JP2003327848A - Oxygen-absorptive resin composition and laminate and package each using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate and a package having oxygen barrier property/ oxygen absorption property by using a composition increased in oxygen absorptive ability and prevented from degradation of oxygen absorptive membrane properties and compositing the composition with various barrier layers. <P>SOLUTION: The oxygen-absorptive resin composition is obtained by compounding, as essential ingredients, at least ingredients shown below to 100 pts.wt. thermoplastic resin (A), wherein the ingredients are (1) 0.001-2 pts.wt. compound T containing a transition metal, (2) 0.001-2 pts.wt. at least one photosensitizer compound selected from (substituted) benzoyl group-containing compounds and azide compounds and (3) 0.01-20 pts.wt. at least one having larger degradability than the thermoplastic resin (A) and selected from (saturated) fatty acids or their esters, natural fatty acids, natural rubber and synthetic rubbers. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having oxygen absorbing ability, a laminate and a package using the same, more specifically, a thermoplastic resin and a transition metal compound,
By combining a photosensitizing compound, and a decomposable compound such as a saturated or unsaturated fatty acid or an ester thereof, and a resin composition having oxygen absorption ability, and combining the resin composition with a barrier layer, The present invention relates to a resin composition having oxygen absorption properties, oxygen barrier properties and oxygen absorption properties, and improved strength properties, and a laminate and a package using the same.

[0002]

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

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

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

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

As described above, oxygen absorbing resins have been developed in order to remove a small amount of oxygen passing through the barrier substrate or oxygen in the headspace gas inside the package. Typical types of these include the following. (1) Type using oxidation of thermoplastic resin with transition metal (2) Type using oxidation decomposition or oxygen addition reaction of thermoplastic resin having carbon-carbon double bond (3) Oxygen using transition metal complex Coordination bond type (4) Hydrogen peroxide conversion (reduction into other gas) using reduction / oxidation reaction of reducible compounds

Regarding the type (1), the polymer oxidation mechanism utilizing the autoxidation of the transition metal is used, but the problem is that the oxygen absorption capacity is low or the capacity rising speed is slow. The contents are mentioned. In the case of the type (1), it is sufficient to trap a trace amount of oxygen that permeates from the outside of the package by laminating it with a high gas barrier thermoplastic resin or by oxidizing the high gas barrier thermoplastic resin itself. However, it is not suitable for removing oxygen in the headspace. (Patent Document 1
reference)

The type (2) which uses an oxidation or oxygen addition reaction of a thermoplastic resin having a carbon-carbon double bond has an excellent oxygen absorbing ability, and various publications are disclosed in addition to the cited documents. However, in this publication, the maintenance of the film physical properties after oxygen absorption is defined by the ratio of carbon-carbon double bonds, but the effect of free radicals associated with oxidative decomposition has not been examined, and the permanent film physical properties are not considered. Has not yet reached the maintenance solution. Furthermore, in this method, only carbon-carbon double bonds are studied, and the type (1) is not described. (See Patent Document 2).

The oxygen coordination bond type using the transition metal complex of (3) has a low ability to coordinate one molecule of oxygen to one molecule of transition metal in the complex, and although it functions as an indicator, oxygen is used. It is difficult to develop it as an absorber (see Patent Document 3).

Regarding the hydrogenation of the compound (4) using the reduction / oxidation reaction of the reducible compound, there is a problem in hygiene / safety because hydrogen peroxide is generated after absorbing oxygen.
Another problem is that the use of this reaction causes the thermoplastic resin itself to change color (because it also functions as a pigment).

These oxygen absorbing resins are different from the above-mentioned barrier resins in that oxygen is consumed (absorbed) by utilizing phenomena such as oxidation and coordination, so that they are combined with the barrier substrate. As a result, a small amount of permeated oxygen can be absorbed, and a small amount of oxygen in the headspace can also be removed. Therefore, attention has been paid to the preservation of contents.

As described above, the advent of the oxygen absorbing resin is a field expected in terms of the effect of preserving the contents of the package in the future, but there are still many matters to be improved in the present situation.

[0013]

[Patent Document 1] Japanese Patent No. 2991437 (Table 3)

[Patent Document 2] Japanese Patent No. 3064420 (page 5)

[Patent Document 3] Japanese Patent Publication No. 7-82001 (FIGS. 1 to 3)

[Patent Document 4] Japanese Patent No. 2922306 (FIGS. 1 to 3)

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to take the above-mentioned circumstances into consideration, and it has a high oxygen absorption ability and suppresses the deterioration of the physical properties of the film for oxygen absorption. To obtain a laminate and a package having oxygen barrier / oxygen absorbing properties.

[0015]

The present invention has been conceived to overcome the above-mentioned problems. Claim 1 of the present invention
The invention according to (1) is an oxygen-absorbing resin composition, characterized in that 100 parts by weight of the thermoplastic resin (A) contain at least the following components (1) to (3) as essential components. (1) 0.001 in terms of metal of the compound T containing a transition metal
~ 2 parts by weight. (2) 0.001 to 2 parts by weight of a photosensitizing compound selected from at least one compound selected from at least one compound containing a benzoyl group or a benzoyl group having a substituent or an azide compound. (3) 0.01 to 20 of at least one compound selected from saturated or unsaturated fatty acids or esterified products thereof, natural fatty acids, natural rubbers, and synthetic rubbers and more decomposable than the thermoplastic resin (A). Parts by weight.

The invention according to claim 2 of the present invention is the oxygen-absorbing resin composition according to claim 1, wherein the thermoplastic resin (A) is at least one of polyethylene, ethylene-α-olefin copolymer. Polyolefins such as α-olefins, α-olefin-ethylene copolymers, polyolefin resins such as ethylene-cyclic olefin copolymers, ethylene-α, β-unsaturated carboxylic acids or esterified products thereof, or ion-crosslinked products thereof, ethylene −
A vinyl acetate copolymer or an ethylene copolymer represented by a partially saponified product or a completely saponified product thereof, or a graft-modified polyolefin resin such as an acid anhydride, polystyrene, polyacrylonitrile or the like alone or a mixture of one or more of these. An oxygen-absorbing resin composition characterized by being present.

The invention according to claim 3 of the present invention is the oxygen-absorbing resin composition according to claim 1 or 2, wherein the compound T containing the transition metal is cobalt, manganese,
Aromatic carboxylic acid salts selected from one or more kinds of iron, nickel, copper, rhodium, vanadium, chromium, zinc, titanium, and cerium, transition metal compound salts such as saturated or unsaturated carboxylic acid salts, acetylacetonato, ethylenediamine An oxygen-absorbing resin composition comprising at least one compound selected from various transition metal complexes such as tetraacetic acid, salen, porphyrin, and phthalocyanine.

The invention according to claim 4 of the present invention is the oxygen-absorbing resin composition according to claim 1, 2 or 3, wherein the transition metal oxidizes the thermoplastic resin (A) by a redox reaction. An oxygen-absorbing resin composition comprising a transition metal A and a transition metal B for promoting a redox reaction of the transition metal A.

