JP2013177557A - Oxygen-absorbable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new oxygen-absorbable resin composition which suppresses generation of an odor after oxygen absorption and has excellent oxygen absorbing performance without using a material responding to a metal detector, and to provide an oxygen-absorbing resin composition having excellent oxygen-absorbable performance under wide humidity conditions from low humidity to high humidity.SOLUTION: An oxygen-absorbable resin composition includes: a copolymerized polyolefin compound; and a transition metal catalyst, and the copolymerized polyolefin compound includes a constitutional unit having at least one tetralin ring.

Description

  The present invention relates to an oxygen-absorbing resin composition, and particularly to an oxygen-absorbing resin composition containing a copolymerized polyolefin compound having a tetralin ring and a transition metal catalyst.

  Prevents oxygen oxidation of various products that are easily altered or deteriorated by the influence of oxygen, such as food, beverages, pharmaceuticals, and cosmetics, and removes oxygen in the package that contains them for the purpose of long-term storage Oxygen absorber 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. Moreover, since the package which enclosed the iron-type oxygen absorber has a possibility of ignition, it cannot be heated with a microwave oven. Furthermore, since water is essential for the oxidation reaction of iron powder, the effect of oxygen absorption could only be exhibited if the material to be preserved was a high moisture type.

  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 absorbent is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. A packaging container having an oxygen absorbing function has been developed (see Patent Document 1). However, this also has problems such as being unable to use a metal detector for foreign object inspection in order to respond to a metal detector, being unable to be heated by a microwave oven, and being only effective in high moisture content. doing. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity.

  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. The object is to provide a novel oxygen-absorbing resin composition. Another object of the present invention is to provide an oxygen-absorbing resin composition having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  As a result of intensive studies on the oxygen-absorbing resin composition, the present inventors have found that the above-mentioned problems can be solved by using a copolymerized polyolefin compound having a predetermined tetralin ring and a transition metal catalyst. The present invention has been completed.

（式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、それぞれ独立して水素原子または第１の一価の置換基を示し、前記第１の一価の置換基は、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよい。）
からなる群より選択される少なくとも１種の構成単位（ａ）と、
下記一般式（２）および（３）で表される構成単位；

（式中、Ｒ₅、Ｒ₆およびＲ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈、Ｒ₉、Ｒ₁₀およびＲ₁₁は、それぞれ独立して第３の一価の置換基を示し、前記第２の一価の置換基および前記第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、前記Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁が複数存在する場合、複数の前記Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁は、互いに同一であっても異なっていてもよい。。ｍは０〜３、ｎは０〜７、ｐは０〜６、ｑは０〜４の整数をそれぞれ示し、テトラリン環のベンジル位には少なくとも１つの水素原子が結合している。Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群より選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは水素原子、メチル基およびエチル基からなる群より選択される一価の化学種を示す。）
からなる群より選択される少なくとも１種のテトラリン環を有する構成単位（ｂ）と、を含有する共重合ポリオレフィン化合物である、酸素吸収性樹脂組成物。
＜２＞ 前記遷移金属触媒が、マンガン、鉄、コバルト、ニッケルおよび銅からなる群より選択される少なくとも１種の遷移金属を含むものである、上記＜１＞記載の酸素吸収性樹脂組成物。
＜３＞ 前記遷移金属触媒が、前記共重合ポリオレフィン化合物１００質量部に対し、遷移金属量として０．００１〜１０質量部含まれる、上記＜１＞または＜２＞に記載の酸素吸収性樹脂組成物。
＜４＞ 前記共重合ポリオレフィン化合物に含まれる、前記構成単位（ｂ）の含有割合に対する前記構成単位（ａ）の含有割合が、モル比で１／９９〜９９／１である、上記＜１＞〜＜３＞のいずれか一項に記載の酸素吸収性樹脂組成物。
＜５＞ 前記構成単位（ａ）が下記式（４）および（５）で表される構成単位；

からなる群より選択される少なくとも１種の構成単位であり、
前記構成単位（ｂ）が下記式（６）および（７）で表される構成単位；

からなる群より選択される少なくとも１種の構成単位である、上記＜１＞〜＜４＞のいずれか一項に記載の酸素吸収性樹脂組成物。 That is, the present invention provides the following <1> to <5>.
<1> An oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, wherein the copolymerized 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 And at least one selected from the group consisting of imide groups, which may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , a plurality of the R ₈ , R ₉ , R ₁₀ 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, q is an integer of 0 to 4, and tetralin ring At least one hydrogen atom is bonded to the benzyl position of X. X is — (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 to 0. And represents an integer of 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 resin composition, 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 resin composition 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 resin composition 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. object.
<4> The above <1>, wherein 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 molar ratio. The oxygen-absorbing resin composition according to any one of to <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:
The structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing resin composition 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 resin composition having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity can be realized. And this oxygen-absorbing resin composition can absorb oxygen regardless of the presence or absence of moisture in the object to be preserved, and since there is no odor generation after oxygen absorption, for example, foods, cooked foods, beverages, pharmaceuticals It can be used in a wide range of applications, including health foods, regardless of the object. It is also possible to realize an oxygen-absorbing resin composition that is not sensitive to a metal detector.

  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 resin composition]
The oxygen-absorbing resin composition of the present 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 copolymerized polyolefin compound containing the 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) (Hereinafter also simply referred to as “tetralin ring-containing copolymer polyolefin compound”) and at least a transition metal catalyst.

<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 formulas (2) and (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 above 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 shall apply 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) 2-10, more preferably 2-6 straight chain, branched or cyclic Lucenyl group, for example, vinyl group, allyl group), alkynyl group (preferably alkynyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, for example, ethynyl group, propargyl group), aryl group (preferably Is 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, or a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 carbon atoms). A monovalent group obtained by removing one hydrogen atom from 5 to 6-membered or 6-membered aromatic or non-aromatic heterocyclic compound, for example, 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, more preferably having 1 to 10 carbon atoms). 6 linear, branched or cyclic alkoxy groups such as methoxy and ethoxy groups, aryloxy groups (preferably having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, such as aryloxy groups such as 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 to 12 carbon atoms, more preferably a carbon number. Is an arylcarbonyl group having 7-9, for example, acetyl group, pivaloyl group, benzoyl group), amino group (preferably an alkylamino group having 1-10 carbon atoms, more preferably 1-6 carbon atoms, preferably carbon An anilino group having 6 to 12, more preferably 6 to 8 carbon atoms, preferably a heterocyclic amino group having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, , 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, such as methylthio group or ethylthio group), arylthio A group (preferably an arylthio group having 6 to 12 carbon atoms, more preferably an arylthio group having 6 to 8 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 2 to 10 carbon atoms, more preferably having a carbon number). 1-6 heterocyclic thio groups such as 2-benzothiazolylthio group), imide groups (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, such as N-succinimide) Group, N-phthalimide group) and the like, but are not particularly limited thereto.

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. Incidentally, the substituents R ₁ to R ₁₁ of the above monovalent may have a substituent group T monovalent The carbon number mentioned above, and shall not include the carbon number 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. In addition, when the monovalent substituents R _{1 to} R ₁₁ have a substituent T, there may be a plurality of the substituents T.

In the structural unit represented by the general formula (2) or (3), X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH. A divalent group selected from the group consisting of (C = O)-and-(CHR) s- is shown, and s is an 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).

（式中、Ｒ₅〜Ｒ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈〜Ｒ₁₁は、それぞれ独立して第３の一価の置換基を示し、第２の一価の置換基および第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁が複数存在する場合、複数のＲ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁は、互いに同一であっても異なっていてもよい。ｍは０〜３、ｎは０〜７、ｐは０〜６、ｑは０〜４の整数をそれぞれ示し、テトラリン環のベンジル位には少なくとも１つの水素原子が結合している。Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群から選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは−Ｈ、−ＣＨ₃、および−Ｃ₂Ｈ₅からなる群から選択される一価の化学種を示す。） 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.

(In the formula, R _{5 to} R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R _{8 to} R ₁₁ 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, 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 Even if they are the same 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 hydrogen atom is bonded to the benzyl position of the tetralin ring. X is selected from the group consisting of — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — (CHR) s—. S represents an integer of 0 to 12. Y represents — (CHR) t—, and t represents an integer of 0 to 12. R represents —H, —CH ₃ , And a monovalent chemical species selected from the group consisting of —C ₂ H _5. )

（式中、Ｒ₁〜Ｒ₄は、それぞれ独立して水素原子または第１の１価の置換基を示し、第１の一価の置換基は、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよい。） 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.

（式中、Ｒ₅〜Ｒ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈およびＲ₉は、それぞれ独立して第３の一価の置換基を示し、第２の一価の置換基および第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、Ｒ₈またはＲ₉が複数存在する場合、複数のＲ₈またはＲ₉は、互いに同一であっても異なっていてもよい。ｍは０〜３、ｎは０〜４の整数をそれぞれ示し、Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群から選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは−Ｈ、−ＣＨ₃、および−Ｃ₂Ｈ₅からなる群から選択される一価の化学種を示す。） 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 substituted ethylene structural unit (c) containing with hydrogen.

Wherein R _{5 to} R ₇ each independently represents 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 Is 0-3, Represents an integer of 0 to 4, and X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — ( CHR) represents a divalent group selected from the group consisting of s-, s represents an integer of 0 to 12. Y represents-(CHR) t-, and t represents an integer of 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 using, for example, 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 melt mass flow rate (hereinafter referred to as “MFR”, measured in accordance with JIS K7210 at 190 ° C. under a load of 2.16 kg) of the tetralin ring-containing copolymer polyolefin compound of the present embodiment is not particularly limited. However, from the viewpoint of moldability, 0.1 to 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).

Preferable 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 to.

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 , 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 a 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 amount of oxygen absorbed by the oxygen-absorbing resin composition, the content of the transition metal catalyst may be 0.001 to 10 parts by mass as the amount of transition metal 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.

  The tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst 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.

  Moreover, the oxygen-absorbing resin composition of the present embodiment further contains other thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound as necessary, as long as the purpose of the present embodiment is not impaired. It may be. By using another thermoplastic resin in combination, moldability and handleability can be improved. As other thermoplastic resins, known ones can be used as appropriate. For example, 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- Random or alpha-olefins such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc., such as ethylene random copolymer Polyolefins such as block copolymers; 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 Copolymers and their ionic cross-linked products (ionomers), ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene-based compounds such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer Resins; 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 ( BS), polyesters such as polylactic acid, polyglycolic acid, polycaprolactone, and polyhydroxyalkanoate; polycarbonates; polyethers such as polyethylene oxide; cyclic polyolefins such as cycloolefin polymers and cycloolefin copolymers using cyclic olefins, or these Although a mixture etc. are mentioned, it is not limited to these. 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 various additives and 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.

<Usage>
For the oxygen-absorbing resin composition of the present embodiment, a known granulation method or a known molding method such as extrusion molding can be applied. For example, powder, granule, pellet, film or sheet Alternatively, it can be formed into other small pieces. Therefore, the oxygen-absorbing resin molded body obtained in this way can be used as an oxygen absorbent as it is, or by filling the obtained oxygen-absorbing resin molded body into a breathable packaging material, It can also be used as an oxygen absorbent package. Moreover, the oxygen-absorbing resin composition of the present embodiment formed into a film shape or a sheet shape can also be used in the form of a label, a card, a packing or the like. Here, a film having a thickness of 0.1 to 500 μm is classified as a film, and a film having a thickness exceeding 500 μm is classified as a sheet.

  Here, the pellet-shaped oxygen-absorbing resin molded body is preferably further pulverized into a powder form from the viewpoint of increasing the contact area with oxygen and expressing the oxygen absorption performance more effectively. .

  In addition, as said breathable packaging material, the well-known packaging material which has air permeability can be applied, and it is not specifically limited. From the viewpoint of sufficiently exhibiting the oxygen absorbing effect, the breathable packaging material is preferably highly breathable. Specific examples of breathable packaging materials include highly breathable packaging materials used in various applications, for example, paper such as Japanese paper, western paper, rayon paper, various fibers obtained from pulp, cellulose, and synthetic resin. Nonwoven fabric, plastic film or perforated material thereof used, microporous film stretched after adding calcium carbonate or the like, and those obtained by laminating two or more selected from these, etc. are particularly limited to these. Not. In addition, as a plastic film, for example, a film of polyethylene terephthalate, polyamide, polypropylene, polycarbonate or the like and a film of polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer or ethylene vinyl acetate copolymer as a sealing layer are laminated. Adhered laminated films can also be used.

  Furthermore, the molded oxygen-absorbing resin composition of the present embodiment can be used as a packaging material or a packaging container in a single layer form, as well as an aspect of a laminate in which this is superimposed on another substrate. Can be used in As a typical example of such a laminate, at least one layer composed of the oxygen-absorbing resin composition of the present embodiment and at least one layer selected from other resin layers, paper base material layers, metal foil layers, and the like are overlapped. Which can be used as oxygen-absorbing multilayer packaging materials or oxygen-absorbing multilayer packaging containers. In general, the oxygen-absorbing resin composition (layer) of the present embodiment formed into a film or sheet is provided on the inner side of the outer surface of the container or the like so as not to be exposed on the outer surface of the container or the like. Is preferred. Also, from the viewpoint of avoiding direct contact with the contents, the oxygen-absorbing resin composition (layer) of the present embodiment formed into a film or sheet is provided outside the inner surface of a container or the like. Is preferred. Thus, when using in a multilayer laminated body, it is preferable to arrange | position the oxygen-absorbing-resin composition (layer) of this embodiment shape | molded in the film form or the sheet form as at least 1 intermediate | middle layer. .

  As a preferable aspect of the above laminate, at least three of a sealant layer containing a thermoplastic resin, an oxygen absorbing layer containing the oxygen absorbing resin composition of the present embodiment, and a gas barrier layer containing a gas barrier substance are used. An oxygen-absorbing multilayer body having layers in this order may be mentioned. Here, having at least three layers in this order means that the sealant layer, the oxygen absorption layer, and the gas barrier layer are arranged in this order, and the sealant layer, the oxygen absorption layer, and the gas barrier layer are directly overlaid. Not only the mode (hereinafter referred to as “sealant layer / oxygen absorption layer / gas barrier layer”), but also a resin layer between the sealant layer and the oxygen absorption layer, or between the oxygen absorption layer and the gas barrier layer. , At least one or more other layers (hereinafter also referred to as “intermediate layer”) such as a metal foil layer or an adhesive layer (for example, “sealant layer / resin layer / oxygen absorbing layer / adhesive layer / Gas barrier layer ”,“ sealant layer / resin layer / adhesive layer / oxygen absorption layer / adhesive layer / resin layer / adhesive layer / gas barrier layer / adhesive layer / support ”, etc. Even in The way is.).

  In addition, as another preferable aspect of the laminate, a sealant layer containing a polyolefin resin, an oxygen absorbing layer containing the oxygen absorbing resin composition of the present embodiment, and a gas barrier layer containing a gas barrier substance And an oxygen-absorbing multilayer body having at least three layers in this order.

  As the thermoplastic resin and polyolefin resin used in the sealant layer, the same thermoplastic resins and polyolefin resins as described in the oxygen-absorbing resin composition of the present embodiment can be used. The thermoplastic resin and polyolefin resin used in the sealant layer are appropriately selected in consideration of compatibility with other adjacent layers (oxygen absorption layer, gas barrier layer, resin layer, adhesive layer, support, etc.). It is preferable.

  As the gas barrier material used for the gas barrier layer, a gas barrier thermoplastic resin, a gas barrier thermosetting resin, various deposited films such as silica, alumina, and aluminum, a metal foil such as an aluminum foil, and the like can be used. Examples of the gas barrier thermoplastic resin include 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.

  As a method for producing the oxygen-absorbing multilayer body, known methods such as a co-extrusion method, various laminating methods, and various coating methods can be applied depending on the properties of various materials, processing purposes, processing steps, and the like. There is no particular limitation. For example, a film or sheet is produced by extruding a resin composition melted through a T die, a circular die, or the like from an attached extruder, or an oxygen absorbing film or sheet is coated with an adhesive and another film or sheet is produced. It can shape | mold by the method of bonding together. In addition, a multilayer container having a predetermined shape or a preform for manufacturing a container can be formed by co-injecting or sequentially injecting a molten resin into an injection mold through a multilayer multiple die using an injection machine. The preform is heated to a stretching temperature, stretched in the axial direction, and blow stretched in the circumferential direction by fluid pressure to obtain a stretch blow bottle.

  Furthermore, for example, a film-like oxygen-absorbing multilayer body can be processed into a bag shape or a lid material. For example, a sheet-like oxygen-absorbing multilayer body is thermoformed into an oxygen-absorbing multilayer container having a predetermined shape such as a tray, a cup, a bottle, or a tube by a molding method such as vacuum forming, pressure forming, or plug assist molding. Can do. In addition, the bag-like container is a pouch with an easy-to-open mouth that is compatible with microwave oven cooking, which is provided with an opening after filling the contents such as food, thereby releasing steam from the opening during microwave cooking. It can be preferably used.

  In using the oxygen-absorbing resin composition of the present embodiment and various molded articles such as laminates using the same, energy rays are irradiated to accelerate the start of the oxygen-absorbing reaction, or to increase the oxygen absorption rate. can do. 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.

  The oxygen-absorbing resin composition of the present embodiment and various molded articles such as laminates (for example, containers) using the same do not require moisture for oxygen absorption, in other words, regardless of the presence or absence of moisture in the object to be stored. Since it can absorb oxygen, it can be used in a wide range of applications regardless of the type of the object to be stored. In particular, since there is no generation of odor after oxygen absorption, it can be particularly suitably used in, for example, foods, cooked foods, beverages, health foods, pharmaceuticals and the like. That is, the oxygen-absorbing resin composition of the present embodiment and various molded articles such as laminates using the same are oxygen in a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity. Since it has excellent absorption performance and excellent flavor retention of contents, it is suitable for packaging of various articles. In addition, the oxygen-absorbing resin composition of the present embodiment is different from the oxygen-absorbing resin composition using conventional iron powder, and is not stored due to the presence of iron (for example, alcoholic beverages or carbonated beverages). Can be suitably used.

Specific examples of stored items include beverages such as milk, juice, coffee, teas, alcoholic beverages; liquid seasonings such as sauces, soy sauce, noodle soups, dressings; cooked foods such as soups, stews, and curries; jams, mayonnaise Pasty foods such as tuna, fish and shellfish; processed milk products such as cheese, butter and eggs; processed meat products such as meat, salami, sausage and ham; carrots, potatoes, asparagus, shiitake mushrooms Fruits; Eggs; Noodles; Rices such as rice and milled rice; Grains such as beans; Rice processed foods such as cooked rice, red rice, rice cakes and rice bran; Sweets such as buns; powder seasonings, powdered coffee, coffee beans, tea, infant milk powder, infant foods, powder diet foods, nursing foods, dried vegetables, rice crackers, rice crackers, etc. Dry foods (foods with low water activity); chemicals such as adhesives, adhesives, pesticides and insecticides; pharmaceuticals; health foods such as vitamins; pet foods; miscellaneous goods such as cosmetics, shampoos, rinses and detergents; However, the present invention is not particularly limited thereto. In particular, preserved items that are prone to deterioration in the presence of oxygen, such as beer, wine, sake, shochu, fruit juice drinks, fruit juices, vegetable juices, soft carbonated drinks, teas in beverages, fruits, nuts, vegetables in foods , Meat products, infant food, coffee, jam, mayonnaise, ketchup, cooking oil, dressing, sauces, boiled foods, dairy products, etc. The water activity is a scale indicating the free water content in an article, and is indicated by a number from 0 to 1, with 0 for an article without moisture and 1 for pure water. That is, the water activity Aw of a certain article is expressed as follows. The water vapor pressure in the space after the article is sealed and reached an equilibrium state is P, the water vapor pressure of pure water is P ₀ , and the relative humidity in the space is RH (%). , And
Aw = P / P ₀ = RH / 100
Is defined.

  In addition, before and after filling (packaging) of these objects 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 ultra-high temperature heat treatment at 130 ° C. or higher, sterilization by electromagnetic waves such as ultraviolet rays, microwaves, and gamma rays, Examples thereof include gas treatment such as ethylene oxide, and chemical sterilization such as hydrogen peroxide and hypochlorous acid.

  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 remove unreacted 6-hydroxymethyl-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 resulting 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
A mixture obtained by dry blending cobalt stearate (II) so that the amount of cobalt is 0.1 parts by mass with respect to 100 parts by mass of the tetralin ring-containing copolymer polyolefin compound A 2 has two screws having a diameter of 20 mm. Using a shaft extruder, a film having a width of 130 mm and a thickness of 90 to 100 μm is formed by forming a film under the conditions of an extrusion temperature of 220 ° C., a screw rotation speed of 60 rpm, a feed screw rotation speed of 16 rpm, and a take-off speed of 1.0 m / min. An oxygen-absorbing film which is an oxygen-absorbing resin composition was prepared. Next, two gas barrier bags made of an aluminum foil laminated film were prepared. Then, two test pieces (length 100 mm × width 100 mm) of the obtained oxygen-absorbing film were filled in two gas barrier bags together with 500 cc of air, respectively, and the relative humidity in one bag was adjusted to 100%. After the relative humidity in the other bag was adjusted to 30%, each was sealed. The sealed body thus obtained was stored at 23 ° C. for 3 days, and the total amount of oxygen absorbed during that period was measured to confirm the odor of the film after opening. Further, a sealed body in which the relative humidity in the bag was adjusted to 100% was prepared in the same manner as described above, and stored for one month at 40 ° C. and 100% relative humidity, and the appearance of the film after one month storage was visually confirmed. . These results are shown in Table 1.

(Example 2)
An oxygen-absorbing film was produced in the same manner as in Example 1 except that cobalt (II) stearate was dry blended so that the cobalt amount was 0.05 parts by mass instead of 0.1 parts by mass, and the oxygen absorption amount was Measurement, odor confirmation, and visual confirmation of appearance. The results are shown in Table 1.

(Example 3)
An oxygen-absorbing film was produced in the same manner as in Example 1 except that cobalt (II) stearate was dry blended so that the cobalt amount was 0.01 parts by mass instead of 0.1 parts by mass, and the oxygen absorption amount was Measurement, odor confirmation, and visual confirmation of appearance. The results are shown in Table 1.

Example 4
An oxygen-absorbing film was prepared in the same manner as in Example 1 except that cobalt acetate (II) was used instead of cobalt stearate (II), and the oxygen absorption amount was measured, the odor was confirmed, and the appearance was visually confirmed. went. The results are shown in Table 1.

(Example 5)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.1 parts by mass, manganese stearate (II) is dry blended so that the amount of manganese is 0.1 parts by mass. Then, an oxygen-absorbing film was produced in the same manner as in Example 1, and the oxygen absorption amount was measured, the odor was confirmed, and the appearance was visually confirmed. The results are shown in Table 1.

(Example 6)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.1 parts by mass, iron stearate (III) is dry blended so that the amount of iron is 0.1 parts by mass. Then, an oxygen-absorbing film was produced in the same manner as in Example 1, and the oxygen absorption amount was measured, the odor was confirmed, and the appearance was visually confirmed. The results are shown in Table 1.

(Example 7)
An oxygen-absorbing film was prepared 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, and the oxygen absorption amount was measured. Visual confirmation of the appearance was performed. The results are shown in Table 1.

(Example 8)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.1 parts by mass, manganese stearate (II) is dry blended so that the amount of manganese is 0.1 parts by mass. In the same manner as in Example 7, an oxygen-absorbing film was produced, and the amount of oxygen absorbed was measured, the odor was confirmed, and the appearance was visually confirmed. The results are shown in Table 1.

Example 9
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.1 parts by mass, iron stearate (III) is dry blended so that the amount of iron is 0.1 parts by mass. In the same manner as in Example 7, an oxygen-absorbing film was produced, and the amount of oxygen absorbed was measured, the odor was confirmed, and the appearance was visually confirmed. The results are shown in Table 1.

(Example 10)
An oxygen-absorbing film was prepared 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, and the oxygen absorption amount measurement, odor confirmation and Visual confirmation of the appearance was performed. The results are shown in Table 1.

(Example 11)
An oxygen-absorbing film was prepared 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, and the oxygen absorption amount was measured. Visual confirmation of the appearance was performed. The results are shown in Table 1.

(Comparative Example 1)
An oxygen-absorbing film was prepared in the same manner as in Example 1 except that N-MXD6 (product name: “MX Nylon S6011” manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of the tetralin ring-containing copolymer polyolefin compound A. Then, the oxygen absorption was measured, the odor was confirmed, and the appearance was visually confirmed. The results are shown in Table 1.

  As is clear from Examples 1 to 11, the oxygen-absorbing resin composition of the present invention exhibits good oxygen absorption performance at both high and low humidity, no odor generation, and after oxygen absorption However, the shape of the film was maintained and did not collapse.

  Since the oxygen-absorbing resin composition of the present invention has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, it is widely and effectively used in general technical fields that require oxygen absorption. Is possible. In addition, oxygen can be absorbed regardless of the presence or absence of moisture in the object to be stored, and furthermore, since no odor is generated after oxygen absorption, for example, in foods, cooked foods, beverages, pharmaceuticals, health foods, etc. It can be used effectively. In addition, since it is possible to realize a mode insensitive to the metal detector, it can be used widely and effectively in applications in which metals, metal pieces, and the like are inspected from the outside by a metal detector, such as packaging and containers.

Claims (5)

An oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, wherein the copolymerized 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 are each independently a hydrogen atom or a second monovalent _{substituent, R 8, R 9, R} 10 and R ₁₁ are the 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 And at least one selected from the group consisting of imide groups, which may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , a plurality of the R ₈ , R ₉ , R ₁₀ 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 an integer of 0 to 4, At least one hydrogen atom is bonded to the benzyl position, X is — (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 a hydrogen atom, a methyl group and an ethyl group.)
An oxygen-absorbing resin composition, 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 resin composition according to claim 1, wherein the transition metal catalyst comprises at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.   The oxygen-absorbing resin composition 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 resin composition 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 resin composition according to any one of claims 1 to 4, which is at least one structural unit selected from the group consisting of: