JPH06255679A - Laminated container for storing colored food - Google Patents

Abstract

PURPOSE:To provide a laminated container for storing colored food that does not discolor even when colored food, such as a vegetable or a fruit, is stored, which is suitable for recycling because it does not discolor in a recycling process, and that is excellent in oxygen barrier properties. CONSTITUTION:A laminated container for storing colored food comprises an internal layer and an oxygen barrier resin layer. The internal layer is composed of a polyolefine resin composition consisting of the following components: (a) 100 parts by weight polyolefin resin that substantially contains no phenolic antioxidant; (b) 0.01-1 part by weight hindered amine light stabilizer; (c) 0.01-0.5 parts by weight aromatic phosphite or aromatic phosphite antioxidant. Here, (d) is a polyamid resin layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated container for storing colored foods which is resistant to discoloration even when storing colored foods such as vegetables and fruits and which has an excellent oxygen barrier property.

[0002]

2. Description of the Related Art Polyolefin resin has excellent moldability,
Since it is a general-purpose resin that also has hygiene, it is used by forming various food containers by blow molding, sheet molding or extrusion molding into a film shape, thermoforming such as vacuum and pressure, and laminating. ing. However, although polyolefin has an excellent ability to block water vapor, it has an insufficient ability to block oxygen, which limits its use as a long-term food container. recent years,
As a method for improving the oxygen barrier property of polyolefin, a laminate with a resin excellent in oxygen barrier property such as a saponified product of ethylene / vinyl acetate copolymer or polyvinylidene chloride has been proposed. This has made polyolefin containers even more excellent and widely used. On the other hand, polyolefin resins are generally susceptible to thermal oxidative deterioration due to their chemical structure, and cannot withstand the heat during processing and use. Therefore, usually, a product that can withstand practical use can be obtained for the first time by incorporating an antioxidant into the polyolefin resin to suppress thermal deterioration. In particular, in order to prevent sagging due to a decrease in melt tension at the time of blow molding or sheet vacuum or pressure molding, or in order to prevent heat deterioration during heat sterilization processing after filling food or during microwave oven cooking,
Incorporation of an antioxidant is essential.

[0003]

However, such a container made of a polyolefin resin in which an antioxidant is mixed to suppress thermal deterioration is not suitable for storing colored foods such as spinach, Chinese cabbage and other vegetables and fruits. In addition, there is a drawback that the polyolefin resin container is discolored by contact with the colored food. Further, recently, due to the effective use of resources, there is an increasing demand for recycling of polyolefin resin containers. Therefore, when attempting to recycle a polyolefin resin container laminated with such an oxygen-blocking resin, It has been found that when the barrier resin and the polyolefin resin are melted and kneaded to be processed into various molded products for use, these resin-fat mixtures cause a severe discoloration. Such a severe discoloration
It may be caused by the reaction between the oxygen barrier resin (especially the discoloration is severe when mixed with a saponification product of ethylene / vinyl acetate copolymer and polyvinylidene chloride resin) and the residual catalyst in the polyolefin resin. Be done. Therefore,
In order to reuse the polyolefin resin as a food container, it is absolutely necessary to overcome such a problem of discoloration. The present invention is unlikely to cause discoloration due to contact with such a colored food, has excellent food storability, and has excellent heat deterioration resistance during processing, and further, discoloration even when recycled. It is intended to provide a laminated container for colored foods with a small amount.

[0004]

[Means for Solving the Problems]

[Summary of the Invention] The present inventors have conducted intensive studies in view of the above problems, and as a result, instead of a phenol-based antioxidant,
A mixture of specific additives prevents oxidative deterioration of the polyolefin resin that does not contain phenolic antioxidant, and prevents sagging due to thermal deterioration and decrease in melt tension during vacuum or pressure molding. Moreover, it was found that the discoloration can be prevented even by kneading with an oxygen-blocking resin even when it is contacted with colored food or recycled, and thus the present invention has been completed. is there. That is, the laminated container for colored food of the present invention is a laminated container comprising an inner layer for storing colored food and an oxygen barrier resin layer, wherein the inner layer is a polyolefin resin comprising the following components (a) to (c): A laminated container for storing colored food, which is formed from the composition. Component (a): Polyolefin resin that does not substantially contain phenolic antioxidant: 100 parts by weight Component (b): Hindered amine light stabilizer: 0.01 to 1 part by weight Component (c): Aromatic sub Phosphate ester and / or aromatic phosphite antioxidant: 0.01 to 0.5 part by weight

[Detailed Description of the Invention] [I] Laminated container for storing colored food (A) Inner layer for storing colored food In the laminated container for colored food of the present invention, the inner layer for storing colored food is It is important to use a polyolefin resin composition as the material. (1) Polyolefin resin composition [components]

(A) Polyolefin Resin Component (Component (a)) The polyolefin resin component (component (a)) constituting the polyolefin resin composition used in the inner layer of the colored food laminated container of the present invention is ethylene, Propylene, 1
-Butene, 1-pentene, 1-hexene, 4-methylpentene-1, α-olefin homopolymer, α-olefin homologs or random copolymers of these α-olefins and other copolymerizable monomers, It includes a block copolymer, an alternating copolymer, a graft copolymer and the like. The other copolymerizable monomer copolymerized with the α-olefin,
For example, vinyl ester such as vinyl acetate, acrylic acid,
Examples thereof include unsaturated organic acids such as maleic anhydride and acrylic acid esters, and their esters. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, propylene homopolymer, propylene / ethylene random and block copolymers, propylene / 1-butene copolymer Examples include polymer, propylene / ethylene / 1-butene copolymer, poly-4-methylpentene-1 and the like. Among the above, preferred polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, propylene homopolymer, propylene / ethylene random and block copolymers, propylene / Examples thereof include 1-butene copolymers and propylene / ethylene / 1-butene copolymers. Among them, propylene homopolymers and propylene / ethylene random copolymers are preferably used as food containers.

The MFR of these polyolefin resins is generally 0.1 to 50 g / 10 min, especially 0.2 to 10 g / 1.
It is preferable to use those showing 0 minutes. If the MFR exceeds the above range, melt tension and mechanical strength tend to be insufficient, which is not preferable. On the other hand, if it is less than the above range, the melt viscosity becomes high and the molding processability is deteriorated, which is not preferable. It is important that these polyolefin resins are substantially free of phenolic antioxidants. The presence of the phenolic antioxidant in the polyolefin resin is unfavorable because it hinders the development of the effects of the present invention.
In addition, "substantially" here means that it may be contained in a range that does not significantly impair the curing of the present invention.

(B) Hindered amine light stabilizer (component (b)) As a hindered amine light stabilizer (component (b)) constituting the polyolefin resin composition used as the inner layer of the laminated container for colored food of the present invention, , [1] to [11] shown below
And the like. [1] dimethyl succinate and 1- (2-hydroxyethyl)
Polycondensate with -4-hydroxy-2,2,6,6-tetramethylpiperidine [2] Poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5- Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} [ 3] Bis (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid
2,6,6-Pentamethyl-4-piperidyl) ester [4] Tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) 1,2,3,4-butanetetracarboxylate [5] bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [6] N, N'-bis (2,2,2 6,6-Tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-
Polycondensate with dibromoethane [7] Poly [2-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine-4- (N-morpholino) symtriazine [ 8] 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone) [9] tris (2,2,6,6-tetramethyl-4-piperidyl ) -Dodecyl-1,2,3,4-butanetetracarboxylate [10] tris (1,2,2,6,6-pentamethyl-
4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate [11] bis (1,2,2,6,6-pentamethyl-4
-Piperidyl) sebacate Among these, those having a molecular weight of 500 or more are particularly preferable because compatibility and excellent effects can be exhibited. The most suitable compounds among these are [1], [2], and [4] above.
And the compounds listed in [7].

(C) Aromatic phosphite and / or aromatic phosphite antioxidant (component (c)) Aromatic constituting the polyolefin resin composition used as the inner layer of the laminated container for colored food of the present invention Examples of the phosphite and / or aromatic phosphite antioxidants include the compounds [12] to [20] shown below. [12] Tris (mixed, mono and dinonylphenyl) phosphite [13] Tris (2,4-di-t-butylphenyl) phosphite [14] 4,4'-butylidene bis (3-methyl-6- t
-Butylphenyl-di-tridecyl) phosphite [15] 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane [16] bis (2,4 -Di-t-butylphenyl) pentaerythritol-di-phosphite [17] tetrakis (2,4-di-t-butylphenyl)
-4,4'-Biphenylene phosphonite [18] bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite [19] 2,2'-ethylidene bis (4 6-di-t-butylphenyl) fluorophosphite [20] methylenebis (4,6-di-t-butylphenyl) -2-ethylhexylphosphite Among these, [13], [17], [18], It is preferable to use the compounds [19] and [20], especially the compounds [13] and [17].

(D) Additional component (component (d): optional component) In the polyolefin resin composition used as the inner layer of the colored food laminated container of the present invention, within a range not significantly impairing the effects of the present invention, In addition to the above essential components (a) to (c), an optional additional component (component (d): optional component) can be blended. Regarding the above-mentioned additional components, specifically, a neutralizing agent, an ultraviolet absorber, a crystal nucleating agent, an antifoaming agent, a dispersant, which is mixed with a usual polyolefin,
Examples thereof include antistatic agents, lubricants, molecular weight modifiers (peroxides), various auxiliaries such as colorants, and various inorganic fillers such as talc, calcium carbonate and glass fibers.

[Composition Ratio] It is important that the composition ratio of each component of the polyolefin resin composition used as the inner layer of the colored food laminated container of the present invention is as follows.
The blending amount of the hindered amine light stabilizer of the component (b) is 0.01 to 1 part by weight based on 100 parts by weight of the polyolefin,
It is preferably 0.02 to 0.5 part by weight, particularly preferably 0.03 to 0.3 part by weight. If the blending amount of the component (b) is less than the above range, the heat resistance will be insufficient. Further, if it exceeds the above range, not only is it uneconomical, but also problems of discoloration and bleeding occur. The blending amount of the aromatic phosphite ester and / or the aromatic phosphite antioxidant as the component (c) is 0.01 to 0.5 parts by weight, preferably 0.03 to 0. 3 parts by weight, particularly preferably 0.05 to 0.2 parts by weight. If the blending amount of the component (c) is less than the above range, the stabilizing effect during molding is poor and the melt tension and mechanical properties of the polyolefin are lowered. Further, if it exceeds the above range, not only is it uneconomical, but also problems of discoloration and bleeding occur.

[Mixing / Melting / Kneading] (a) Mixing / Melting / Kneading Device The above-mentioned components are used for producing the polyolefin resin composition which is a material for forming the inner layer of the laminated container for colored food of the present invention. Component (a) to component (c), optionally a component
It can be obtained by blending (d) in the above composition ratio and mixing, melting and kneading. The above-mentioned mixing, melting and kneading are usually performed by a Henschel mixer, a super mixer,
V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, uniaxial or biaxial kneading extruder or the like is mixed or melt-kneaded, and this is processed into a desired molding product by a molding machine such as an extrusion molding machine. Is preferred. At this time, it is also possible to employ a so-called masterbatch system in which the polyolefin resin is preliminarily blended with a larger amount of the compound than the target amount and the compound is molded while being diluted with the polyolefin resin. (b) Melting / kneading conditions The components of the polyolefin resin composition are melted / kneaded as described above.
Melting / kneading is performed using a kneading device. The melting and kneading conditions are generally 190 to 280 ° C, preferably 200 to 260 ° C, and particularly preferably 210 to 240 ° C.
Melting and kneading are performed at the temperature of.

(2) Thickness Using the above-mentioned polyolefin resin composition as a raw material, the inner layer of the laminated container for colored food of the present invention which will come into contact with food is formed. The thickness of the inner layer is not particularly limited, but is generally 1 to 3,000 μm, preferably 2 to
The thickness is 2,000 μm, particularly preferably 3 to 1,500 μm.

(3) Colored foods The colored foods stored in the inner layer of the laminated container for colored foods of the present invention include spinach, Chinese cabbage, cabbage, carrots, radish, spring chrysanthemum, kelp and other vegetables, and umeboshi, fruits, Examples thereof include foods having pigments such as seaweed and processed foods thereof. The term "colored food" as used herein means a food that causes a contact surface of the polyolefin to develop a color or discolor when contacted with the polyolefin.

(B) Oxygen-blocking resin layer (1) Material As a material for forming the oxygen-blocking resin layer in the laminated container for colored food of the present invention, a saponified ethylene / vinyl acetate copolymer, poly Examples thereof include vinyl alcohol resins, polyvinylidene chloride resins, copolymers of polyvinylidene chloride and acrylic ester derivatives, polyester resins, polyamide resins, and acrylonitrile resins. Commercially available products can be used as they are. Among these, preferred are saponified products of ethylene / vinyl acetate copolymers, polyvinylidene chloride resins and polyamide resins, and particularly preferred are saponified products of ethylene / vinyl acetate copolymers.

(2) Thickness The thickness of the oxygen-blocking resin layer is generally 10 to 150 μm, preferably 20, from the viewpoint of oxygen blocking effect and cost.
˜100 μm, particularly preferably 30-70 μm.
If the thickness of the oxygen barrier resin layer is less than the above range, the oxygen barrier effect is insufficient. Further, if the amount exceeds the above range, the material cost increases, which is not preferable.

(C) Other Layers (1) Material The laminated container for colored food of the present invention is basically a laminated container comprising an inner layer for accommodating colored food and an oxygen barrier resin layer, Furthermore, an adhesive resin layer for adhering both layers, a layer using a recycled material, another polyolefin resin layer,
It is also possible to have a layer structure in which layers such as a resin layer other than the polyolefin resin and a colored layer are provided. (2) Thickness The thickness of the above-mentioned other layers is preferably 3,000 μ in general.
m or less, preferably 5 to 2,000 μm.

[II] Manufacture of laminated container for storing colored food (1) Forming The laminated container for colored food of the present invention is a hollow forming machine equipped with a multi-layer extruder using a multi-manifold or a feed block, sheet forming. Although it can be manufactured by using a molding machine such as a molding machine or a film molding machine, it can also be manufactured by stacking single-layer sheets. When such single-layered sheets are laminated and manufactured, they can also be formed by a vacuum, compressed air, or vacuum-compressed thermoforming method using a normal differential pressure. In particular, when forming into a deep-drawing container, plug assist may be performed. When laminating single layer films,
After being subjected to post-treatment such as heat bonding and high frequency bonding, they are laminated and molded as a laminated container. Among these, the method of producing a thermoformed container by multi-layer sheet molding can bring out the effects of the present invention most remarkably, and therefore, the method of producing the thermoformed container is most preferable. Further, the resin layer made of oxygen barrier is not limited to the above-mentioned multilayer extrusion molding, but it may be produced alone or as a laminate with a polyolefin,
The laminated container for storing colored food of the present invention can also be manufactured by laminating the molded product formed of the polyolefin composition used for the inner layer of the laminated container of the present invention.

(2) Laminated Container for Colored Food As shown in FIG. 1, the laminated container for colored food of the present invention obtained by the above molding has a multi-layered structure in which the side wall portion constituting the container is composed of at least two layers. It is formed, and the overall shape thereof includes various shapes such as a circular or angular cylindrical container, a dish-shaped container, and a bag-shaped container. These containers are used as barrels, containers for transportation, containers on the table, and the like.

[III] Reuse of Laminated Container for Storage of Colored Food The laminated container for colored food of the present invention has a polyolefin resin composition layer and a resin oxygen-blocking resin layer which are substantially free of a phenolic antioxidant. Although it is a laminated container consisting of and, even if these containers are crushed, melted and kneaded and processed into various molded products when these containers are recovered and recycled for effective use of resources, these resin fat mixtures Almost no discoloration occurs and no coloring problems occur, so it can be reused with confidence.

[0021]

EXAMPLES In order to describe the laminated container for storing colored food of the present invention in more detail, the present invention will be described more specifically by showing experimental examples below. [I] Raw materials The raw materials used here are as follows. Examples 1 to 5 and Comparative Examples 1 to 5 and 7 to 9 MFR is 1.4 g / 10 min (measured by the method of JIS-K7210), and the density is 0.905 g / cc (JIS-K7.
Propylene homopolymer 100 (measured by the method 112)
Blended with the components and amounts shown in Table 1 with respect to parts by weight,
Mix for 3 minutes with a super mixer made by Kawata Co., Ltd.
A propylene polymer composition was obtained by melting and kneading with an extruder having a screw diameter of 50 mm heated to 30 ° C. This composition was put into a feed block having three types and five layers from an extruder heated to 250 ° C. and having a screw diameter of 90 mm to form both outer layers. Separately, as an oxygen barrier resin, saponified ethylene / vinyl acetate copolymer (trade name: Eval F10 manufactured by Kuraray Co., Ltd.)
1) was put into a feed block from an extruder having a screw diameter of 40 mm heated to 250 ° C. to form an innermost layer. Furthermore, as an adhesive resin layer, "MODIC P3" manufactured by Mitsubishi Petrochemical Co., Ltd.
00F ”heated to 250 ° C. and fed from the extruder with a screw diameter of 40 mm to both outer layers and innermost layer of the feed block.
Put in one middle layer. These were extruded with a T-shaped die having a width of 750 mm, sandwiched between two casting drums (having a hard chrome plating process) in which hot water of 60 ° C. circulates, and cooled and solidified to produce a laminated sheet. . The thickness of the laminated sheet layer is 450 for each layer of the composition.
μm, the oxygen barrier resin layer is 50 μm, and the adhesive resin layers are 50 μm.

The oxygen transmission rate (AS
(TM D3985, measured at 23 ° C.-0% RH-1 atm) and 120 ° C. in a gear oven to measure deterioration time. The results are shown in Table 1. Next, this laminated sheet was heated by a far-infrared heater with a pressure molding machine manufactured by Asano Laboratory Co., Ltd., and the pressure was 3 kg / cm ² and the diameter was 8 c.
A round container having a diameter of m and a depth of 4 cm was formed. This container was crushed and applied to a strand extruder having a screw diameter of 40 mm heated to 230 ° C., and as a recycled material, it was applied to an injection molding machine at 230 ° C. to form a sheet having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm. The degree of discoloration was visually observed and judged. Further, the Chinese cabbage soup mixed in a mixer was put in another container and stored at 30 ° C. for 5 days. After that, the contents were taken out, washed with water, and the degree of food discoloration of the container was visually observed and judged. The criteria for judging discoloration when mixed with the above-mentioned recycled material and the criteria for judging discoloration during storage of colored foods were as follows. A: Almost no change is observed. ◯: Discolored a little. Δ: Discoloration is clearly present. X: The color changes considerably.

Comparative Example 6 A sheet and a container were molded in the same manner as in Example 1 except that the oxygen barrier resin was not used. Then, the discoloration of the sheet and the container was evaluated. The results are shown in Table 1. Example 6 The propylene polymer composition of Example 1 was heated at 250 ° C. in an extruder having a screw diameter of 90 mm to obtain a T having a width of 750 mm.
When the propylene homopolymer film (25 μm) was extruded with a mold die and cooled and solidified with the same casting drum as in Example 1, both sides of a vinylidene chloride resin film (25 μm, Saran UB manufactured by Asahi Kasei Co., Ltd.) were dry-laminated in advance. The laminated three-layer film and the propylene polymer composition were heat-bonded to form a laminated sheet.
Similar to Example 1, this sheet was molded into a container so that the resin film was on the outside of the container, and evaluated. The results are shown in Table 1.
Shown in.

Example 7 In the same manner as in Example 1, 100 parts by weight of a propylene / ethylene random copolymer having an MFR of 1.8 g / 10 min and a density of 0.899 g / cc (ethylene content 3% by weight) was used. On the other hand, the components and amounts shown in Table 2 were blended to give a propylene polymer composition, and the propylene polymer composition was applied to an extruder heated to 230 ° C. and having a screw diameter of 40 mm. Also, in the same manner, the MFR was 0.5 g / 10 min and the density was 0.904 g /
A screw was prepared by blending 100 parts by weight of cc of propylene / ethylene block copolymer (ethylene content 4% by weight) with the components and amounts shown in Table 2 to obtain a propylene polymer composition, which was heated to 250 ° C. It was put into an extruder having a diameter of 90 mm. Separately, an oxygen-blocking polyamide resin (MXD-6 manufactured by Mitsubishi Gas Chemical Co., Inc.) was applied to an extruder having a screw diameter of 40 mm heated to 250 ° C. Further, the adhesive resin was extruded with the same resin and method as in Example 1. Then, each extruder was put into a feed block having a four-layer, seven-layer structure, and as shown in FIG. 1, propylene / ethylene random copolymer / propylene / ethylene block copolymer / adhesive resin / polyamide resin / adhesiveness Resin / propylene / ethylene block copolymer / propylene / ethylene random copolymer = 50 μm / 400 μm / 50
7 μm / 50 μm / 50 μm / 400 μm / 50 μm
Layered so as to have a layered structure and molded in the same manner as in Example 1 through a T die having a width of 750 mm, and the total thickness is 1050 μm.
Was produced. Next, this laminated sheet was heated with a far infrared heater in a vacuum forming machine manufactured by Asano Laboratory Co., Ltd. to form a round container having a diameter of 8 cm and a depth of 4 cm. The oxygen permeability of this laminated sheet, the deterioration time and the food discoloration property of the container were measured in the same manner as in Example 1. The results are shown in Table 2.

[0025]

[Table 1]

Component [1]: dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-
Polycondensate with tetramethylpiperidine Component [2]: Poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imino]} component [4]: tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate component [13]: tris (2,4-di-t-butylphenyl)
Phosphite Component [17]: Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite Component [21]: Tetrakis [methylenebis-3- (3 ', 5)
′ -Di-t-butyl-4′-hydroxyphenyl) propionate] methane component [22]: butylhydroxytoluene component [23]: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole

[0027]

[Table 2]

[0028]

EFFECTS OF THE INVENTION The laminated container for storing colored food of the present invention has excellent oxygen barrier properties, does not change color even when storing colored food such as vegetables and fruits, and is unlikely to change color during reprocessing. It is also a container that is suitable for recycling and is extremely useful industrially.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of a side wall portion constituting a laminated container for storing colored food according to an embodiment of the present invention.

[Explanation of symbols]

 a propylene / ethylene random copolymer layer b propylene / ethylene block copolymer layer c adhesive resin layer d polyamide resin layer

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[Procedure amendment]

[Submission date] June 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

Means for Solving the Problem [Summary of the Invention] As a result of intensive studies conducted by the present inventors in view of the above problems, as a result, instead of a phenol-based antioxidant,
A mixture of specific additives prevents oxidative deterioration of the polyolefin resin that does not contain phenolic antioxidant, and prevents sagging due to thermal deterioration and decrease in melt tension during vacuum or pressure molding. In addition, it was found that the discoloration can be prevented even by kneading with an oxygen-blocking resin even when contacting with colored food or recycling, and the present invention has been completed. is there. That is, the laminated container for colored food of the present invention is a laminated container composed of an inner layer for containing colored food and an oxygen barrier resin layer, the inner layer comprising a polyolefin resin comprising the following components (a) to (c): A laminated container for storing colored food, which is formed from the composition. Component (a): Polyolefin resin substantially free of phenolic antioxidant: 100 parts by weight Component (b): Hindered amine light stabilizer: 0.01 to 1 part by weight Component (c): Aromatic Phosphite and / or aromatic phosphonite antioxidant: 0.01 to 0.5 part by weight

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

(C) Aromatic phosphite ester and / or aromatic phosphonite antioxidant (component (c)) An aroma constituting the polyolefin resin composition used as the inner layer of the laminated container for colored food of the present invention. Examples of the group phosphite and / or aromatic phosphonite antioxidants include the compounds [12] to [20] shown below. [12] Tris (mixed, mono and dinonylphenyl) phosphite [13] Tris (2,4-di-t-butylphenyl) phosphite [14] 4,4'-butylidene bis (3-methyl-6-
t-Butylphenyl-di-tridecyl) phosphite [15] 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane [16] bis (2,2 4-di-t-butylphenyl) pentaerythritol-di-phosphite [17] tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite [18] bis (2,6) -Di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite [19] 2,2'-ethylidene bis (4,6-di-t-
Butylphenyl) fluorophosphite [20] methylenebis (4,6-di-t-butylphenyl) -2-ethylhexylphosphite Among these, [13], [17], [18], [1]
It is preferable to use the compounds [9] and [20], especially the compounds [13] and [17].

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[Composition Ratio] It is important that the composition ratio of each component of the polyolefin resin composition used as the inner layer of the colored food laminated container of the present invention is as follows.
The amount of the hindered amine-based light stabilizer as the component (b) is 0.01 to 1 part by weight, preferably 0.02 to 0.5 part by weight, particularly preferably 0.03 to 0. 3 parts by weight. If the blending amount of the component (b) is less than the above range, the heat resistance is not sufficient. Further, if it exceeds the above range, not only is it uneconomical, but also problems of discoloration and bleeding occur. The blending amount of the aromatic phosphite ester and / or the aromatic phosphonite antioxidant as the component (c) is 0.01 to 0.
5 parts by weight, preferably 0.03 to 0.3 parts by weight, particularly preferably 0.05 to 0.2 parts by weight. If the blending amount of the component (c) is less than the above range, the stabilizing effect during molding is poor and the melt tension and mechanical properties of the polyolefin are reduced. Further, if it exceeds the above range, not only is it uneconomical,
Discoloration and bleeding problems occur.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitoshi Inagaki 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A laminated container comprising an inner layer for storing a colored food and an oxygen barrier resin layer, the inner layer comprising the following components:
A laminated container for storing colored food, which is formed from a polyolefin resin composition comprising (a) to (c). Component (a): Polyolefin resin that does not substantially contain phenolic antioxidant: 100 parts by weight Component (b): Hindered amine light stabilizer: 0.01 to 1 part by weight Component (c): Aromatic sub Phosphate ester and / or aromatic phosphite antioxidant: 0.01 to 0.5 part by weight