropriately selected from known ones as long as it can function as a catalyst for the oxidation reaction of the tetralin ring-containing copolymer polyolefin compound. It can be used and is not particularly limited.

  Specific examples of such transition metal catalysts include organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides and hydroxides of transition metals. Here, examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, and rhodium. Among these, manganese, iron, cobalt, nickel, and copper are preferable. Examples of organic acids include acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, Examples include capric acid and naphthenic acid, but are not limited thereto. The transition metal catalyst is preferably a combination of the above-mentioned transition metal and an organic acid, more preferably the transition metal is manganese, iron, cobalt, nickel or copper, still more preferably manganese, iron or cobalt, organic More preferably, the acid is acetic acid, stearic acid, 2-ethylhexanoic acid, oleic acid or naphthenic acid, even more preferably acetic acid or stearic acid, and the combination of any of these transition metals with any of organic acids is particularly preferred preferable. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst in the oxygen-absorbing resin composition of the present embodiment is appropriately determined according to the type and desired performance of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst used. It can be set and is not particularly limited. From the viewpoint of the oxygen absorption amount of the oxygen-absorbing resin composition, the content of the transition metal catalyst is 0.001 to 10 parts by mass as the transition metal amount with respect to 100 parts by mass of the tetralin ring-containing copolymer polyolefin compound. Preferably, more preferably 0.002 to 2 parts by mass, still more preferably 0.005 to 1 part by mass, still more preferably 0.008 to 0.5 parts by mass, particularly preferably 0.01 to 0.2 parts by mass. Part.

<Other thermoplastic resins>
Moreover, the oxygen-absorbing resin composition of the present embodiment may further contain other thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound as necessary. By using another thermoplastic resin in combination, moldability and handleability can be improved.

  As other thermoplastic resins, known ones can be used as appropriate. Low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, various polyethylenes such as polyethylene by metallocene catalyst, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random Random or block copolymer of α-olefins such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. Polyolefins such as polymers; acid-modified polyolefins such as maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; ethylene-vinyl acetate copolymers, ethylene-vinyl chloride copolymers, ethylene- (meth) acrylic acid copolymers, Ion-crosslinked products (ionomers), ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer; Polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, polymetaxylylene adipamide (MXD6); polyethylene terephthalate (PET), polybutylene terephthalate (PBT) ), Polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS) Polyesters such as polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate; polycarbonates; polyethers such as polyethylene oxide; cyclic polyolefins such as cycloolefin polymers and cycloolefin copolymers using cyclic olefins or mixtures thereof For example, but not limited to. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

  The tetralin ring-containing copolymer polyolefin compound, the transition metal catalyst, and other thermoplastic resins contained as necessary can be mixed by a known method. Moreover, the oxygen-absorbing resin composition which has higher dispersibility can also be obtained by kneading | mixing these using an extruder.

<Various additives>
Here, the oxygen-absorbing resin composition of the present embodiment may contain various additives known in the art as long as the effects of the present embodiment are not excessively impaired in addition to the components described above. . Examples of such optional additives include additives such as desiccants, pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, stabilizers, calcium carbonate, clay, mica, silica, and the like. An agent, a deodorant, etc. are mentioned, However, It does not specifically limit to these.

  Furthermore, the oxygen-absorbing resin composition of the present embodiment may further contain a radical generator and a photoinitiator as necessary in order to promote the oxygen absorption reaction. Specific examples of the radical generator include various N-hydroxyimide compounds. Specifically, N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxy Hexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3-hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino-N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydride Examples include phthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide, N, N-dihydroxypyromellitic acid diimide and the like. However, it is not particularly limited to these. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. These radical generators and photoinitiators can be used singly or in combination of two or more.

  In the oxygen-absorbing multilayer body of this embodiment, the thickness of the oxygen-absorbing layer (layer A) can be appropriately set according to the application and desired performance, and is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 10 μm. 100 μm. When the thickness is within the above preferable range, the performance of the layer A to absorb oxygen can be further enhanced, and the workability and economy can be maintained at a high level as compared with the case where the thickness is not. Further, the thickness of the sealant layer (layer C) can be appropriately set according to the application and desired performance, and is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 80 μm. When the thickness is within the above preferable range, the oxygen absorption rate of the layer A can be further increased and the workability and economy can be maintained at a high level as compared with the case where the thickness is not. Furthermore, considering the workability of the resulting oxygen-absorbing multilayer body, the thickness ratio of layer C to layer A is preferably 1: 0.5 to 1: 3, more preferably 1: 1.5 to 1: 2.5.