The invention according to claim 5 of the present invention is the oxygen-absorbing resin composition according to claim 1, 2, 3 or 4, wherein the oxygen-absorbing mechanism of oxygen-absorbing ability is a catalyst for oxidizing a transition metal salt. Oxidation by heat, or UV or EB
Compounds containing a benzoyl group or a benzoyl group having a substituent or azide compounds generated by irradiating active energy rays such as a saturated or unsaturated fatty acid or its esterified product, esterified product, natural fat, natural An oxygen absorbing resin composition having an oxygen absorbing mechanism that consumes oxygen by a co-oxidation reaction of a decomposable compound selected from rubber and synthetic rubber and a thermoplastic resin (A).

In the invention according to claim 6 of the present invention, the incompatible thermoplastic resin (B) is added to the thermoplastic resin (A) in 9 parts.
An oxygen-absorbing resin composition comprising 9 to 50 wt% and 1 to 50 wt% of the resin composition having oxygen-absorbing ability according to claim 1, 2, 3, 4 or 5.

The invention according to claim 7 of the present invention is characterized in that an oxygen absorbing resin layer using the oxygen absorbing resin composition according to claim 1, 2, 3, 4, 5 or 6 is provided. It is a laminated body.

The invention according to claim 8 of the present invention is the laminated body according to claim 7, wherein:
An oxygen-absorbing resin layer comprising the oxygen-absorbing resin composition according to 4, 5, or 6 is laminated in a thickness range of 5 to 200 μm.

The invention according to claim 9 of the present invention is the laminate according to claim 7 or 8, wherein 100 parts by weight of a thermoplastic resin (C) is provided on at least one side or both sides of the oxygen absorbing resin layer. On the other hand, the laminated body is characterized in that an intervening resin layer containing 0.001 to 2 parts by weight of a compound capable of trapping free radicals generated in the oxygen absorbing process of the oxygen absorbing resin layer is provided.

According to a tenth aspect of the present invention, in the laminate according to the ninth aspect, the thickness (t1) of the oxygen absorbing resin layer and the oxygen absorbing resin layer are provided on at least one side or both sides. The ratio (tC / t1) to the total thickness (tC) of the intervening resin layer is 1.0 or more.

The invention according to claim 11 of the present invention is the laminate according to claim 7, 8, 9 or 10 above, in which the tensile rupture before the oxygen absorption at the tensile rupture elongation before and after the oxygen absorption of the laminated body. The ratio (E2 / E1) of the point elongation E1 to the tensile elongation at break E2 after oxygen absorption is (E2 / E1) ≧
It is a laminated body characterized by being 0.5.

According to a twelfth aspect of the present invention, the laminate according to the seventh, eighth, ninth, tenth or eleventh aspect has an oxygen permeability of 50 cm ³ × 25 μm (thickness) / m ² (area). /
At least one or more barrier layers selected from a thermoplastic resin layer having a pressure of 24 h / (1.01325 × 10 ⁵ Pa) (pressure) or less, a metal foil layer, a metal vapor deposition thermoplastic polymer layer, and an inorganic compound vapor deposition thermoplastic polymer layer. It is a laminated body characterized by having.

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

The invention according to claim 14 of the present invention is a package characterized by being formed from the laminate according to claim 7, 8, 9, 10, 11, 12 or 13.

The invention according to claim 15 of the present invention is the package according to claim 14, which is used as a soft packaging container such as a pouch.

The invention according to claim 16 of the present invention is the package according to claim 14, which is used as a bottle-shaped container.

The invention according to claim 17 of the present invention is the package according to claim 14, which is used as a tray-shaped container or a cup-shaped container.

The invention according to claim 18 of the present invention is the packaging body according to claim 14, 15, 16 or 17, wherein the packaging body is provided with a lid member, and the lid member comprises the lid member according to claims 7 and 8 above. , 9, 10, 11, 12 or 13 is a laminated body.

The invention according to claim 19 of the present invention is the package according to claim 14, 15, 16 or 17, wherein the package comprises a cap or an inner cap, and the cap or inner cap is the above-mentioned claim. A packaging body, which is formed of a laminated body according to 7, 8, 9, 10, 11, 12, or 13.

The invention according to claim 20 of the present invention is the packaging body according to claim 14, 15, 16, 17, 18 or 19, wherein the packaging body is any one of claims 7, 8, 9, 1 above.
A packaging body, which is a composite container of a laminated body according to 0, 11, 12 or 13 and paper.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The oxygen-absorbing resin composition of the present invention has the following (1) to (100) parts by weight of the thermoplastic resin (A).
A resin composition having an oxygen absorbing ability, characterized in that the component described in (3) is blended as at least an essential component. (1) 0.001 in terms of metal of the compound T containing a transition metal
~ 2 parts by weight. (2) At least one of a compound or an azide compound containing a benzoyl group or a benzoyl group having a substituent.
0.001 to 2 parts by weight of a photosensitizing compound selected from one or more species. (3) 0.01 to 20 of at least one compound selected from saturated or unsaturated fatty acids or esterified products thereof, natural fatty acids, natural rubbers, and synthetic rubbers and more decomposable than the thermoplastic resin (A). Parts by weight.

As the thermoplastic resin (A) which is the main component of the resin composition, a polyolefin resin or an ethylene copolymer can be mentioned. For example, low density polyethylene, medium density polyethylene, high density polyethylene,
α-olefin is butene-1, hexene-1, octene-
Ethylene-α-olefin copolymers such as 1,4-methylpentene-1, polypropylene, polybutene-1, poly
Α-olefins such as 4-methylpentene-1 and random polypropylene and block polypropylene
Olefin-ethylene copolymer, or two or more α
Copolymers of olefins such as ethylene-propylene-butene copolymers, propylene-butene copolymers, butene-propylene copolymers, propylene-butene-hexene copolymers can also be used. Also, a polyolefin resin such as an ethylene-cyclic olefin copolymer can be used. As the ethylene-based copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl ester, ethylene- (meth) acrylic acid ethyl ester, ethylene- (meth) acrylic acid n-butyl ester, ethylene -I-butyl (meth) acrylate, t-butyl ethylene- (meth) acrylate, various ion-crosslinked products of ethylene- (meth) acrylic acid, ethylene- (meth) acrylic acid- (meth) acrylic acid ester ternary Ethylene-α, β unsaturated carboxylic acids such as copolymers or esterified products thereof, or ion-crosslinked products thereof, ethylene-vinyl acetate copolymers or partially saponified products thereof, acid anhydrides such as maleic anhydride. Examples of the polyolefin resin include graft-modified polyolefin. Further, polystyrene, polyacrylonitrile, etc. can also be used. If necessary, various components may be copolymerized, and various components such as a copolymer with carbon monoxide and a copolymer with an allyl compound can be selected.

A characteristic of the thermoplastic resin (A) is a polymer having a skeleton of a unit having a small C—H bond dissociation energy such as tertiary carbon. further,
In order to improve the oxygen absorption rate, it is more preferable to control the structure of the thermoplastic resin such that the stereoregularity is isotactic, the crystallinity is low, and the Tg (glass transition point) is low. For example, homopolypropylene resin and polybutene-1 resin are suitable materials because they have tertiary carbon. As a means to further increase the oxygen absorption rate,
If polypropylene, butene-1 and polybutene-1
In that case, by using propylene as a copolymerization component, the crystallinity is lowered, the degree of freedom of free radicals associated with the oxidation reaction in the thermoplastic resin (A) can be improved, and the oxygen absorption rate can be improved. . Similarly, polystyrene has tertiary carbon and is a suitable material as an oxygen absorbing material, but polystyrene has a high Tg and the mobility of the molecular chain is restricted, so that the degree of freedom of advantageous radicals is low. As. However, (hydrogenated) styrene-butadiene rubber, (hydrogenated) styrene-isoprene rubber, etc. obtained by copolymerizing with butadiene or isoprene, or by further hydrogenating the unsaturated bond thereof have Tg
Since it is a material with low oxygen content, it can be said that it is an effective material for oxygen absorption. These materials can be used starting from the styrene site even if the unsaturated bond is saturated by hydrogenation.

As an essential component to be blended with these thermoplastic resins, a compound T containing a transition metal is first mentioned. The compound T containing the transition metal functions as a catalyst of the oxygen absorption mechanism by oxidative decomposition, and is essential in the resin composition having oxygen absorption ability of the present invention. Examples of these transition metals include elements of Groups 3A to 7A, 8 and 1B of the periodic law, and include cobalt, manganese, iron, nickel, copper,
Aromatic carboxylic acid salts selected from one or more kinds of rhodium, vanadium and chromium, transition metal compound salts such as saturated or unsaturated carboxylic acid salts, acetylacetonato, ethylenediaminetetraacetic acid, salen, porphyrin,
Various transition metal complexes such as phthalocyanine, and compounds T composed of these transition metals include aromatic carboxylic acid salts, transition metal compound salts such as saturated or unsaturated carboxylic acid salts, acetylacetonato, ethylenediaminetetraacetic acid, salen, and porphyrin. , Various transition metal complexes such as phthalocyanine. Particularly, saturated or unsaturated fatty acid salts of these transition metals having 10 to 20 carbon atoms are preferable, and various transition metal salts such as stearate, linoleate, and linolenate or derivatives thereof are preferable in terms of handling and cost. . The amount of the transition metal compound T added is 100 parts by weight of the thermoplastic resin.
0.001 to 2 parts by weight in terms of metal. If the amount is less than this amount, the oxygen absorption capacity associated with oxidation decreases. The amount added may be more than this, but the saturation limit is reached, and therefore the required amount is 2 parts by weight.

The compound T containing a transition metal is more preferably a transition metal A in which the transition metal oxidizes the thermoplastic resin (A) by a redox reaction and a transition metal B for promoting the redox reaction of the transition metal A. It is more preferable to include and. The transition metal A is oxidized or reduced by itself to decompose hydroperoxide generated by the polymer oxidation reaction, and R—O. (Radical), R
-OO. (Radical) is produced. However, the rate of oxidation / reduction reaction varies greatly depending on the transition metal,
Either reaction becomes dominant. This content means that the redox cycle does not go efficiently and eventually ends the reaction. In the sense that the oxygen absorption ability is maintained, it is necessary to further mix the transition metal B to make the redox cycle of the transition metal A efficient. A typical combination is transition metal A.
Is iron, the transition metal B for promoting the redox reaction of the transition metal A is copper, and iron is III (trivalent) → II
Reaction of (divalent) is rapid, but II (divalent) → III
(Trivalent) is slow. Then, by adding copper II (divalent), iron II (divalent) → III (trivalent), copper II (divalent)
→ I (monovalent), and the redox cycle of transition metal A rotates efficiently. Even when cobalt is used as the transition metal A, cobalt II (divalent) → III (trivalent) reacts rapidly, but cobalt III (trivalent) → II (2)
Valence) is a slow reaction, and therefore by incorporating iron as the transition metal B, the cobalt redox cycle rotates efficiently. Of course, other combinations than the above may be used.

The following essential components include a photosensitizing compound selected from at least one compound selected from a compound containing a benzoyl group or a benzoyl group having a substituent or an azide compound. These are UV or E
It can be easily decomposed by an active energy ray such as B to form various radicals. It is possible to accompany the oxidative decomposition of the thermoplastic resin starting from the various radicals thus obtained. As typical examples, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4
-Benzoyl-4'methyl-diphenyl sulfide,
Alkylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonylbenzophenone), acetophenone, benzoin, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy- Cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
1- [4- (2-hydroxyethoxy) -phenyl]-
2-Hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl]-
2-morpholinopropan-1-one, 2 methyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6
-Dimethoxybenzoyl) -2,4,4-trimethyl-
Examples thereof include pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The addition amount of these is the same as the resin composition 1 described above.
The photosensitizer P is 0.001 to 2 parts by weight with respect to 00 parts by weight. If it is less than this amount, the oxygen absorption capacity will be reduced. The upper limit is the same as that described in the section of the transition metal compound T.

The following essential components are thermoplastic resins (A) such as saturated or unsaturated fatty acids or their ester compounds, natural fats, compounds of natural rubber, synthetic rubber and the like.
Compounds that are more degradable than the above. This component accelerates the decomposition of the thermoplastic resin (A) by a co-oxidation reaction, and the thermoplastic resin (A), which is usually difficult to oxidize and decompose, is mixed with a compound that easily decomposes, so that the decomposition reaction It is possible to promote. Any of these components may be used as long as they are materials capable of generating a polymer radical effective as a co-oxidation reaction. The compound having an unsaturated bond in the structure is most effective, but these components are not used as the main component for oxygen absorption, and therefore the compound does not have to have many unsaturated bonds in the skeleton. Examples of the unsaturated fatty acid or its esterified product include oleic acid, linolenic acid, linoleic acid, soybean oil, safflower oil, rapeseed oil and olive oil, and natural or synthetic rubber components include isoprene rubber and isoprene-
Various choices such as butadiene rubber, styrene-isoprene rubber and styrene-butadiene rubber can be selected. The compounding amount thereof is 0.01 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If it is less than this, the effect as a trigger is small. If it is more than this, problems such as processing stability and coloring occur.

Although not an essential component, substances which are preferably blended in the oxygen-absorbing resin composition include hindered phenols and phosphorus-based antioxidants. These compounds trap radicals generated by irradiation with UV or EB, and thus have a function of hindering oxygen absorption ability. However, the above-mentioned essential components to be added have a possibility of being easily decomposed by heating, which may cause deterioration of processability. Further, since the thermoplastic resin containing a transition metal has an automatic oxidation mechanism, the oxidation reaction proceeds. Therefore, they may be appropriately blended for the purpose of imparting processability stability, for the purpose of stability of the oxygen absorbing resin, and for the purpose of controlling the oxygen absorbing ability. Representative examples are described below.

Similarly, although it is not an essential component, it is preferable to add it as an oxygen absorbing resin composition.
Examples include various plasticizers. As described above, the easiness of oxidation of the oxygen-absorbing polymer is one of the factors that also affects the mobility of the resin. Therefore, the plasticizer is also an effective additive component in the sense of improving the mobility of the resin. Representative examples thereof include, but are not limited to, various esters such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, and phthalic acid. Further, not only the above-mentioned plasticizer but also a low molecular weight compound such as a polyolefin wax can be blended, and if blended, the molecular mobility of the thermoplastic resin (A) can be appropriately used. It is possible to

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

Although the oxygen absorbing resin composition described above can be used alone, it causes deterioration of the physical properties of the film due to oxidative deterioration. In addition, odor may occur and yellowing may occur. In order to improve it, the oxygen absorbing resin composition is preferably blended with the thermoplastic resin (B).
The thermoplastic resin (B) at this time may be blended in an amount of 1 to 50 wt% with respect to 50 to 99 wt% of the resin composition having an oxygen absorbing ability. If the resin composition having oxygen absorption capacity is less than 1 wt%, the oxygen absorption capacity will be inferior and 50 wt%
%, The physical properties of the film are significantly deteriorated.

At this time, it is preferable that the resin composition (B) is a resin incompatible with the thermoplastic resin (A).
As an index in the case of an incompatible blend system, a solubility parameter can be mentioned. For example, the small method, H
It can be calculated by using a method such as the oy method. The solubility parameter is calculated from the molecular weight, density, and molar attraction constant of the resin, and is calculated by the small method or Hoy.
It is possible to obtain by using the group mol attraction force constant by the method. On the other hand, the solubility parameter does not take intermolecular interactions into consideration, so that it is difficult to use the solubility parameter in the combination of polar polymers. In that case, a combination of resins having no intermolecular interaction such as hydrogen bond, dipole-dipole interaction, ion-dipole interaction, or π-electron-π-electron interaction is preferable.

The reason why the incompatible polymer blend is preferable as the resin composition having oxygen absorbing ability of the present invention is as follows. The oxygen absorption mechanism of the oxygen absorbing polymer is explained by a radical chain reaction in which radical generation by light of a photosensitizing compound, oxidation catalytic action of a transition metal, and co-oxidation reaction of a decomposable compound are combined. That is,
Various free radicals generated in the oxidation process attack the skeleton of the thermoplastic resin, whereby the oxidation reaction progresses in a chain, and as a result, oxygen is absorbed (consumed).

The oxygen-absorbing resin composition of the present invention is made of a thermoplastic resin (A) containing various additives. That is, when the thermoplastic resin (B) is compatible with the thermoplastic resin (A), the additive compounded in the thermoplastic resin (A) is also uniformly dispersed in the thermoplastic resin B, and the thermoplastic resin (A) And the entire composition phase of the thermoplastic resin (B) begins to absorb oxygen due to oxidative decomposition. However,
This content means that the decomposition reaction occurs in the entire resin composition having the oxygen absorption ability as described above, and as a result, the strength physical properties are deteriorated. That is, the fact that the thermoplastic resin (A) and the thermoplastic resin (B) are incompatible
Only the thermoplastic resin (A) containing the small amount of various additives dispersed in the thermoplastic resin (B) undergoes oxidative decomposition for absorbing oxygen to serve as a base thermoplastic resin (B). It is possible to delay the deterioration of the physical properties of the film due to the decomposition into silane or the crosslinking reaction. However, the free radical generated in the thermoplastic resin (A) has a delaying effect on the deterioration of the film physical properties as compared with the case of the compatible system by performing the incompatible polymer blend design, but the resin having the oxygen absorbing ability Since free radicals generated in the composition also migrate to the thermoplastic resin (B), the thermoplastic resin (B) also undergoes a radical chain reaction. Therefore, as a result of a sincere examination to solve this problem, it was confirmed that the oxygen absorption layer is an incompatible blend layer, and the laminated structure described below is the most effective method associated with oxygen absorption. It was

Before exemplifying the laminated constitution, as the thermoplastic resin (B), various resin materials described above as the resin material used for the thermoplastic resin (A) can be used.
Any combination may be used as long as it is a combination of the thermoplastic resin (A) and the thermoplastic resin (B) which is a resin incompatible with the resin used for the thermoplastic resin (A). Further, as described above, the thermoplastic resin (B) is also not an essential component, but it is a hindered phenol as long as it does not affect the resin composition having oxygen absorbing ability which is blended with the thermoplastic resin (B). A phosphorus-based antioxidant may be added.

As a method for producing these resin compositions having oxygen absorption ability, various predetermined compounding amounts set according to the molding method of the final product and the required oxygen absorption ability are used to prepare a ribbon mixer, a tumbler mixer, and a Henschel. Kneading with a single-screw extruder, twin-screw extruder, etc., Banbury mixer, etc. after dry blending with a mixer or the like, or with a predetermined amount blended using each feeder installed in the kneader in advance Using a machine, the melting point of the base thermoplastic resin is 260 ° C or less, preferably 240 ° C or less, more preferably 220 ° C or less.
It can be obtained by kneading at a temperature of ℃ or below.

Further, when designing an incompatible blend, an oxygen-absorbing resin composition is prepared in advance and blended with the thermoplastic resin (B) immediately before molding as described below to form a direct laminate. It does not matter even if a resin composition having an oxygen-absorbing ability is prepared in advance and then compounded with the thermoplastic resin (B), and the final compound thus obtained may be used for the molding described below. .

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

An important item for forming a laminate is to provide a thermoplastic resin (C) layer on at least one side, preferably both sides, of the above-mentioned resin composition having oxygen absorption ability. With respect to parts by weight, a compound capable of scavenging free radicals generated from the oxygen absorption process of the resin composition layer having oxygen absorption capacity as an essential component, 0.001 to
2 parts by weight is included. The compounds that can scavenge this free radical are the hindered phenols and phosphorus-based antioxidants mentioned above. For hindered phenols, pentaerythritol tetrakis [3
-(3,5-di-t-butyl-4hydroxyphenyl)
Propionate], thiodiethylenebis [3- (3,5
-Di-t-butyl-4hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N '.
-Hexane-1,6-diylbis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionamide], diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5. 5 ', 5 "-hexa-t-
Butyl-a, a ', a "-(mesitylene-2,4,6-
Triyl) tri-p-cresol, hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-
Di-t-butyl-4-hydroxybenzyl) -1,3,3
Various compounds such as 5-triazine-2,4,6 (1H, 3H, 5H) -trione can be used. For phosphorus, tris (2,4-di-t-butylphenyl) phosphite, bis [2,2 4-bis (1,1-dimerchiethyl)-
6-Methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis (2,4-di) -T-butylphenyl) pentaerythritol phosphite and the like. In addition, a lactone type antioxidant can also be used.

The thermoplastic resin (C) is an essential layer for maintaining the physical properties of the film of the resin composition having oxygen absorption ability,
It is possible to use the resins described for the thermoplastic resin (A) and the thermoplastic resin (B). As described above, in the resin composition layer having the oxygen absorbing ability, the radical chain reaction proceeds in the thermoplastic resin (A), and the free radicals thereof migrate to the thermoplastic resin (B). The free radicals also migrate to the further laminated thermoplastic resin (C), and finally the physical properties of the film of the laminate are degraded through decomposition / crosslinking reactions. It has been described above that an antioxidant may be added to the thermoplastic resin (A) and the thermoplastic resin (B), but a large amount of the antioxidant is added to the thermoplastic resin (B) in order to maintain the physical properties of the film. Blending greatly affects the rising rate of oxygen absorption. On the other hand, when blending with the thermoplastic resin (C), it is the thermoplastic resin (B) that has an influence even when the migration of the antioxidant is taken into consideration, and the free radicals generated in the oxygen absorption layer are also the thermoplastic resin. Even if it shifts to (C), it is possible for the antioxidant to efficiently consume the radicals and suppress the deterioration of the film physical properties. In this case, the thermoplastic resin (C)
The antioxidant to be blended with is either hindered phenol-based or phosphorus-based, or a total of 0.005 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin. If it is less than this, the deterioration of the physical properties of the film cannot be suppressed. Moreover, the addition amount larger than this will reach the saturation limit.

Not only the antioxidant formulation but also the thickness ratio of the oxygen-absorbing resin layer of the resin composition having oxygen-absorbing ability to the resin layer of the thermoplastic resin (C) is an important factor for maintaining the physical properties of the film. Is. Here, the thickness (t1) of the oxygen absorbing resin layer made of the resin composition having oxygen absorbing ability and the intervening resin layer of the thermoplastic resin (C) provided on at least one side or both sides of the oxygen absorbing resin layer The thickness ratio with respect to the total thickness (tC), that is, (tC / t1) is preferably 1.0 or more. When it is smaller than this, the deterioration of the film physical properties due to the deterioration of the resin composition layer having the oxygen absorption ability is more excellent than the ability of the thermoplastic resin (C) to have the physical properties of compensating the film physical properties of the entire laminate, As a result, the physical properties of the film are deteriorated.

As an index for maintaining the physical properties of the film, the elongation at break E1 of the laminate before oxygen absorption and the elongation at break E2 of the laminate after oxygen absorption in the tensile elongation at break before and after oxygen absorption due to the oxygen absorption capacity are calculated. The ratio (E2 / E1) is (E2 / E1) ≥0.
5 is mentioned. If it is smaller than this, it cannot be said that the physical properties of the film are maintained.

The simple substance of the resin composition having oxygen absorbing ability of the present invention has oxygen absorbing ability, but since the thermoplastic resin constituting the resin composition is a material having high oxygen permeability, it is referred to as oxygen transmitting and absorbing. There is a problem that concertation occurs and oxygen permeation becomes large. In terms of overcoming such problems, at least one layer of the laminate using the resin composition according to the present invention has oxygen permeability [50 cm ³ × 25 μm (thickness).
/ M ² (area) / 24 hours / (1.01325 × 10 ⁵
Pa (pressure)]] or less is preferable. Examples of these materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide 6 and polyamide 6-polyamide 66 copolymer, polyamide resins represented by aromatic polyamide such as MXD6, polyacrylonitrile resin, polyvinyl alcohol resin, Thermoplastic resin layer selected from ethylene-vinyl alcohol copolymer resin and polyvinylidene chloride resin, metal foil layer such as aluminum foil, PVD vapor deposition method of aluminum, silica, alumina or the like, or organosilane such as hexamethylenedisiloxane. And a vapor-deposited thermoplastic resin layer obtained by a CVD vapor deposition method using an acetylene gas or another carbon gas source. Furthermore, in order to improve the gas barrier properties of these vapor deposition layers, particularly PVD vapor deposition, a polyvinyl alcohol / silane compound-based overcoat layer may be provided. Further, various primer layers for improving the adhesion between the vapor deposition layer and the thermoplastic resin layer may be provided.

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

Various constitutional examples of the laminated body in which the oxygen absorbing resin layer of the oxygen absorbing resin composition of the present invention is laminated, and the molding method and use thereof will be described below. In addition, FIG. 4 is a laminated cross-sectional view showing an example of a laminated structure of a laminated body in which the oxygen-absorbing resin layers shown in the laminated structure constitutional example 1 are laminated among various structural examples, and the reference numerals used are as follows. is there. a ... Polyester film layer b ... Inorganic compound vapor deposition film layer (barrier layer) made of alumina or the like c ... Overcoat layer made of polyvinyl alcohol or the like d ... Adhesive layer made of urethane adhesive or the like e ... Polyolefin resin layer f ... Extruded polyolefin resin Layer g ... Resin layer made of thermoplastic resin (C) h ... Resin layer made of thermoplastic resin (B) i ... Oxygen absorbing resin layer j made of thermoplastic resin (A) -based oxygen absorbing resin composition ... Acid anhydride Graft-modified polyolefin resin layer k ... Ethylene-vinyl alcohol copolymer layer 1 ... Aluminum foil m ... Ethylene- (meth) acrylic acid copolymer layer

<Layered Structure Example 1> a / b / c / d / e / f / g / h ・ i / g ・ Laminate molding method: extrusion molding, injection molding, blow molding, etc. ・ Laminate applications: Sheets, bottles, cups, trays, etc. <Layered structure example 2> e / j / k / j / h ・ i / e ・ Laminate molding method: extrusion molding, injection molding, blow molding, etc. ・ Laminate applications: Sheets, bottles, cups, trays, etc. <Layered structure example 3> b / c / d / e / h ・ i / e ・ Molding method: Extrusion lamination, dry lamination, etc. ・ Use: Flexible packaging, lid material <Layered structure example 3> a / d / l / m / h ・ i / e ・ Molding method: Extrusion lamination, etc. ・ Use: Inner cap, etc. <Layered structure example 4> Paper / e / b / c / d / e / h ・ i / e ・ Molding method: Extrusion lamination, etc. ・ Use: Composite paper container, etc.

As described above, the laminate of the present invention obtained in various constitutions can be used as it is for packaging for various purposes. These examples are not limited to the contents described above, and can be developed into various packaging forms. Further, by combining these packaging forms, it becomes possible to form a packaging body that absorbs oxygen.

[0062]

EXAMPLES Specific examples of the present invention are shown below, but the invention is not limited thereto.

The following materials were used to prepare the oxygen absorbing resin composition and a laminate (evaluation sample) using the same. [Thermoplastic Resin (A)]-(A1): Homopolypropylene Resin (MI = 2)-(A2): Propylene-Butene-1 Copolymer Resin (MI
= 4) [Thermoplastic resin (B)]-(B1): ethylene-hexene-1 copolymer (MI =
4) ・ (B2): Homopolypropylene resin (MI = 6) ・ (B3): Maleic anhydride modified polyethylene resin (MI
= 4) [Thermoplastic resin (C)]-C1: ethylene-hexene-1 copolymer-C2: random polypropylene resin [transition metal compound T] -T1: cobalt stearate-T2: iron hydroxystearate-T3: Copper stearate [photosensitizer P] -P1: 2 methyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [degradable compound L] -L1: unsaturated fatty acid ester (soybean oil )

The oxygen absorbing resin composition using the above materials and a laminate (evaluation sample) using the same were prepared and manufactured as follows. First, the thermoplastic resin (A) is added to 10
As an essential transition metal component, 0.2 parts by weight of a transition metal compound T, 0.1 parts by weight of a photosensitizer P, and
1.5 parts by weight of unsaturated fatty acid ester and further processability,
Considering the stability of oxygen absorption capacity, phosphorus-based antioxidants 0.
05 parts by weight and a hindered phenolic antioxidant 0.
025 parts by weight was dry-blended with a tumbler mixer in advance to prepare a twin-screw extruder (φ = 30 mm,
L / D = 49mm), discharge pressure 9kg, 180
Melting and kneading were performed at 50 ° C. at 50 ° C., the compound to be melted was extruded, the obtained compound was air-cooled, and pelletized to prepare a pellet-shaped oxygen-absorbing resin composition. Then, the pelletized oxygen-absorbing resin composition was stored in an aluminum package in which the inert gas had been replaced.

Next, the pellet-shaped oxygen absorbing resin composition and the thermoplastic resin (B) are mixed so that the oxygen absorbing resin composition / the thermoplastic resin (B) = 30/70. The oxygen-absorbing resin layer (film of the film) is extruded from the intermediate layer extruding part of a three-kind three-layer coextrusion cast film forming machine (φ = 65 mm, L / D = 23). Layer) is formed, the thermoplastic resin (C) is extruded from both side layer extruding parts on both sides of the intermediate layer extruding part of the three-kind three-layer coextrusion cast film forming machine to obtain the oxygen absorbing resin. A layered product of a two-kind three-layer coextruded film in which an intervening resin layer made of a thermoplastic resin (C) is formed on both sides of the layer, and an oxygen-absorbing resin layer and the thermoplastic resin (C) on both sides thereof are formed ( Evaluation sample) was created. At that time, no antioxidant was added to the thermoplastic resin (B). Processing temperature by co-extrusion film formation is 240 ° C, processing speed is 50m / mi
It was set to n.

The following materials were used to form the evaluation sample barrier laminate in which the above evaluation sample laminate was provided with barrier properties. [Barrier base material S] S1: Alumina vapor deposition polyester base material (thickness 12 μ
m) (with polyvinyl alcohol / silane coupling agent type overcoat layer) S2: polyester base material (thickness 25 μm) / urethane adhesive / aluminum foil layer (7 μm) These barrier base material layers S1 and S2 in advance In the above, a low density polyethylene film (40 μm) was laminated by a dry lamination method. [Resin resin] ・ Ex1: Low density polyethylene resin (B1: MI = 23,
Extrusion laminate grade)

Using the above laminate and the barrier substrate, a barrier laminate (evaluation sample) was prepared as follows.

On the above-mentioned various barrier substrates S, the above-mentioned laminate (evaluation sample) made of a two-kind three-layer coextruded film of the obtained oxygen-absorbing resin layer and the thermoplastic resin (C) on both sides thereof was prepared. Was laminated by a sand lamination method with a resin for lamination to a thickness of 15 μm. The laminating temperature was 320 ° C. for low density polyethylene and 290 ° C. for random polypropylene.

[Preparation of Evaluation Sample Laminate and Method for Evaluation] Two-kind three-layer coextruded film of the oxygen-absorbing resin layer obtained in the preparation of the above-mentioned evaluation sample and the thermoplastic resin (C) on both surfaces thereof. The laminated body sample obtained by irradiating the laminated body according to (1) with UV (or EB) using a high-pressure mercury lamp so that the irradiation energy was 2000 mJ / cm ² was cut into a size of 100 mm × 100 mm and enclosed in an aluminum pouch, and a vacuum seal machine was used. A vacuum package in which the laminate sample was hermetically sealed was prepared. After that, air (O ₂ = 21%) 10
0 ml was filled, and the oxygen absorption capacity and the strength physical properties of the oxygen absorption capacity resin layer single layer (multilayer film of 2 types and 3 layers) with time of the laminated body sample in the package were evaluated. The oxygen concentration was measured using an oximeter, and the strength properties were measured in Tensilon tensile test mode at a crosshead speed of 50 mm /
The elongation at break was measured at min.

On the barrier substrate S, a laminate of a two-kind three-layer coextruded film of the oxygen-absorbing resin layer obtained in the preparation of the above-mentioned evaluation sample and the thermoplastic resin (C) on both surfaces thereof was formed. Irradiation energy of 20 is applied from the side of the laminate having the oxygen absorbing resin layer to the barrier laminate laminated by the sand lamination method with a high pressure mercury lamp.
The barrier laminate irradiated with UV (or EB) so as to be 00 mJ / cm ² is cut into 220 mm × 220 mm, folded in half and overlapped, and the periphery of the two sides is sealed by an impulse seal machine with a seal width of 10 mm. After sealing, 100 ml of air (O ² = 21%) and adjusting gas (N ₂ = 99%, O ₂ = 1%) are put into the vacuum package.
A pouch-like vacuum package is created by immediately injecting and immediately sealing (sealing under a controlled gas atmosphere) with a vacuum sealing machine having a seal width of 10 mm, and a barrier laminate that forms a package using an oxygen concentration meter. Was evaluated for oxygen absorption capacity over time. The surface area of the package formed of the barrier laminate is about 40,000 mm ² .

<Example 1> The above materials A1, B1, T1 and
Using T2, P1, L1 and C1, a laminate which was an oxygen absorbing resin composition and an evaluation sample was prepared. Oxygen absorbing resin composition / thermoplastic resin (B1) = 30/70
Dry blending so that the blending ratio of the oxygen absorbing resin composition contained in the thermoplastic resin (B1) is 30 wt.
%. An oxygen-absorbing resin layer of this oxygen-absorbing resin composition has a thickness of 25 μm, and an intervening resin layer of thermoplastic resin (C1) has a thickness of 2 μm on both sides of the oxygen-absorbing resin layer.
It was provided at 5 μm. In the thermoplastic resin (C1), 0.2 part by weight of a phosphorus-based antioxidant and 0.1 part by weight of a hindered phenol-based antioxidant are used with respect to 100 parts by weight of the resin (C1).
Parts by weight were compounded. <Example 2> The above materials A2, B1, T1, T2, P1,
In the same manner as in Example 1 except that L1 and C1 were used, an oxygen absorbing resin composition and a laminate as an evaluation sample were prepared. <Example 3> The above materials A1, B1, T2, T3, P1,
In the same manner as in Example 1 except that L1 and C1 were used, an oxygen absorbing resin composition and a laminate as an evaluation sample were prepared.

<Example 4> A barrier substrate S1 is laminated on the laminate obtained in Example 3 to prepare a barrier laminate, and a pouch-like package is prepared using the barrier laminate. It was created and the pouch was evaluated.

Example 5 A lid member was prepared using the barrier laminate prepared in Example 4 above. The package (container) at that time was a barrier container of 3 types and 5 layers consisting of polyethylene, ethylene vinyl alcohol copolymer, and acid anhydride graft-modified polyethylene. The surface area of the lid is 2000
It was 0 mm ² . After filling the contents in the container and hermetically packaging with the lid material, the amount of gas in the head space between the lower surface of the lid material and the upper surface of the contents in the container (adjusting gas: oxygen 1
%) Was adjusted to 50 ml, it was possible to efficiently absorb oxygen in the head space.

<Example 6> The laminated body obtained in Example 3 was cut into a circular shape, which was used inside the cap to form an inner cap by an insert injection plastic molding method. The surface area was about 700 mm ² . The package (container) at that time was a barrier polyethylene terephthalate bottle in which hexamethylenedisiloxane was deposited by a CVD deposition method to form a silica film (barrier film). UV (or EB) irradiation is performed in the state of the cap before filling the contents, and after filling the polyethylene terephthalate bottle with the powder (contents),
The inside of the container was replaced with the adjusted gas (oxygen 1%), and capping was performed. The amount of headspace gas was also 25 ml. Since the effective surface area was small, the oxygen absorption rate was slower than that in Example 5, but finally oxygen could be almost absorbed.

Example 7 Using the laminate produced in the same manner as in Example 3 except that the thermoplastic resin (B) in Example 3 was changed to the thermoplastic resin B3, polyethylene was obtained by injection molding. And a thermoplastic resin B3 as an adhesive resin and an ethylene vinyl alcohol copolymer, and a container having a structure of 5 layers of 3 types was prepared, and the powder (contents) was filled in the container, and then the above-mentioned procedure was performed. Regulating gas (oxygen 1
%), The interior of the container was replaced with a gas, and the container was sealed using a lid member prepared in the same manner as in Example 5 above, and the contents were preserved. The effective surface area of the container occupied by the oxygen-absorbing resin layer was Since it was larger, the ability to absorb oxygen was improved as compared with Example 5.

Comparative Example 1 An oxygen absorbing resin composition and a laminate as an evaluation sample were prepared in the same manner as in Example 3 except that the transition metal compound T was not used.

Comparative Example 2 An oxygen absorbing resin composition and a laminate as an evaluation sample were prepared in the same manner as in Example 3 except that the photosensitizing compound P was not used.

Comparative Example 3 An oxygen absorbing resin composition and a laminate as an evaluation sample were prepared in the same manner as in Example 3 except that the decomposable compound L was not used.

<Comparative Example 4> B as a thermoplastic resin (B)
2. A laminate, which is an oxygen absorbing resin composition and an evaluation sample, was prepared in the same manner as in Example 3 except that C2 was used as the thermoplastic resin (C).

Comparative Example 5 An oxygen absorbing resin composition and a laminate as an evaluation sample were prepared in the same manner as in Example 3 except that the thermoplastic resin (C1) was not mixed with an antioxidant. .

Comparative Example 6 An oxygen absorbing resin composition and a laminate as an evaluation sample were prepared in the same manner as in Example 3 except that the thickness of the intervening resin layer of the thermoplastic resin (C1) was 10 μm. Created. <Comparative Example 7> A pouch-like package was prepared using the barrier laminate obtained by laminating the barrier substrate S1 on the laminate obtained in Comparative Example 1 above, and the pouch was evaluated.

<Comparative Example 8> A pouch-like package was prepared using the barrier laminate obtained by laminating the barrier substrate S1 on the laminate obtained in Comparative Example 2 above, and the pouch was evaluated.

<Comparative Example 9> A pouch-like package was prepared using the barrier laminate obtained by laminating the barrier substrate S1 on the laminate obtained in Comparative Example 3 above, and the pouch was evaluated.

Table 1 shows the prototype constructions of Examples 1 to 3 and Comparative Examples 1 to 6 and the results are shown in Table 2 and FIG.

[0085]

[Table 1]

[0086]

[Table 2]

Of the evaluation results of the pouches obtained in Example 4 and Comparative Examples 7 to 9, the oxygen concentration of 21% is shown in FIG. 2, and the oxygen concentration of 1% is shown in FIG.

[0088]

EFFECT OF THE INVENTION The resin composition having oxygen absorbing ability of the present invention, and the laminate and the packaging body using the same have excellent oxygen absorbing ability and effectively remove oxygen in the head space in the packaging material. It is possible. In addition, Comparative Examples 1 to 1 described above
From 3, it is possible to confirm the influence of the blending of the transition metal compound, the photosensitizing compound, and the decomposable compound on the oxygen absorption capacity. Further, Comparative Examples 4 to 6 show that the incompatible blend design, the compounding recipe of the thermoplastic resin (C) in the laminate, and the layer thickness ratio affect the film physical properties of the laminated film including the oxygen absorbing layer. It could be confirmed.

As described above, the development of the packaging material using the resin composition having oxygen absorbing ability and oxygen absorbing ability with improved physical strength is also confirmed in Examples 5 to 7. It is a thing. In addition, for containers such as pouches using a barrier substrate, the barrier properties of a barrier substrate laminated with an aluminum foil are similar to those of a barrier substrate laminated with an inorganic oxide vapor-deposited layer. Therefore, it is possible to design a packaging material that makes use of the transparency of the inorganic oxide vapor deposition layer and a packaging material that makes use of the complete barrier property of the aluminum foil. Further, it can be applied to any form of packaging material regardless of the molding method of the packaging material.

[Brief description of drawings]

FIG. 1 is a graph showing the oxygen absorption capacity of an oxygen absorption capacity resin composition of the present invention.

FIG. 2 is a graph showing changes in oxygen concentration in the pouch when the filled oxygen gas concentration is 21%.

FIG. 3 is a graph showing changes in oxygen concentration in the pouch when the filled oxygen gas concentration is 1%.

FIG. 4 is a schematic laminated cross-sectional view showing an example of a laminated structure of a package using the laminated body of the present invention.

[Explanation of symbols]

a ... Polyester film layer b ... Inorganic compound vapor deposition film layer (barrier layer) made of alumina or the like c ... Overcoat layer made of polyvinyl alcohol or the like d ... Adhesive layer made of urethane adhesive or the like e ... Polyolefin resin layer f ... Extruded polyolefin resin Layer g ... Resin layer of thermoplastic resin (C) h ... Resin layer of thermoplastic resin (B) i ... Oxygen absorbing resin layer of thermoplastic resin (A) -based oxygen absorbing resin composition

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 101/00 C08L 7:00 7:00) 21:00 (C08L 101/00 21:00) (72) Inventor Akio Kurosawa 1-5-1 Taito, Taito-ku, Tokyo, Toppan Printing Co., Ltd. (72) Inventor Isao Morimoto 1-5-1 Taito, Taito-ku, Tokyo Toppan Printing, Inc. (72 ) Inventor Nobunata Nobunae 1-5-1, Taito, Taito-ku, Tokyo, F-term, Toppan Printing Co., Ltd. (reference) 3E067 AB01 AB49 AB81 AB83 BA01A BA11A BB25A CA06 CA30 FC01 GB13 GD01 3E086 AB01 AD01 AD04 AD05 AD06 AD23 BA04 BA14 BA15 BA35 BB05 CA01 CA28 4F100 AA00C AA19C AA20C AB01C AB02A AB10C AB12A AB13A AB14A AB15A AB16A AB17A AB18A AB33C AH02A AH03A AH08A AK01A AK01B AK01C AK46CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAK27CAKC C AL05A AR00B BA02 BA03 CA09A CA30A CA30B EH66C GB15 GB16 JB16A JB16B JB16C JD01C JD03 YY00A YY00B YY00C 4J002 AC023 AC063 AC083 AE053 BB03W BB05W BB06W BB07W BB08W BB12W BB14W BB15W BB21W BB23W BC03W BE03W BG10W BK00W BP02W CJ00W EE037 EE046 EE047 EF058 EG046 EG076 EN027 EN116 EU026 EW147 FD020 FD203 FD206 FD207 FD208

Claims (20)

[Claims] 1. To 100 parts by weight of the thermoplastic resin (A),
An oxygen-absorbing resin composition comprising the following components (1) to (3) as at least essential components. (1) 0.001 in terms of metal of the compound T containing a transition metal
~ 2 parts by weight. (2) 0.001 to 2 parts by weight of a photosensitizing compound selected from at least one compound selected from at least one compound containing a benzoyl group or a benzoyl group having a substituent or an azide compound. (3) 0.01 to 20 of at least one compound selected from saturated or unsaturated fatty acids or esterified products thereof, natural fatty acids, natural rubbers, and synthetic rubbers and more decomposable than the thermoplastic resin (A). Parts by weight. 2. The thermoplastic resin (A) is polyethylene, an ethylene-α-olefin copolymer, a poly-α-olefin consisting of at least one α-olefin, an α-olefin-ethylene copolymer, an ethylene-cyclic olefin copolymer. Polyethylene resin such as polymer, ethylene-α, β-unsaturated carboxylic acid or its esterified product, its ionically cross-linked product, ethylene-vinyl acetate copolymer or its partially saponified or fully saponified ethylene-based copolymer 2. The oxygen-absorbing resin composition according to claim 1, which is a combination, or a graft-modified polyolefin resin such as an acid anhydride, a single substance such as polystyrene and polyacrylonitrile, or a mixture of one or more of these. 3. The compound T containing a transition metal is an aromatic carboxylate selected from the group consisting of cobalt, manganese, iron, nickel, copper, rhodium, vanadium, chromium, zinc, titanium and cerium, saturated or A transition metal compound salt such as an unsaturated carboxylic acid salt, or one or more compounds selected from various transition metal complexes such as acetylacetonato, ethylenediaminetetraacetic acid, salen, porphyrin and phthalocyanine. Alternatively, the oxygen-absorbing resin composition according to item 2. 4. The transition metal comprises a transition metal A which oxidizes a thermoplastic resin (A) by a redox reaction and a transition metal B which promotes the redox reaction of the transition metal A. Item 2. The oxygen-absorbing resin composition according to Item 1, 2 or 3. 5. The oxygen absorption mechanism of the oxygen absorption capacity is autoxidation by heat using a transition metal salt as an oxidation catalyst, or UV.
Saturated or unsaturated fatty acid or its esterified product, esterified product, natural fat by various radicals derived from a compound containing a benzoyl group or a benzoyl group having a substituent or an azide compound generated by irradiation with active energy rays such as EB and EB 5. An oxygen absorption mechanism that consumes oxygen by a co-oxidation reaction of a thermoplastic resin (A) with a decomposable compound selected from natural rubber, synthetic rubber, and synthetic rubber. The oxygen absorbing resin composition of. 6. An incompatible thermoplastic resin (B) is contained in an amount of 99 to 50 wt% with respect to the thermoplastic resin (A).
An oxygen-absorbing resin composition comprising 1 to 50 wt% of the resin composition having the oxygen-absorbing ability described in 2, 3, 4, or 5. 7. A laminate comprising an oxygen absorbing resin layer comprising the oxygen absorbing resin composition according to claim 1, 2, 3, 4, 5, or 6. 8. An oxygen-absorbing resin layer comprising the oxygen-absorbing resin composition according to claim 1, 2, 3, 4, 5, 6 having a thickness of 5 to 5.
The laminated body according to claim 7, which is laminated in a range of 200 μm. 9. Free radicals generated during the oxygen absorption process of the oxygen absorbing resin layer can be trapped on at least one side or both sides of the oxygen absorbing resin layer with respect to 100 parts by weight of the thermoplastic resin (C). 0.001-2 compounds
9. The laminate according to claim 7, further comprising an intervening resin layer mixed by weight. 10. A thickness (t1) of the oxygen absorbing resin layer,
The ratio (t) to the total thickness (tC) of the intervening resin layer provided on at least one side or both sides of the oxygen absorbing resin layer.
C / t1) is 1.0 or more, The laminated body of Claim 9 characterized by the above-mentioned. 11. The tensile elongation at break E1 before oxygen absorption in the tensile elongation at break before and after oxygen absorption of the laminate,
Ratio with tensile elongation at break E2 after absorbing oxygen (E2 / E1)
Is (E2 / E1) ≥0.5, the laminate according to claim 7, 8, 9 or 10. 12. The laminate has an oxygen permeability of 50 cm ^3.
× 25 μm (thickness) / m ² (area) / 24 h / (1.01
At least one barrier layer selected from a thermoplastic resin layer having a pressure of 325 × 10 ⁵ Pa) (pressure) or less, a metal foil layer, a metal-deposited thermoplastic polymer layer, and an inorganic compound-deposited thermoplastic polymer layer. Claims 7, 8, 9,
The laminated body according to 10 or 11. 13. The barrier layer is a thermoplastic resin layer selected from a polyester layer, a polyamide layer, a polyacrylonitrile layer, a polyvinyl alcohol layer, an ethylene-vinyl alcohol copolymer layer, a polyvinylidene chloride layer, a metal such as an aluminum foil. The laminate according to claim 12, which is selected from at least one or more of various thermoplastic polymer layers provided with a foil layer, an aluminum vapor deposition layer, a silica vapor deposition layer, and an alumina vapor deposition layer. 14. A package formed from the laminate according to claim 7, 8, 9, 10, 11, 12 or 13. 15. The package according to claim 14, which is used as a soft packaging container for pouches or the like. 16. The package according to claim 14, which is used as a bottle-shaped container. 17. The package according to claim 14, which is used as a tray-shaped container or a cup-shaped container. 18. The packaging body is provided with a lid member, and the lid member is formed of the laminate according to claim 7, 8, 9, 10, 11, 12 or 13. 14,
The package according to 15, 16 or 17. 19. The packaging body includes a cap or an inner cap, and the cap or the inner cap is formed from the laminated body according to claim 7, 8, 9, 10, 11, 12 or 13. The package according to claim 14, 15, 16 or 17. 20. The packaging body according to claim 7, 8, 9, 1
The composite container of the laminated body according to 0, 11, 12 or 13 and paper, 14.
The package according to 7, 18 or 19.