[Gas barrier layer (layer D)]
The gas barrier layer (layer D) of the oxygen-absorbing multilayer body of this embodiment contains a gas barrier substance. The oxygen permeability of the layer D is preferably 100 mL / (m ² · day · atm) or less when measured at 23 ° C. and a relative humidity of 60% for a film having a thickness of 20 μm. It is preferably 80 mL / (m ² · day · atm) or less, more preferably 50 mL / (m ² · day · atm) or less.

  Examples of the gas barrier material used for the layer D of the oxygen-absorbing multilayer body of the present embodiment include a gas barrier thermoplastic resin, a gas barrier thermosetting resin, various deposited films such as silica, alumina, and aluminum, and a metal such as an aluminum foil. A foil or the like can be used. Examples of the gas-barrier thermoplastic resin that has the visibility of the object to be stored include an ethylene-vinyl alcohol copolymer, MXD6, and polyvinylidene chloride. Examples of the gas barrier thermosetting resin include a gas barrier epoxy resin such as “MAXIVE” manufactured by Mitsubishi Gas Chemical Co., Ltd.

  When a thermoplastic resin is used as the gas barrier substance, the thickness of the gas barrier layer (layer D) is preferably 5 to 200 μm, more preferably 10 to 100 μm. When a thermosetting resin such as an amine-epoxy curing agent is used as the gas barrier substance or as the gas barrier adhesive layer, the thickness of the layer D is preferably 0.1 to 100 μm, more preferably 0.00. 5 to 20 μm. When the thickness is within the above preferable range, the gas barrier property tends to be further improved as compared with the case where the thickness is not so, and the workability and economic efficiency can be maintained at a high level.

  Note that the oxygen-absorbing multilayer body of the present embodiment includes a resin layer between the layer C and the layer A, between the layer A and the layer D, or on the outer layer of the layer C or on the outer layer of the layer D. You may have at least 1 or more other layers, such as a metal foil layer or an adhesive bond layer. For example, in order to prevent damage to the layer D and pinholes, a protective layer made of a thermoplastic resin can be provided inside or outside the layer D. Examples of the resin used for this protective layer include polyethylenes such as high-density polyethylene, polypropylenes such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, nylon 6, nylon 6,6 Polyamides such as PET, polyesters such as PET, and combinations thereof.

  In consideration of processability, the oxygen-absorbing multilayer body of the present embodiment preferably has an intermediate layer made of a polyolefin resin interposed between the layer D and the layer A. The thickness of the intermediate layer is preferably substantially the same as the thickness of the layer C from the viewpoint of workability. Here, in consideration of variations due to processing, thickness ratios within ± 10% are substantially the same.

  Further, the oxygen-absorbing multilayer body of this embodiment can be used as an oxygen-absorbing paper substrate or an oxygen-absorbing paper container by laminating a paper substrate on the outer layer of the layer D. From the viewpoint of maintaining a high level of processability when laminated with a paper base material to form a paper container, the total thickness of the layers inside the layer D is preferably 100 μm or less, more preferably 80 μm or less. .

  The oxygen-absorbing multilayer body of the present embodiment can be produced using a known method such as a co-extrusion method, various laminating methods, various coating methods, etc., depending on the properties of various materials, processing purposes, processing steps, and the like. The manufacturing method is not particularly limited. It is possible to apply a method for laminating ordinary packaging materials, for example, wet lamination method, dry lamination method, solventless dry lamination method, extrusion lamination method, T-die coextrusion molding method, coextrusion lamination method, inflation method, etc. it can. For example, for film or sheet molding, an adhesive is applied to an oxygen-absorbing film or sheet formed by extruding a melted resin composition from an extruder attached with a T die, a circular die, or the like. However, there is a method of manufacturing by pasting together with another film or sheet. Further, if necessary, for example, pretreatment such as corona treatment and ozone treatment can be applied to the film and the like, and for example, an isocyanate type (urethane type), polyethyleneimine type, polybutadiene type, organic titanium type anchor, etc. Coating agents, or known anchor coating agents such as adhesives for laminating, such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., can also be used. .

[Oxygen-absorbing bottom material]
The oxygen-absorbing bottom material of this embodiment is formed by molding the oxygen-absorbing multilayer body described above. The shape of the oxygen-absorbing bottom material of the present embodiment is not particularly limited, and can be made into a container of any shape by performing thermoforming according to the article to be stored and stored.

  More specifically, by forming the film- or sheet-like oxygen-absorbing multilayer body by a method such as vacuum forming, pressure forming, or plug-assist forming, a space capable of storing an object to be stored such as a tablet is provided. An oxygen-absorbing bottom material can be produced.

In addition, when producing the oxygen absorptive bottom material which has a flange part, you may give the special process which provides an easy peeling function to the flange part. Further, by using the oxygen-absorbing multilayer body as a member such as a container lid or a top seal, an oxygen absorbing function can be imparted to these containers.
[Gas barrier cover material]
The gas barrier lid material of this embodiment is composed of at least two layers in which an inner layer containing a thermoplastic resin and a gas barrier layer containing a gas barrier material are laminated in this order, and the gas barrier is provided in the oxygen-absorbing PTP package. It is possible to reduce the amount of oxygen that permeates or enters the lid material from the outside. Moreover, the gas-barrier molded object of this embodiment may have layers other than these two layers in arbitrary positions as needed. In particular, by providing the above-described oxygen absorbing layer (layer A) of the present embodiment in the middle of these two layers, the lid member can also be given an oxygen absorbing function.

  The thermoplastic resin used for the inner layer of the gas barrier lid material of the present embodiment is not particularly limited, and a specific example is a thermoplastic resin suitably used in the above-described oxygen-absorbing multilayer sealant layer (layer C). What is shown.

  Moreover, the inner layer of the gas barrier lid material of the present embodiment may contain various additives known in the art in addition to the above-described thermoplastic resin. Specific examples thereof include those shown as additives that are preferably used in the above-described sealant layer (layer C) of the oxygen-absorbing multilayer body.

  The content ratio of the thermoplastic resin in the inner layer can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90% with respect to the total amount of the inner layer. ˜100 mass%. Although the thickness of an inner layer can be suitably set according to a use or desired performance, and it does not specifically limit, 1-50 micrometers is preferable, More preferably, it is 5-20 micrometers.

  The thermoplastic resin used for the inner layer of the gas barrier lid material of the present embodiment is the same type as the thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body from the viewpoint of ensuring the heat fusion strength of the PTP package. Is preferred.

The gas barrier layer of the gas barrier cover material of this embodiment contains a gas barrier substance. The oxygen permeability of the gas barrier layer is preferably 100 mL / (m ² · day · atm) or less when measured at 23 ° C. and a relative humidity of 60% for a film having a thickness of 20 μm. It is preferably 80 mL / (m ² · day · atm) or less, more preferably 50 mL / (m ² · day · atm) or less.

  Specific examples of the gas barrier substance used for the gas barrier layer of the gas barrier cover material of the present embodiment include those shown as the gas barrier substance suitably used in the gas barrier layer (layer D) of the oxygen-absorbing multilayer body described above. It is done. In particular, in a PTP package, it is particularly preferable to use an aluminum foil because the stored object is pushed out and taken out. The thickness of the gas barrier layer of the gas barrier lid member is preferably 1 to 100 μm, more preferably 5 to 20 μm.

[Oxygen-absorbing PTP package]
The oxygen-absorbing PTP package of this embodiment includes an oxygen-absorbing bottom material formed by molding the above-described oxygen-absorbing multilayer body and a gas barrier lid material, and the sealant layer of the bottom material and the gas barrier lid material This is an oxygen-absorbing PTP package in which the inner layer is bonded. The oxygen-absorbing PTP package of the present embodiment absorbs oxygen in the container, and if there is a small amount of oxygen that enters from outside the container, the oxygen-absorbing PTP package also absorbs the oxygen that has entered, It is possible to prevent deterioration of the preserved material) due to oxygen. Note that the PTP (press-through package) package is called a blister package in foreign countries.

  In using the oxygen-absorbing multilayer body of the present embodiment and the oxygen-absorbing PTP package including the multilayer body, energy rays are irradiated to promote the start of the oxygen-absorbing reaction or increase the oxygen absorption rate. be able to. As the energy ray, for example, visible light, ultraviolet ray, X-ray, electron beam, γ-ray or the like can be used. The amount of irradiation energy can be appropriately selected according to the type of energy beam used.

  In addition, before and after storing (packaging) the object to be preserved, the container or the object to be preserved can be sterilized in a form suitable for the object to be preserved. As the sterilization method, for example, heat sterilization at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultrahigh temperature heat treatment at 130 ° C. or higher, sterilization by electromagnetic waves such as ultraviolet rays, microwaves, gamma rays Examples thereof include gas treatment such as ethylene oxide, and chemical sterilization such as hydrogen peroxide and hypochlorous acid.

[Stored items]
The material to be stored in the oxygen-absorbing PTP package of the present embodiment is not particularly limited. For example, various medicines such as health foods such as vitamin C and vitamin E, tablets for internal use, orally disintegrating tablets (OD tablets) can be stored.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
In a four-necked separable flask with an internal volume of 1000 mL, 100 g of ethylene-methyl methacrylate copolymer (product name: “Acrylift WK402” manufactured by Sumitomo Chemical Co., Ltd.) having a methyl methacrylate content of 25 mass%, 6-hydroxylmethyl -1,2,3,4-tetrahydronaphthalene 81g, decalin 160g, tetrabutyl titanate 0.2g as a transesterification catalyst were charged, and the temperature of the reaction solution was raised to 210 ° C in a nitrogen atmosphere while stirring, and methanol was distilled. The reaction was carried out for 3 hours while leaving. After methanol was not distilled off, the pressure was gradually reduced to distill off unreacted 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene and decalin. Then, it returned to normal pressure and cooled and the solid reaction crude product was obtained. Next, toluene is added to the obtained reaction crude product so that the concentration thereof becomes 3 to 4% by mass, and the solution is heated to 80 ° C. to dissolve, then the solution is cooled to about 40 ° C., methanol is added, The precipitated tetralin ring-containing copolymer polyolefin compound A was recovered by filtration.

As a result of measuring the weight average molecular weight and number average molecular weight of the obtained tetralin ring-containing copolymer polyolefin compound A by GPC (gel permeation chromatography), the weight average molecular weight in terms of polystyrene was 9.5 × 10 ⁴ , and the number average molecular weight. Was 3.1 × 10 ⁴ . As a result of measuring the melting point by DSC, the melting point was 71 ° C.

(Synthesis Example 2)
Instead of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene in Synthesis Example 1, 1,5-dimethyl-8-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was used, and the mass was 95. A tetralin ring-containing copolymer polyolefin compound B was synthesized in the same manner as in Synthesis Example 1 except that the amount was 0.0 g. The tetralin ring-containing copolymer polyolefin compound B had a polystyrene equivalent weight average molecular weight of 9.1 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , and a melting point of 71 ° C.

(Synthesis Example 3)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Synthesis Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 5% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Synthesis Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 16.2 g. Containing copolymerized polyolefin compound C was synthesized. The tetralin ring-containing copolymer polyolefin compound C had a polystyrene equivalent weight average molecular weight of 9.6 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , and a melting point of 98 ° C.

(Synthesis Example 4)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Synthesis Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 10% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Synthesis Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 32.4 g. Containing copolymerized polyolefin compound D was synthesized. This tetralin ring-containing copolymer polyolefin compound D had a polystyrene-equivalent weight average molecular weight of 9.3 × 10 ⁴ , a number average molecular weight of 3.1 × 10 ⁴ , and a melting point of 92 ° C.

Example 1
First, obtained by dry blending 100 parts by mass of copolymer polyolefin compound A and 0.05 parts by mass of cobalt stearate (II) as a cobalt amount in a twin screw extruder having two screws with a diameter of 37 mm. The obtained mixture was supplied and kneaded under the conditions of an extrusion temperature of 220 ° C. and a screw rotation speed of 100 rpm to obtain an oxygen-absorbing resin composition A.

  Next, using a multilayer film production apparatus equipped with two extruders, a feed block, a T die, a cooling roll, a corona discharge treatment device, a winder, etc., the material of the sealant layer was directly changed from the first extruder. Linear low density polyethylene (product name: “Novatec LL UF641” manufactured by Nippon Polyethylene Co., Ltd., MFR 2.1 g / min (measured in accordance with JIS K7210), 240 ° C. MFR 4.4 g / 10 min, 250 ° C. MFR 5. 2 g / 10 minutes, hereinafter referred to as “LLDPE1”), the oxygen-absorbing resin composition A was extruded from the second extruder as the material of the oxygen-absorbing layer, and two kinds having a width of 900 mm were fed through the feed block. A two-layer oxygen-absorbing film (thickness; oxygen-absorbing layer 30 μm / LLDPE 1 layer 30 μm) was produced. Thereafter, the surface of the LLDPE 1 layer was subjected to corona discharge treatment at 60 m / min to produce a film roll. When the obtained film roll was observed, there was no uneven thickness such as bumps.

  On the other hand, using a sheet manufacturing apparatus equipped with one extruder, feed block, T die, cooling roll, corona discharge treatment apparatus, winder, etc., cycloolefin copolymer (hereinafter referred to as COC) (product name: TOPAS ADVANCED) POLYMERS “TOPAS8007-F”) was extruded at 10 m / min to produce a single-layer sheet having a thickness of 250 μm. One side of this single-layer sheet is subjected to corona discharge treatment, and the corona discharge treatment surface is gravure coated with an aqueous dispersion of vinylidene chloride resin (hereinafter referred to as PVDC) (product name: “Saran Latex L-509” manufactured by Asahi Kasei Corporation). Was used to prepare a gas barrier sheet of two types and two layers (thickness: gas barrier layer 15 μm / COC layer 250 μm). It was.

  Next, using an adhesive for urethane-based dry laminating (product name: “TM251 / CAT-RT88” manufactured by Toyo Ink Co., Ltd.), the oxygen-absorbing layer of the obtained oxygen-absorbing film and the gas-barrier layer of the gas-barrier sheet are bonded together. An oxygen-absorbing multilayer body was prepared, and the structure of the oxygen-absorbing multilayer body was LLDPE 1 layer 30 μm / oxygen absorption layer 30 μm / adhesive layer 3 μm / gas barrier layer 15 μm / COC layer 250 μm. Using the blister pack manufacturing apparatus FBP-M2 manufactured by Co., Ltd., the number of shots is fixed at 50 shots / minute, and the LLDPE1 layer is placed inside the pocket shape with a bottom 10 mmφ, top 9 mmφ, and depth 4 mm. Then, plug assist pressure forming was performed to produce an oxygen-absorbing bottom material.

  On the other hand, by extrusion lamination with LLDPE1, a gas barrier lid material of aluminum foil (20 μm) / urethane anchor coating agent (“EL-557A / B” manufactured by Toyo Ink Co., Ltd., 0.5 μm) / LLDPE1 (20 μm) Produced.

  After storing the tablet of 7 mmφ containing vitamin E 20 mg and thickness 3 mm in the produced oxygen-absorbing bottom material, the LLDPE 1 of the oxygen-absorbing bottom material and the gas barrier lid material are heat-sealed and sealed, An oxygen-absorbing PTP package containing tablets was prepared. From the oxygen-absorbing bottom material side, the tablet was visible. This was stored at 40 ° C. and 60% RH, and the oxygen concentration in the pocket after 1 day storage and the vitamin E retention after 3 months storage were measured. Vitamin E retention was measured using high performance liquid chromatography. These results are shown in Table 1.

(Example 2)
An oxygen-absorbing bottom material was obtained in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound B was used in place of the tetralin ring-containing copolymer polyolefin compound A. Thereafter, an oxygen-absorbing PTP package containing tablets was prepared in the same manner as in Example 1 and the oxygen concentration in the pocket and the vitamin E retention rate were measured in the same manner as in Example 1. These results are shown in Table 1.

(Example 3)
An oxygen-absorbing bottom material was obtained in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound C was used in place of the tetralin ring-containing copolymer polyolefin compound A. Thereafter, an oxygen-absorbing PTP package containing tablets was prepared in the same manner as in Example 1, and the oxygen concentration in the bag and vitamin E retention rate were measured in the same manner as in Example 1. These results are shown in Table 1.

Example 4
An oxygen-absorbing bottom material was obtained in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound D was used in place of the tetralin ring-containing copolymer polyolefin compound A. Thereafter, an oxygen-absorbing PTP package containing tablets was prepared in the same manner as in Example 1, and the oxygen concentration in the bag and the vitamin E retention rate were measured in the same manner as in Example 1. These results are shown in Table 1.

(Comparative Example 1)
Iron powder having an average particle size of 20 μm and calcium chloride were mixed at a mass ratio of 100: 1, and this mixture and LLDPE1 were kneaded at a mass ratio of 30:70 to obtain an iron-based oxygen-absorbing resin composition. . Using the iron-based oxygen-absorbing resin composition, an attempt was made to produce a two-kind three-layer film in the same manner as in Example 1. However, irregularities derived from iron powder occurred on the film surface, and could withstand subsequent studies. A film having a smooth surface could not be obtained. Therefore, a 30 μm-thick linear low-density polyethylene film (product name; “Tosero TUX HC” manufactured by Tosero Co., Ltd., hereinafter referred to as “LLDPE2”) is used as the oxygen-absorbing layer as the iron-based material. The oxygen-absorbing resin composition was laminated by extrusion lamination with a thickness of 30 μm, and then the surface on the layer side of the iron-based oxygen-absorbing resin composition was subjected to corona discharge treatment at 60 m / min to obtain a laminate film.

Next, the laminate film was laminated on the corona-treated surface side by dry lamination in the same manner as in Example 1, and bleached kraft paper (basis weight 50 g / m ² ) / urethane-based dry lamination adhesive (product name; “TM251 / CAT-RT88” manufactured by Toyo Ink Co., Ltd., 3 μm) / aluminum foil (7 μm) / urethane anchor coating agent (“EL-557A / B” manufactured by Toyo Ink Co., Ltd., 0.5 μm) / low density polyethylene ( An iron-based oxygen-absorbing bottom material of 20 μm) / oxygen absorbing layer (30 μm) / LLDPE2 (30 μm) was produced. In addition, the number of the micrometer unit in a parenthesis shows thickness.

  Next, using the obtained iron-based oxygen-absorbing bottom material, an oxygen-absorbing PTP package containing tablets was prepared in the same manner as in Example 1, and the oxygen concentration in the bag was adjusted as in Example 1. Measurement and measurement of vitamin E retention were performed. These results are shown in Table 1.

  As is clear from the results of Examples 1 to 4, the oxygen-absorbing PTP package of the present invention exhibited good stored object visibility and oxygen absorption performance, and suppressed deterioration of vitamin E sealed in a container.

Claims (5)

At least three layers in which a sealant layer containing a thermoplastic resin, an oxygen absorbing layer composed of an oxygen absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a gas barrier layer containing a gas barrier material are laminated in this order. An oxygen-absorbing bottom material formed by molding an oxygen-absorbing multilayer body comprising:
An inner layer containing a thermoplastic resin and a gas barrier layer containing a gas barrier substance, laminated in this order, and a gas barrier lid material comprising at least two layers,
An oxygen-absorbing PTP package in which the sealant layer in the oxygen-absorbing bottom material and the inner layer in the gas barrier lid material are joined,
The copolymer polyolefin compound is a structural unit represented by the following general formula (1);

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of:
Structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group , Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and It is at least one selected from the group consisting of imide groups, and these may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , R ₈ , R ₉ , R ₁₀ or R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is 0 to 4. Each represents an integer, and at least one hydrogen atom is bonded to the benzylic position of the tetralin ring, where X is — (C═O) O—, — (C═O) NH—, —O (C═O). A divalent group selected from the group consisting of-, -NH (C = O)-and-(CHR) s-, wherein s represents an integer of 0 to 12. Y is-(CHR) t-. T represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
An oxygen-absorbing PTP package, which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing PTP package according to claim 1, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.   The oxygen-absorbing PTP package according to claim 1 or 2, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymerized polyolefin compound.   The content rate of the said structural unit (a) with respect to the content rate of the said structural unit (b) contained in the said copolymerization polyolefin compound is 1 / 99-99 / 1 in molar ratio, Any of Claims 1-3 The oxygen-absorbing PTP package according to claim 1. The structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of:
The structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing PTP package according to any one of claims 1 to 4, which is at least one structural unit selected from the group consisting of: