JP2020158129A - Products with packaging - Google Patents

Abstract

The object of the present invention is to provide a product which uses a packaging container having a high gas barrier property to maintain the quality of the contents at a high level and which allows the contents to be easily taken out. A packaging container (A) comprising a multilayer structure (a) having a gas barrier layer containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 mol % or more and 60 mol % or less; ) and a gel content (C) in the sealed space, wherein the hardness T of the packaging container (A) measured in accordance with ISO527-1 and , The product, wherein the gel content (C) has a hardness U ratio T/U of 1,000 or more and 100,000 or less. [Selection drawing] Fig. 1

Description

The present invention relates to a product including a packaging container having a gas barrier property and a gel-like content.

For the container of gel-like contents such as tofu, jelly, and pudding, a sheet made of various resins (for example, olefin resin such as polyethylene and polypropylene, polystyrene resin, polyvinyl chloride resin, polyester resin, etc.) is vacuumed or injected. It can be manufactured by molding and, if necessary, laminating an olefin resin or the like. Then, the raw material of the contents (tofu or the like) is charged into this container, coagulated by heating or cooling, and the contents can be filled and sealed by sealing the container. Therefore, air does not enter the container (filling container) and the contents are tightly filled. Therefore, when the contents are taken out, the contents cannot be taken out even if the container is inverted, or the contents cannot be taken out. It often collapses.

Patent Document 1 proposes a method for improving the ease of taking out (separation) of contents from a container in which the contents are tightly packed. Specifically, a container in which the contents are taken out by making the volume of the contents smaller than the volume of the container and interposing a liquid or water in a film form between the container and the contents is described. However, when the raw material is directly charged into the container and solidified, moisture or the like cannot be interposed between the container and the contents.

In Patent Document 2, a protrusion for opening is provided on the bottom surface of the pudding container, and when the pudding is taken out, the protrusion is pressed laterally to open the hole and the vacuum state is released to take out the pudding in the container. The method is disclosed. However, this method is not only industrially disadvantageous because the manufacturing process is complicated because the protrusion is provided on the container, but also the operation of peeling off the sealing material that seals the opening of the container and tilting the protrusion laterally is performed. Since it is necessary, the operation of taking out the contents is also complicated. Furthermore, it may not be possible to take out smoothly.

Patent Document 3 discloses a method of improving the peelability of the contents filled in a container by controlling the center line average roughness of the surface roughness inside the container. However, in the method of adjusting the surface roughness, since a specific elastomer is used as a raw material, it is necessary to provide a supply facility for them and the contents are not sufficiently separated from each other.

Further, a method has been proposed in which a specific fatty acid ester or the like is added or applied to the resin constituting the container to facilitate the removal of the contents filled in the container. For example, Patent Document 4 discloses an olefin resin composition for food containers obtained by adding a compounding agent such as a polyhydric alcohol or a derivative thereof or a polyoxyethylene derivative to a polyolefin resin. This document describes that stearic acid monoglyceride, sorbitan monostearate, and the like can be used as the compounding agent, and the contents can be easily taken out by using a container obtained from the resin composition. Further, Patent Document 5 discloses a container for tofu in which the inner surface of a container made of a synthetic resin sheet is coated with a moisture-absorbing dehydrating agent for foods such as soyalecithin and monoglycerin fatty acid ester. This document describes that the moisture-absorbing dehydrating agent for food absorbs water, and the absorbed water is interposed between the container and the tofu to make the tofu float in the container and easily taken out. Further, Patent Document 6 describes that the contents can be easily taken out by using a container tightly packed with the contents using a thermoplastic resin sheet containing or coated with a surfactant of HLB 11 or higher. Has been done.

Japanese Unexamined Patent Publication No. 55-5314 Japanese Unexamined Patent Publication No. 53-31476 Japanese Unexamined Patent Publication No. 7-125160 Japanese Unexamined Patent Publication No. 7-62163 Special Publication No. 63-3748 Japanese Unexamined Patent Publication No. 2001-122983

However, neither document describes the use of a container provided with a gas barrier material such as an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as "EVOH"). In recent years, there has been a demand for easy production of a packaging container in which gel-like contents are tightly packed, which has a gas barrier property and the contents can be easily taken out. In order to meet such demand, it is preferable to use EVOH having a high gas barrier property and good moldability, but the packaging container provided with the EVOH layer has a multilayer structure having a resin layer other than EVOH. It tends to be used, and the hardness of the container varies depending on the layer structure.

When the hardness of the container is changed by providing the gas barrier layer, for example, in a situation where the gel-like contents are tightly packed, the conventional container may not be easy to take out the contents. On the contrary, when the ease of taking out is prioritized and the layer structure is changed, the gas barrier property may be insufficient.

An object of the present invention is to provide a product that can easily take out the contents while maintaining the quality of the contents at a high level by using a packaging container having a high gas barrier property.

That is, the present invention
[1] A packaging container (A) including a multilayer structure (a) including a gas barrier layer containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 mol% or more and 60 mol% or less, and a packaging container (A). A product having a lid material (B) for sealing and a gel-like content (C) in the sealed space, and the hardness T of the packaging container (A) measured in accordance with ISO527-1. A product in which the ratio T / U of the hardness U of the gel-like content (C) is 1,000 or more and 100,000 or less.
[2] The product of [1], in which the gel-like content (C) is tightly packed;
[3] The product of [1] or [2], wherein the maximum height roughness (Rz) on the surface of the packaging container (A) measured in accordance with JIS-B0601 (2001) is 1 μm or more and 30 μm or less;
[4] The arithmetic mean roughness (Ra) on the surface of the Joso container (A) measured in accordance with JIS-B0601 (2001) is 0.1 μm or more and 2.5 μm or less, [1] to [3]. ] Any product;
[5] The product according to any one of [1] to [4], wherein the hardness T of the packaging container (A) is 100 N or more and 100,000 N or less.
[6] The product according to any one of [1] to [5], wherein the hardness U of the gel-like content (C) is 0.3 N or more and 20 N or less;
[7] The product according to any one of [1] to [6], wherein the average thickness of the gas barrier layer is 1% or more and 20% or less in the average total thickness of the multilayer structure (a);
[8] The product according to any one of [1] to [7], wherein the multilayer structure (a) includes a thermoplastic resin layer;
[9] The multilayer structure (a) includes at least two layers of the thermoplastic resin, and the gas barrier layer is arranged between the at least two layers of the thermoplastic resin [1] to [8]. ] Any product;
[10] The product according to any one of [1] to [9], wherein the ratio of the average thickness of the thermoplastic resin layer to the average total thickness of the multilayer structure (a) is 80% or more.
[11] The product according to any one of [1] to [10], wherein the gel-like content (C) is a food containing 1.0% by mass or more of lipid.
[12] Among the aldehyde-based aroma components contained in the food containing 1.0% by mass or more of the lipid containing an aldehyde-based aroma component having 3 to 7 carbon atoms and refrigerated for 10 days after the product is produced. When the aldehyde-based aroma component having the highest content is aldehyde (f), the content (F ₂ ) of aldehyde (f) contained in the food after refrigerating for 2 days after the product is produced and 10 after the product is produced. The product of [11], wherein the rate of change ((F ₁₀ −F ₂ ) / F ₂ ) from the content (F ₁₀ ) of the aldehyde (f) contained in the food after refrigerated storage for days is less than 0.5%. ;
[13] The carotenoid compound having the highest content among the carotenoid compounds contained in the food containing 1.0% by mass or more of the lipid and having been refrigerated for 10 days after the production of the product. Is carotenoid (c), the content (C ₂ ) of carotenoid (c) contained in the food after refrigerating for 2 days after the product is produced and the content (C ₂ ) in the food after refrigerating for 10 days after the product is produced. is less than 0.5% content (C ₁₀₎ and rate of change _{((C 2 -C 10) /} C 2) of the carotenoids (c), the product of [11];
Is achieved by providing.

The product of the present invention uses a packaging container having a high gas barrier property, and while maintaining the quality of the contents at a high level, the contents can be easily taken out.

It is a schematic perspective view which shows the cup-shaped container which is one Embodiment of the packaging container of this invention. It is a schematic cross-sectional view of the cup-shaped container of FIG. It is a schematic diagram for demonstrating the manufacturing method of the cup-shaped container of FIG. It is a schematic diagram for demonstrating the manufacturing method of the cup-shaped container of FIG. It is the schematic which shows an example of the coextrusion apparatus which manufactures the multilayer structure provided in the packaging container of this invention.

The product of the present invention seals a packaging container (A) including a multilayer structure (a) including a gas barrier layer containing EVOH having an ethylene unit content of 20 mol% or more and 60 mol% or less, and a packaging container (A). The hardness T of the packaging container (A) having the lid material (B) and the gel-like content (C) in the sealed space and measured in accordance with ISO527-1 and the content (C). The ratio T / U of hardness U is 1,000 or more and 100,000 or less. When the packaging container (A) is provided with a gas barrier layer containing EVOH, the packaging container (A) has a high gas barrier property, and the quality of the contents tends to be maintained for a long period of time. Further, by setting the ratio T / U of the hardness T of the packaging container (A) to the hardness U of the content (C) to 1,000 or more and 100,000 or less, the ease of taking out the content is improved. It becomes a tendency. In the present invention, "good ease of removal" means that it is easy to take out the contents by tilting the container, and the shape and appearance of the contents after taking out are not deformed and are good. To do.

The ratio T / U of the hardness (T) of the packaging container (A) to the hardness (U) of the content (C) is 1,000 or more, preferably 5,000 or more, and more than 10,000. preferable. The ratio T / U is 100,000 or less, preferably 75,000 or less, and more preferably 50,000 or less. If the ratio T / U is less than 1,000, when the content (C) is taken out from the packaging container (A), a force such as strongly pushing the packaging container (A) or giving a strong impact is required, and the contents (C) are taken out. The shape of the later content (C) tends to collapse. When the ratio T / U exceeds 100,000, even if the container is lightly impacted when the content (C) is taken out from the packaging container (A), it is between the packaging container (A) and the content (C). No space is created, and the contents (C) tend to be difficult to take out.

(Packaging container (A))
The packaging container (A) preferably includes a multilayer structure (a) including a gas barrier layer containing EVOH, and is a container obtained by thermoforming the multilayer structure (a). The shape of the packaging container (A) is not particularly limited as long as it can be filled with the contents (C) and can be taken out while maintaining the shape of the contents (C). For example, from the viewpoint of taking out the contents into the container. A cup shape is preferable.

The cup-shaped container will be specifically described by taking the cup-shaped container shown in FIGS. 1 and 2 as an example. However, the cup-shaped container is only an example of a thermoformed container, and the following description of the cup-shaped container does not limit the scope of the present invention.

The cup-shaped container 1 of FIGS. 1 and 2 includes a cup body 2 as an accommodating portion and a flange portion 3. The cup-shaped container 1 is used by accommodating the content (C) in the cup body 2 and sealing the lid 7 on the flange portion 3 so as to close the opening 4 of the cup body 2. The bottom surface of the cup-shaped container 1 is circular, but the cup-shaped container of the present invention may be oval or polygonal.

The cup-shaped container 1 is usually obtained by thermoforming the multilayer structure (a), and specifically, as shown in FIG. 3, the multilayer structure (a) 21 is heated by a heating device 30 to be softened. After that, it is manufactured by thermoforming using a mold device 40.

The heating device 30 includes a pair of heaters (heater 31 and heater 32), and the multilayer structure (a) 21 can pass between these heaters 31 and the heater 32. As the heating device 30, one that is heated by a hot press can also be used.

The mold device 40 is suitable for thermoforming by the plug assist method, and includes a lower mold 50 and an upper mold 51 housed in a chamber (not shown). The lower die 50 and the upper die 51 can be individually moved in the vertical direction, and the multilayer structure (a) 21 can pass between the lower die 50 and the upper die 51 in a separated state. .. The lower mold 50 has a plurality of recesses 52 for forming a housing portion of the cup-shaped container 1. The upper die 51 includes a plurality of plugs 53 projecting toward the lower die 50. The plurality of plugs 53 are provided at positions corresponding to the plurality of recesses 52 of the lower mold 50. Each plug 53 can be inserted into the corresponding recess 52.

As shown in FIGS. 3 and 4A, the lower die 50 is moved upward to bring the lower die 50 into close contact with the multi-layer structure (a) 21 softened by the heating device 30, and the multi-layer structure is brought into close contact with the lower die 50. (A) 21 is slightly lifted to apply tension to the multilayer structure (a) 21. Next, as shown in FIG. 4B, the plug 53 is inserted into the recess 52 by moving the upper mold 51 downward.

Subsequently, as shown in FIG. 4C, the upper die 51 is moved upward to separate the plug 53 from the recess 52, and then the inside of the chamber (not shown) is evacuated to form the multilayer structure (a) 21. It is brought into close contact with the inner surface of the recess 52. After that, the shape is fixed by cooling the molded portion by injecting air. Subsequently, as shown in FIG. 4D, the inside of the chamber (not shown) is opened to the atmosphere, and the lower mold 50 is moved downward to release the lower mold 50, whereby a primary molded product is obtained. By cutting this primary molded product, the cup-shaped container 1 shown in FIGS. 1 and 2 can be obtained.

The packaging container (A) preferably has a hardness T of 100 N or more and 100,000 N or less as measured in accordance with ISO527-1. The hardness T is more preferably 1,000 N or more, further preferably 10,000 N or more. Further, the hardness T is more preferably 75,000 N or less, further preferably 50,000 N or less. By setting the hardness T to 100 N or more, the contents can be easily taken out by simply pushing the packaging container lightly or giving a light impact, and the shape of the contents after taking out tends to be maintained. is there. By setting the hardness T to 100,000 N or less, a space is created between the packaging container and the contents by simply giving a light impact to the container when the contents are taken out from the packaging container, and the contents (C). Tends to be easier to take out. The hardness of the range packaging container (A) can be adjusted by the type and thickness ratio of the gas barrier layer, the layer structure and thickness of the multilayer structure (a), and the like. The hardness T of the packaging container (A) in the present invention will be described in more detail. The packaging container (A) has a tensile elastic modulus (MPa) measured at 23 ° C. and 50% RH in accordance with ISO527-1. It means a numerical value obtained by multiplying the thickness and width of the measurement sample cut out from the above and converting it into units.

The surface of the packaging container (A) has a specific range of maximum height roughness (Rz) and arithmetic mean roughness (Ra) of the packaging container (A) measured in accordance with JIS-B0601 (2001). Is preferable. In the present invention, the surface of the packaging container (A) means both the inner surface and the outer surface of the packaging container. The maximum height roughness (Rz) of the surface of the packaging container (A) is preferably 1 μm or more, more preferably 2 μm or more. By setting the maximum height roughness (Rz) to 1 μm or more, the ease of removal from the container can be improved. The maximum height roughness (Rz) of the surface of the packaging container (A) is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less. By setting the maximum height roughness (Rz) to 30 μm or less, it is possible to suppress the generation of fine powder when collecting and reusing (recycling) trim (cut-out part) and defective products generated during container manufacturing, and in the extrusion process. Trouble can be prevented.

The arithmetic mean roughness (Ra) of the surface of the packaging container (A) is preferably 0.1 μm or more, more preferably 0.2 μm or more. By setting the arithmetic mean roughness (Ra) to 0.1 μm or more, the ease of removal from the container can be improved. The arithmetic mean roughness (Ra) of the surface of the packaging container is preferably 2.5 μm or less, more preferably 2.0 μm or less. By setting the arithmetic mean roughness (Ra) to 2.5 μm or less, it is possible to suppress the generation of fine powder when collecting and reusing (recycling) trim (cut-out part) and defective products generated during container manufacturing, and in the extrusion process. Trouble can be prevented.

The surface roughness (maximum height roughness (Rz) and arithmetic mean roughness (Ra)) of the surface of the packaging container (A) is an evaluation range of a maximum width of 1414 μm and a height of 1060 μm from the surface of the packaging container (A). It means a non-contact type, the average value of the values measured with a cutoff value (λc) of 2.5 mm, in accordance with JIS-B0601 (2001). It should be noted that steps larger than the average thickness of the multilayer structure shall be excluded from the evaluation value of surface roughness, and a range that does not include such steps shall be selected in the observation range arbitrarily selected.

The maximum height roughness (Rz) and arithmetic mean roughness (Ra) of the surface of the packaging container (A) are, for example, the surface roughness of the inner surface of the mold in a coextrusion device or injection molding, particularly the inner surface of the outlet portion (die). It can be adjusted by controlling the roughness. It is considered that this is because the surface shape of the inner surface of the mold outlet portion is transferred to the extruded multilayer structure (a), and the influence remains on the packaging container (A) obtained by thermoforming. Therefore, by increasing the smoothness of the inner surface of the mold, the surface roughness of the obtained multilayer structure (a) and the packaging container (A) can be reduced. The surface roughness can also be adjusted by using an air knife of a coextrusion device described later.

The ten-point average roughness (Rz ^JIS94 ) of the inner surface of the die is preferably 15 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, and particularly preferably 1 μm or less. On the other hand, the ten-point average roughness (Rz ^JIS94 ) may be 0.1 μm or more or 0.3 μm or more. The arithmetic mean roughness (Ra) of the inner surface of the die is preferably 1.2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. On the other hand, the arithmetic mean roughness (Ra) may be 0.01 μm or more or 0.03 μm or more. When the surface roughness of the inner surface of the die is within the above range, the surface roughness of the obtained multilayer structure (a) and packaging container (A) tends to be adjusted to a suitable range of the present invention.

Here, the ten-point average roughness (Rz ^JIS94 ) and the arithmetic average roughness (Ra) of the inner surface of the die, which represent the surface roughness of the inner surface of the outlet portion (die), are the averages of the measured values at 10 arbitrarily selected locations. Use as a value. Further, in the present specification, the measured values of the ten-point average roughness (Rz ^JIS94 ) and the arithmetic mean roughness (Ra) of the inner surface of the die are cutoff values (λc) in accordance with JIS-B0601 (1994). It is a value measured by a contact type, 2.5 mm, evaluation length (1) 7.5 mm.

The packaging container (A) is a method of heating a multilayer structure such as a film or a sheet to soften it, and then molding it according to the shape of a mold (thermoforming) or a method of injecting it into a target mold. It can be molded by (injection molding) or the like.

As the thermoforming method, for example, vacuum or compressed air is used, and if necessary, a plug is also used to form a mold shape (straight method, drape method, air slip method, snapback method, plug assist method, etc.), press molding. The method of doing this can be mentioned. Various molding conditions such as molding temperature, degree of vacuum, pressure of compressed air, and molding speed are appropriately set according to the shape of the plug, the shape of the mold, the properties of the raw material film and the sheet, and the like. The molding temperature is not particularly limited as long as the resin can be softened sufficiently for molding, and the suitable temperature range varies depending on the configuration of the multilayer structure such as a film or a sheet.

When the film is thermoformed, it is preferable that the temperature is not so high that the film is melted by heating or the unevenness of the metal surface of the heater plate is transferred to the film, but the temperature is not so low that the shaping is not sufficient. The specific film temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. The film temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower. On the other hand, when the sheet is thermoformed, it may be possible to form the sheet even at a higher temperature than the case of the film. In this case, the sheet temperature is preferably, for example, 130 ° C. or higher and 180 ° C. or lower.

(Multilayer structure (a))
By providing the multi-layer structure (a) with a gas barrier layer containing EVOH, it becomes easy to adjust the hardness T of the packaging container (A) within an appropriate range, and it has a high gas barrier property and the contents (C) can be easily taken out. Tends to be good. Here, the "gas barrier layer" is a layer having a function of preventing the permeation of gas, and specifically, it was measured in accordance with JIS-K7126-2 (2006) Part 2 (isobaric method). It means a layer having an oxygen permeability of 100 cc · 20 μm / (m ² · day · atm) or less at 20 ° C. and 65% RH.

(Gas barrier layer)
The multilayer structure (a) includes a gas barrier layer containing EVOH. The proportion of EVOH contained in the gas barrier layer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and is substantially composed of only EVOH. May be.

The average thickness of one gas barrier layer containing EVOH is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more. The average thickness of one gas barrier layer containing EVOH is preferably 100 μm or less, more preferably 50 μm or less. When the average thickness per gas barrier layer containing EVOH is within the above range, the hardness T of the packaging container (A) is in an appropriate range, and the ease of taking out the contents (C) tends to be good. In addition, it tends to have good durability, flexibility, and appearance characteristics.

The ratio of the average thickness of the gas barrier layer containing EVOH to the average total thickness of the multilayer structure (a) is preferably 1% or more, more preferably 1.5% or more, still more preferably 2% or more. The average thickness ratio of the gas barrier layer containing EVOH is preferably 20% or less, more preferably 15% or less. When the ratio of the average thickness of the gas barrier layer containing EVOH to the average total thickness of the multilayer structure (a) is in the above range, the hardness T of the packaging container (A) is in an appropriate range, and the contents (C) In addition to the tendency to improve the ease of taking out the product, the durability, flexibility, and appearance characteristics tend to be good. The ratio of the average thickness of the gas barrier layer containing EVOH to the average total thickness of the multilayer structure (a) is obtained by dividing the average thickness of the gas barrier layer containing EVOH by the total thickness of the multilayer structure (a). To calculate.

(EVOH)
EVOH contained in the gas barrier layer included in the multilayer structure (a) can usually be obtained by saponifying an ethylene-vinyl ester copolymer. The ethylene-vinyl ester copolymer can be produced and saponified by a known method. Vinyl acetate is a typical vinyl ester, but other fatty acid vinyls such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatic acid. It may be an ester.

The ethylene unit content of EVOH is 20 mol% or more, preferably 22 mol% or more, and more preferably 24 mol% or more. The ethylene unit content of the EVOH is 60 mol% or less, preferably 55 mol% or less, and more preferably 50 mol% or less. When the ethylene unit content is 20 mol% or more, the melt moldability and the gas barrier property under high humidity tend to be good, and the hardness T of the packaging container (A) tends to be adjusted to an appropriate range. .. On the other hand, when the ethylene unit content is 60 mol% or less, the gas barrier property tends to be enhanced. The ethylene unit content of EVOH can be determined by nuclear magnetic resonance (NMR) method.

The degree of saponification of the vinyl ester component of EVOH is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 99 mol% or more. Further, the degree of saponification of EVOH may be 100 mol% or less or 99.99 mol% or less. The degree of saponification of EVOH can be calculated by performing ¹ H-NMR measurement and measuring the peak area of hydrogen atoms contained in the vinyl ester structure and the peak area of hydrogen atoms contained in the vinyl alcohol structure. When the degree of saponification of EVOH is within the above range, it tends to have a good gas barrier property.

Further, EVOH may have a unit derived from a monomer other than ethylene and vinyl ester and a saponified product thereof, as long as the object of the present invention is not impaired. When EVOH has the other monomer unit, the content of the other monomer unit with respect to the total structural unit of EVOH is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less. More preferably, 5 mol% or less is particularly preferable. When EVOH has a unit derived from the other monomer, its lower limit may be 0.05 mol% or 0.10 mol%. Examples of the other monomer include alkenes such as propylene, butylene, penten, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4- Diacyloxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diasiloxy-2- Methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diasiloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6- Alkenes having ester groups such as asyloxy-1-hexene, 5,6-diasiloxy-1-hexene, 1,3-diacetoxy-2-methylenepropane, or saponified products thereof; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, etc. Unsaturated acid or its anhydride, salt, mono or dialkyl ester, etc .; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefins such as vinyl sulfonic acid, allyl sulfonic acid and metaallyl sulfonic acid. Sulphonic acid or a salt thereof; vinyl silane compounds such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri (β-methoxy-ethoxy) silane, γ-methacryloxypropyl methoxysilane; alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride , Vinylidene chloride and the like.

The EVOH may be a post-modified EVOH by a method such as urethanization, acetalization, cyanoethylation, or oxyalkyleneization. Such modified EVOH tends to have good melt moldability.

As the EVOH, two or more types of EVOH having different ethylene unit content, degree of saponification, copolymer component, presence / absence of modification, type of modification, etc. may be mixed and used.

EVOH is another thermoplastic resin, metal salt, acid, boron compound, plasticizer, filler, blocking inhibitor, lubricant, stabilizer, surfactant, coloring agent, ultraviolet absorber, antistatic agent, desiccant, cross-linking agent. , Filler, reinforcing material such as various fibers, etc. may have other components. Above all, it is preferable to contain a metal salt and an acid from the viewpoint of thermal stability and adhesiveness with other resins.

Examples of the thermoplastic resin include polyolefins, polyamides, polyesters, polystyrenes, polyvinyl chlorides, acrylic resins, polyurethanes, polycarbonates, polyvinyl acetates and the like.

As the metal salt, an alkali metal salt is preferable from the viewpoint of further enhancing interlayer adhesion, and an alkaline earth metal salt is preferable from the viewpoint of thermal stability. When EVOH contains a metal salt, the content thereof is preferably 1 ppm or more, more preferably 5 ppm or more, further preferably 10 ppm or more, and particularly preferably 20 ppm or more, in terms of metal atoms of the metal salt with respect to EVOH. The content of the metal salt is preferably 10,000 ppm or less, more preferably 5000 ppm or less, further preferably 1000 ppm or less, and particularly preferably 500 ppm or less in terms of metal atoms of the metal salt with respect to EVOH. When the content of the metal salt is within the above range, the thermal stability at the time of recycling tends to be good while maintaining the good interlayer adhesiveness.

As the acid, a carboxylic acid compound or a phosphoric acid compound is preferable from the viewpoint of enhancing thermal stability during EVOH melt molding. When EVOH contains a carboxylic acid compound, the content of carboxylic acid (content of carboxylic acid in the dry composition of the gas barrier layer containing EVOH) is preferably 1 ppm or more, more preferably 10 ppm or more, still more preferably 50 ppm or more. The content of the carboxylic acid is preferably 10,000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less. When the EVOH contains a phosphoric acid compound, the content of the phosphoric acid compound (the phosphoric acid root equivalent content of the phosphoric acid compound in the gas barrier layer containing EVOH) is preferably 1 ppm or more, more preferably 10 ppm or more, still more preferably 30 ppm or more. On the other hand, the content of the phosphoric acid compound is preferably 10,000 ppm or less, more preferably 1000 ppm or less, and even more preferably 300 ppm or less. When EVOH contains a carboxylic acid compound or a phosphoric acid compound within the above range, the thermal stability during melt molding tends to be good.

When EVOH contains the boron compound, its content (boron-equivalent content of the boron compound in the dry composition of the gas barrier layer containing EVOH) is preferably 1 ppm or more, more preferably 10 ppm or more, still more preferably 50 ppm or more. The content of the boron compound is preferably 2000 ppm or more, more preferably 1000 ppm or more, and even more preferably 500 ppm or more. When the content of the boron compound is within the above range, the thermal stability during melt molding tends to be good.

The method of incorporating the phosphoric acid compound, carboxylic acid or boron compound into the gas barrier layer containing EVOH is not particularly limited, and for example, a method of adding and kneading the composition to the composition when preparing pellets of the composition containing EVOH. Is preferably adopted. The method of adding to this composition is not particularly limited, but a method of adding as a dry powder, a method of adding in the form of a paste impregnated with a solvent, a method of adding in a state of being suspended in a liquid, or a method of dissolving in a solvent and a solution Examples thereof include a method of adding the powder and a method of immersing the powder in a solution. Above all, from the viewpoint of homogeneous dispersion, a method of dissolving in a solvent and adding as a solution or a method of immersing in a solution is preferable. The solvent is not particularly limited, but water is preferably used from the viewpoints of solubility of the additive, cost, ease of handling, safety of the working environment, and the like.

(Thermoplastic resin layer)
From the viewpoint of adjusting the hardness T of the packaging container (A) to an appropriate range, the multilayer structure (a) preferably includes a thermoplastic resin layer. The thermoplastic resin layer is a layer containing a thermoplastic resin as a main component, and when the multilayer structure (a) includes a thermoplastic resin layer, stretchability and thermoformability can be improved. The proportion of the thermoplastic resin contained in the thermoplastic resin layer is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, even if it is substantially composed of only the thermoplastic resin. Good.

The average thickness per layer of the thermoplastic resin layer is preferably 100 μm or more, more preferably 200 μm or more. The average thickness of one thermoplastic resin layer is preferably 1000 μm or less, preferably 500 μm or less, and more preferably 400 μm or less. When the average thickness per layer of the thermoplastic resin layer is 100 μm or more, the thickness can be easily adjusted, and the hardness of the multilayer structure (a) can be easily adjusted. When the average thickness of the thermoplastic resin layer layer is 1000 μm or less, the thermoformability of the multilayer structure (a) is improved, and the thickness unevenness of the container is reduced. As a result, when an impact is applied to the container to take out the contents, the force is evenly applied and the contents tend to be taken out cleanly.

The ratio of the average thickness of the thermoplastic resin layer to the average total thickness of the multilayer structure (a) is preferably 80% or more, more preferably 85% or more. The ratio of the average thickness of the thermoplastic resin layer to the average total thickness of the multilayer structure (a) is preferably 99% or less, more preferably 98.5% or less. By setting the average thickness of the thermoplastic resin layer in the average total thickness of the multilayer structure (a) within the above range, good thermoformability tends to be obtained.

The multilayer structure (a) is more preferably provided with at least two thermoplastic resin layers, and further preferably provided with a structure in which the gas barrier layer is arranged between at least two thermoplastic resin layers. By providing the above-mentioned structure in the multilayer structure (a), it has a high gas barrier property, and the ease of taking out the content (C) tends to be improved.

The thermoplastic resin constituting the thermoplastic resin layer is not particularly limited as long as it is a resin that softens by heating to the glass transition temperature or the melting point and exhibits plasticity. For example, a polyolefin resin (polyethylene resin, polypropylene resin, etc.), Grafted polyolefin resin graft-modified with unsaturated carboxylic acid or its ester, halogenated polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-acrylic acid ester copolymer resin, polyester Examples thereof include resins, polyamide resins, polyvinyl chloride resins, polyvinylidene chloride resins, acrylic resins, polystyrene resins, vinyl ester resins, ionomers, polyester elastomers, polyurethane elastomers, aromatic or aliphatic polyketones. Of these, polyolefin resins are preferable, and polyethylene resins and polypropylene resins are more preferable in terms of mechanical strength and moldability.

The thermoplastic resin layer may contain additives as long as the object of the present invention is not impaired. Examples of the additive include a surfactant, a resin other than the thermoplastic resin, a heat stabilizer, an ultraviolet absorber, an antioxidant, a colorant, a filler and the like. When the thermoplastic resin layer contains an additive, the content of the additive is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, based on the total amount of the thermoplastic resin layer.

Examples of the surfactant include polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentandiol, glycerin, tetrit, pentaerythritol, sorbitol and polyethylene glycol. When the thermoplastic resin layer is located on the inner surface of the packaging container (A), the ease of taking out the content (A) may be improved by including the surfactant.

When the multilayer structure (a) includes a thermoplastic resin layer, for example, an adhesive layer may be provided between the gas barrier layer and the thermoplastic resin layer to enhance the interlayer adhesive strength. Further, when the multilayer structure (a) is provided with an adhesive layer, the thickness unevenness of the obtained recovery layer tends to be reduced when the multilayer structure (a) is recovered and reused (recycled). A known adhesive resin can be used as the adhesive layer, and it can be appropriately selected according to the method for producing the multilayer structure.

When the multilayer structure (a) is produced by a laminating method or the like, a two-component reaction type polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable as the adhesive layer. Further, the adhesiveness may be further enhanced by adding a small amount of an additive such as a known silane coupling agent to the adhesive layer.

When the multilayer structure (a) is produced by the coextrusion molding method, the adhesive layer is not particularly limited as long as it has adhesiveness to the gas barrier layer and the thermoplastic resin layer, but contains a carboxylic acid-modified polyolefin. Adhesive resin is preferred. The carboxylic acid-modified polyolefin is a modified olefin containing a carboxyl group obtained by chemically (for example, addition reaction, graft reaction, etc.) binding an ethylenically unsaturated carboxylic acid, an ester thereof, or an anhydride thereof to an olefin polymer. The system polymer can be preferably used. Here, the olefin polymer is a polyolefin such as polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene, polypropylene, boribten, olefin and other monomers (vinyl ester, unsaturated carboxylic acid ester, etc.). (For example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ethyl ester copolymer, etc.). Among them, linear low-density polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate content 5 to 55% by mass), ethylene-acrylic acid ethyl ester copolymer (acrylic acid ethyl ester content 8 to 35% by mass). %) Is preferable, and linear low-density polyethylene and ethylene-vinyl acetate copolymer are particularly preferable. Examples of the ethylenically unsaturated carboxylic acid, its ester or its anhydride include an ethylenically unsaturated monocarboxylic acid or its ester, an ethylenically unsaturated dicarboxylic acid, or its mono or diester, or its anhydride. Esteric unsaturated dicarboxylic acid anhydride is preferred. Specific examples thereof include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, and fumaric acid monomethyl ester, and in particular, maleic anhydride. Acids are preferred.

The amount of ethylenically unsaturated carboxylic acid or its anhydride added to the olefin polymer or the amount of graft (modification) is 0.0001 to 15% by mass, preferably 0.001 to 10% by mass, based on the olefin polymer. %. The addition reaction and graft reaction of ethylenically unsaturated carboxylic acid or its anhydride to an olefin-based polymer shall be carried out by, for example, a radical polymerization method in the presence of a solvent (xylene or the like) or a catalyst (peroxide or the like). Can be done. The melt flow rate (MFR) of the carboxylic acid-modified polyolefin thus obtained measured at 210 ° C. is preferably 0.2 to 30 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes. More preferred. These adhesive resins may be used alone, or two or more of them may be mixed and used.

The average total thickness of the multilayer structure (a) is preferably 100 μm or more, more preferably 200 μm or more. The average total thickness of the multilayer structure of the present invention is preferably 2000 μm or less, more preferably 1000 μm or less, and even more preferably 800 μm or less. When the average total thickness of the multilayer structure (a) is 100 μm or more, the impact resistance tends to be excellent. Further, when the average total thickness of the multilayer structure (a) is 2000 μm or less, the manufacturing cost tends to decrease and good thermoformability tends to be obtained. Further, when the average thickness of the multilayer structure (a) is within the above range, the hardness of the obtained multilayer structure (a) and the packaging container (A) tends to be adjusted to a suitable range of the present invention.

As a specific layer structure of the multilayer structure (a), for example, when the gas barrier layer E containing EVOH, the adhesive layer is Ad, and the layer obtained from the thermoplastic resin is represented by T, T / E / T, E Structures such as / Ad / T and T / Ad / E / Ad / T can be mentioned. When having a recovery layer, the recovery layer is expressed as Reg, for example, T / Reg / Ad / E / Ad / Reg / T, T / Reg / Ad / E / Ad / T, T / Ad / E / Ad / Reg. The structure of / T can be mentioned. Each of these layers may be a single layer or a multi-layer. From the viewpoint of facilitating the adjustment of the hardness of the packaging container (A) and enhancing the impact resistance, the multilayer structure (a) preferably has a layered structure having a thermoplastic resin layer as the outermost layer. Further, the multilayer structure (a) is preferably composed of only a gas barrier layer containing EVOH and a thermoplastic resin layer, and in that case, even if the gas barrier layer containing EVOH and the thermoplastic resin layer each have a plurality of layers. Good.

The multilayer structure can be manufactured by a known method such as a co-extrusion molding method, a co-injection molding method, an extrusion laminating method, or a dry laminating method. Examples of the coextrusion molding method include a coextrusion laminating method, a coextrusion sheet molding method, a coextrusion inflation molding method, and a coextrusion blow molding method.

An example of manufacturing a multilayer structure by a coextrusion device will be described with reference to FIG. The co-extruder shown in FIG. 1 has an extrusion die 70 for extruding a polymer (polymer 60 / polymer 50 / polymer 60), and a first transfer roll 80 and a second transfer for conveying a multilayer structure 100 extruded from the extrusion die 70. A roll 90 and an air knife 110 arranged on the opposite side of the multilayer structure 100 from the first transfer roll 80 are provided. With this coextrusion device, the polymer 60 forming the thermoplastic resin layer and the polymer 50 forming the gas barrier layer are coextruded from the extrusion die 70, and the multilayer structure 100 made of the polymer extruded from the extrusion die 70 is formed. A multilayer structure film can be obtained by winding the film while transporting it by the first transport roll 80, the second transport roll 90, or the like. In FIG. 1, hatching showing a cross-sectional structure is omitted for the extrusion die 70, the first transfer roll 80, the second transfer roll 90, and the air knife 110.

When the film is formed using the air knife 110, the pressure of the air A introduced into the air knife is preferably 0.01 MPa or more, more preferably 0.05 MPa or more. The pressure of the air A is preferably 0.4 MPa or less, more preferably 0.3 MPa or less. By setting the pressure of the air A introduced into the air knife 110 within the above range, the smoothness of the multilayer structure can be controlled and the roughness of the obtained packaging container surface can be reduced.

(Lid material (B))
The product of the present invention includes a lid material (B) that seals the packaging container (A) after filling the packaging container (A) with the content (C). In order to maintain the quality of the content (C), the lid material (B) preferably has a gas barrier layer. The lid material (B), regardless of whether it is a single layer or a multi-layer, was measured in accordance with JIS-K7126-2 (2006) Part 2 (isobaric method) as a whole, at 20 ° C., 65%. in the oxygen permeability at RH, preferably ^{100cc · 20μm / (m 2 ·} day · atm) or less, more preferably ^{50cc · 20μm / (m 2 ·} day · atm) or ^{less, 10cc · 20μm / (m 2} · day · atm) The following is more preferable.

In order to satisfy the oxygen permeability, the lid material (B) preferably has a gas barrier layer. The gas barrier layer is not particularly limited as long as it has gas barrier properties, and is, for example, a composite structure containing EVOH, phosphorus and a polyvalent metal element, polyamide, polyester, polyvinylidene chloride, acrylonitrile copolymer, polyvinylidene fluoride. , Polychlorotrifluoroethylene, polyvinyl alcohol, inorganic vapor-deposited film layer and the like. Of these, a composite structure containing EVOH or phosphorus and a multivalent metal element is preferable from the viewpoint of gas barrier properties.

The lid material (B) preferably includes a heat-sealing layer in order to seal the packaging container (A). The heat-sealing layer is not particularly limited as long as it is a heat-sealing resin, and for example, a polyolefin resin (polyethylene resin, polypropylene resin, etc.), a grafted polyolefin resin graft-modified with an unsaturated carboxylic acid or an ester thereof, and a halogen. Polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-acrylic acid ester copolymer resin, polyester resin, polyamide resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylic resin , Polystyrene resin, vinyl ester resin, ionomer, polyester elastomer, polyurethane elastomer, aromatic or aliphatic polyketone and the like. Of these, polypropylene resin is preferable because it has durability against heat treatment.

Examples of other layers constituting the lid material (B) include a polyester layer, a polyamide layer, a polyolefin layer, an adhesive layer, and the like. The number of these layers and the stacking order are not particularly limited, but when heat sealing is performed, a configuration for that purpose is adopted.

The lid material (B) can be produced by a known method such as a coextrusion molding method, a co-injection molding method, an extrusion laminating method, or a dry laminating method.

(Gel-like contents (C))
The content (C) is gel-like, and the ratio T / U of the hardness T of the packaging container (A) to the hardness U of the gel-like content (C) is 1,000 or more and 100,000 or less.

The hardness U of the content (C) is defined by using a food hardness measuring unit FCA-DSV-50N (manufactured by Imada Co., Ltd.) and a flat probe FR-HA-20J having a diameter of 20 mm under 23 ° C. and 50% RH conditions. In, it means the maximum load when the content (C) in the packaging container (A) is pushed in by 10 mm.

The hardness (U) of the content (C) is preferably 0.3 N or more, preferably 0.5 N or more, and more preferably 0.7 N or more. The hardness (U) of the content (C) is 20 N or less, preferably 15 N or less, and more preferably 10 N or less. If the hardness (U) of the content (C) is less than 0.3N, it tends to be difficult to maintain the shape when the content is taken out from the packaging container. By setting the hardness (U) of the content (C) within the above range, the content (C) can be taken out from the packaging container or become uneasy, and the taken-out content (C) can maintain its shape.

From the viewpoint that the packaging container (A) having a gas barrier layer enhances the effect of maintaining quality, the content (C) is preferably a food, more preferably a food containing 1.0% by mass or more of lipid, and 1.1 of lipid. Foods containing% by mass or more are more preferable, and foods containing 1.2% by mass or more of lipids are particularly preferable. When the content (C) contains a certain amount or more of lipid, the content can be easily taken out in a good state, and the packaging container (A) has a gas barrier layer, so that the quality maintaining effect tends to be remarkably exhibited. Become.

When the content (C) is a food containing 1.0% by mass or more of lipid, if the content (C) contains an aldehyde-based aroma component having 3 to 7 carbon atoms, the effect of maintaining the quality of the content (C) Tends to appear more prominently. Aldehyde-based aroma components having 3 to 7 carbon atoms include propanal, butanal, pentanal, hexanal, heptanal, isobutyraldehyde, barrelaldehyde, 2-methylbutanal, 4-methylbarrelaldehyde, 3-methylpentanal, and 2-. Examples thereof include methylpentanal, 5-methylhexanal, 4-methylhexanal, 3-methylhexanal, 2-methylhexanal, 2,3-dimethylpentanal and 2-ethylpentanal. The boiling point of the aldehyde-based aroma component is preferably 30 ° C. or higher, more preferably 40 ° C. or higher.

In the product of the present invention, when the aldehyde-based aroma component having the highest content among the aldehyde-based aroma components contained in the food after refrigerating for 10 days after the product is made is aldehyde (f), the product is 2 after the product is made. Changes between the aldehyde (f) content (F ₂ ) contained in the food after refrigerated storage for 1 day and the aldehyde (f) content (F ₁₀ ) contained in the food after refrigerated storage for 10 days after the production of the product. The rate ((F ₁₀ −F ₂ ) / F ₂ ) is preferably less than 0.5%, more preferably less than 0.4%, and even more preferably less than 0.3%. When the rate of change ((F ₁₀ −F ₂ ) / F ₂ ) is less than 0.5%, the quality of food tends to be maintained.

The content (C) preferably contains a carotenoid compound such as lutein or zeaxanthin from the viewpoint that the effect of maintaining quality tends to appear more remarkably.

The product of the present invention is refrigerated for 2 days after the production of the product when the carotenoid compound having the highest content among the carotenoid compounds contained in the food after being refrigerated for 10 days after the production of the product is used as the carotenoid (c). Rate of change between the content of carotenoid (c) contained in the food after storage (C ₂ ) and the content of carotenoid (c) contained in the food after refrigerated storage for 10 days after the production of the product (C ₁₀ ) (C _2- C ₁₀ ) / C ₂ ) is preferably less than 0.5%, more preferably less than 0.4%, and even more preferably less than 0.3%. When the rate of change (C _2- C ₁₀ ) / C ₂ ) is less than 0.5%, the quality of food tends to be maintained.

Examples of foods containing 1.0% by mass or more of lipids include tofu, egg tofu, pudding, almond tofu, milk pudding, bavarois and the like.

From the viewpoint of more exerting the effect of the present invention of ease of removal from the container, it is preferable that the content (C) is tightly packed in the packaging container (A). The method of filling the contents (C) into the packaging container (A) is not particularly limited. For example, the contents (C) and the raw materials of the contents (C) are filled so as to overflow from the container, and the lid is tightly closed. Examples include a method of heat-sealing the material.

The method of making the content (C) is not particularly limited, and the method of filling the raw material of the content (C) in the packaging container (A), heat-sealing the lid material, and then heat-treating the content (C) to solidify the content (C). Examples thereof include a method in which the raw material of C) is heated, filled in a container, the lid material is heat-sealed, and then cooled and solidified.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples shown below. The measurement, calculation and evaluation methods were as follows.

<Materials used in Examples and Comparative Examples>
-SP5211: "Eberle (registered trademark) SP521" (manufactured by Kuraray Co., Ltd., EVOH, ethylene unit content 27 mol%,)
E105: "Eberle (registered trademark) E105" (manufactured by Kuraray Co., Ltd., EVOH, ethylene unit content 44 mol%)
L171: "Eberle (registered trademark) L171" (manufactured by Kuraray Co., Ltd., EVOH, ethylene unit content 27 mol%)
-PP: "Novatec (trademark) PP EA7AD" (manufactured by Japan Polypropylene Corporation, polypropylene)
-PET: "PIFG5 (product number)" (manufactured by Bell Polyester Products Co., Ltd., polyester)
-ONY: "Emblem (trademark) ONBC-15" (manufactured by Unitika Ltd., stretched nylon film, thickness 15 μm)
-CPP: "RXC-22" (manufactured by Mitsui Chemicals Tohcello Co., Ltd., unstretched polypropylene film, thickness 50 μm)
-Ad1: "Admer (trademark) QF500" (manufactured by Mitsui Chemicals, Inc., adhesive polyolefin)
-Ad2: "Admer (trademark) NF911E" (manufactured by Mitsui Chemicals, Inc., adhesive polyolefin)
・ "Takelac (trademark) A-520" (manufactured by Mitsui Chemicals, Inc., two-component adhesive)
・ "Takenate (trademark) A-50" (manufactured by Mitsui Chemicals, Inc., two-component adhesive)

<Evaluation method>
(1) Surface Roughness of Die For the inner surface of the die of the extruder used in Examples and Comparative Examples, JIS using a small surface roughness measuring machine surf test "SJ-400" (contact type, manufactured by Mitsutoyo Co., Ltd.). -Measure the ten-point average roughness (Rz ^JIS94 ) and arithmetic average roughness (Ra) with a cutoff value (λc) of 2.5 mm and an evaluation length (l) of 7.5 mm in accordance with -B0601 (1994). Then, the average value at 10 arbitrarily selected places was used as the measured value.

(2) Surface Roughness of Packaging Container For the surface of the cup-shaped packaging container obtained in Examples and Comparative Examples, use a shape measurement laser microscope "VK-X200" (non-contact type, manufactured by Keyence) to JIS. -In accordance with B0601 (2001), the cutoff value (λc) is 2.5 mm, and the maximum height roughness (Rz) and arithmetic average roughness (Ra) of the container in the evaluation area of width 1414 μm and height 1060 μm. ) Was measured, and the average value in the evaluation areas of 10 arbitrarily selected places was used as the measured value. A step larger than the average thickness of the packaging container was excluded from the evaluation value of the surface roughness, and a range not including such a step was selected in the observation range arbitrarily selected.

(3) Hardness of the packaging container The contents are taken out from the inside of the cup-shaped packaging container produced in Examples and Comparative Examples, the contents adhering to the inside of the packaging container are wiped off, and then the side surface is cut into a strip shape with a width of 15 mm. Then, under the condition of 23 ° C. and 50% RH, Young's modulus was measured according to ISO527-1. Using the obtained Young's modulus, the hardness T of the packaging container was determined as shown in the following formula.
Hardness of packaging container T (N) = tensile elastic modulus (MPa) x thickness of packaging container (A) (m) x 0.015 m

(4) Hardness of contents The hardness of the contents used in Examples and Comparative Examples was measured using a food hardness measuring unit FCA-DSV-50N (manufactured by Imada Co., Ltd.). The maximum load when the contents were set in the device in a packaging container and pushed in by 10 mm with a flat probe FR-HA-20J having a diameter of 20 mm was defined as the hardness (U) of the contents.

(5) Quantification of lipids Regarding the contents used in Examples and Comparative Examples, lipids were quantified by an acid decomposition method in accordance with the method described in the Food Analysis Method (edited by the Food Analysis Method Exercise Committee of the Japan Food Industry Association). did. Specifically, 3 g of the content is measured in a 50 mL beaker, 2 mL of ethanol is added and mixed, then 10 mL of concentrated hydrochloric acid (36% by weight) is added and mixed, and in a hot water bath at 70 to 80 ° C. with appropriate stirring. Was heated for 30-40 minutes. Transfer the warmed contents to a Majoria tube, wash the beaker and glass rod with 8 mL of ethanol, further wash with 25 mL of ethyl ether, collect all the washings in the Majoria tube, and then plug the Majoria tube. A liquid separation operation was performed. In the liquid separation operation, 25 ml of petroleum ether is added, the work of shaking the majority tube (mixing work) and degassing are repeated, and after sufficient mixing, the mixture is allowed to stand and separated into an ether mixed liquid layer and a dark brown water tank. Only the ether mixed liquid layer was collected from the stopper of the Majoria tube while being filtered through a funnel filled with absorbent cotton (recovery layer). The recovery layer was recovered in a dry beaker flask (weight W ₁ )). As an operation for extracting the aqueous layer remaining in the Majoria tube, 15 mL of ethyl ether and 15 mL of petroleum ether were added to the Majoria tube, and the ether mixed solution layer was collected in the beaker flask by the same method as described above. The stopper of the tube and the funnel were washed with ethyl ether, and the washing liquid was collected in the beaker flask. The beaker flask is heated on a hot water bath at 70 to 80 ° C., the ether mixture of the recovery layer is distilled off, dried in an electric low temperature dryer at 100 to 105 ° C. for 60 minutes, and in a desiccator for 1 hour. It was allowed to cool and the weight (W) was measured. The amount of lipid in the contents was calculated according to the following formula.
% Lipid in sample = ((W ₁ −W) / 3) × 100

(6) Quantification of aldehyde-based aroma components The quantification of aldehyde-based aroma components was analyzed by requesting the Japan Food Research Laboratories. The products obtained in Examples and Comparative Examples were immediately refrigerated, and 3 g of the contents refrigerated for 2 or 10 days was weighed, 5% perchloric acid and hexane were added, and homogenized under ice cooling. Then, sodium chloride was added, and after shaking, centrifugation was performed to extract the hexane layer. The extracted hexane layer is injected into gas chromatography to quantify the aldehyde-based aroma component, and the aldehyde-based aroma component (aldehyde (f)) having the highest content in the contents refrigerated for 10 days has 3 to 7 carbon atoms. Was identified and its content was quantified. The quantification was performed based on the calibration curve prepared from the standard sample.

(7) Ease of removal from the container After refrigerating the products obtained in Examples and Comparative Examples for 2 days, removing the lid material, tilt the container containing the contents, and take out the contents on the plate. The ease of removal and the appearance of the contents after removal were judged as follows.
Judgment: Criteria a: Can be taken out on the plate when a light impact is applied to the container b: Cannot be taken out on the plate unless the container is strongly pressed c: Cannot be taken out on the plate unless the contents are scraped out Judgment: Criteria A : The shape of the contents is not broken at all B: The shape of the contents is slightly broken C: The shape of the contents is greatly broken

(8) Thickness unevenness at the time of recovery The multilayer structure obtained in Examples and Comparative Examples was passed through a nip roll, and the screen opening hole diameter was adjusted to 15 mm with a film / sheet crusher (manufactured by Horai Co., Ltd.). It was crushed to obtain laminated flake-shaped chips. Five L-shaped pipes were installed every 10 m on a pipe 50 m having an inner diameter of 100 mm. With this L-shaped pipe, 1 ton of flake-shaped chips are airflow-conveyed in an air-feeding facility equipped with a hopper with a cyclone, and the flake-shaped chips after 1 ton are transported to a 200 mm extruder "D2020" manufactured by Toyo Seiki Seisakusho. (D (mm) = 20, L / D = 20, compression ratio = 2.0, screw: full flight), a single-layer film was formed under the following conditions to obtain a single-layer film.
Extrusion temperature: Supply part / compression part / measuring part / die = 180/220/220/220 ° C
Screw rotation speed: 60 rpm
Discharge rate: 1.3 kg / hr
Pick-up roll temperature: 80 ° C
Pick-up roll speed: 1.1 / min.
Film thickness: 90 μm
Continuous film formation is performed under the above conditions, and the film is cut out (sampled) one hour after the start of film formation, and the central portion of the sampled film in the TD direction (vertical direction of the film taking-up direction at the time of film formation, width direction). The thickness of the film was measured by 2 m in the MD direction (the direction in which the film was taken during molding, the length direction) using a continuous thickness gauge, and the thickness unevenness was evaluated. The points were collected at intervals of 25 mm, the standard deviation (μm) was determined, and the thickness spots were evaluated according to the following criteria.
A: 5.0 μm or less B: 5.0 μm or more and 10 μm or less C: 10 μm or more and 15 μm or less

(9) Measurement of Oxygen Permeability of Packaging Container and Lid Material For the packaging container and lid material obtained in Examples and Comparative Examples, MOCON INC. Using the oxygen permeability measuring device OX-TRAN2 / 20 type (detection limit value 0.0005 cc / pack ・ day ・ atm) under the condition of 15 ° C. and 50% RH, JIS-K7126-2 (2006) Part 2 Oxygen permeability was measured according to (isobaric method). Calculated from the total amount of those multiplied by the lid member area to the oxygen permeability (cc / pck · day · atm ) and the oxygen permeability of the lid ^{(B) (cc / m 2} · day · atm) of the package (A) Then, it was divided by the volume inside the packaging container to obtain the oxygen permeability (cc / m ³ · day · atm) per packaging container unit. The oxygen permeability of "0.0005 cc / (m ³ · day · atm)" means that the daily oxygen permeation amount under 1 atm of oxygen in the entire container is 0.0005 cc per container (pack). It means that there is.

(10) Method for quantifying carotenoid compounds We requested the Japan Food Research Laboratories to perform the measurement. Immediately refrigerate the products obtained in Examples and Comparative Examples, weigh 2 g of egg tofu stored refrigerated for 2 days or 10 days, and weigh water, a mixed solution of hexane / acetone / ethanol / toluene, and a potassium hydroxide-methanol solution. Was added and ultrasonically shaken. Subsequently, a potassium hydroxide-methanol solution was added, and the solution was allowed to stand in a water bath, and then extracted using a mixed solution of hexane / acetone / ethanol / toluene. The organic solvent layer obtained by extraction is evaporated to dryness, a mixed solution of hexane / acetone is added, and carotenoid compounds are quantified by high performance liquid chromatography (detector: ultraviolet visible absorptiometer) and stored in a refrigerator for 10 days. The carotenoid compound (carotenoid (c)) having the highest content in the contents was identified, and its content was quantified. The quantification was performed based on the calibration curve prepared from the standard sample.

(11) Flavor of Contents (C) After refrigerating the products obtained in Examples and Comparative Examples for 10 days, the package was opened and the flavor of the food inside was confirmed by 5 panelists, and according to the following criteria by consensus. It was judged.
A: It is almost the same as before storage.
B: The flavor is slightly lost.
C: Almost no flavor.

[Example 1]
(Making a packaging container)
Using EVOH "EVOH (trademark) SP521B" as a gas barrier layer, polypropylene "Novatec (trademark) PP EA7AD" (PP) as a thermoplastic resin layer, and adhesive polyolefin "Admer (trademark) QF500" (Ad1) as an adhesive layer, A multilayer structure of 3 types and 5 layers (PP / Ad1 / EVOH / Ad1 / PP = 386 μm / 16 μm / 32 μm / 16 μm / 386 μm) was obtained under the following conditions. As the film-forming equipment, an extruder having a film-forming die was followed by a take-up roll whose temperature could be controlled, and the multilayer structure obtained by the winder was wound. For the film-forming die used, the roughness of the inner surface of the die was measured according to the above evaluation method (1). In addition, the thickness unevenness at the time of recovery was measured for the obtained multilayer structure according to the above evaluation method (8). The results are shown in Table 1.
<Film formation conditions>
Extruder for EVOH: Single-screw extruder (Lab machine ME type CO-EXT, manufactured by Toyo Seiki Co., Ltd.)
Diameter 20 mmφ, L / D = 20, screw full flight type Supply part / compression part / measuring part / die = 175/210/220/230 ℃
Extruder for PP: Single-screw extruder (GT-32-A, manufactured by Plastic Engineering Laboratory Co., Ltd.)
Caliber 32 mmφ, L / D = 28, screw full flight type Supply part / compression part / measuring part / die = 170/200/210/230 ° C
Extruder for Ad1: Single-screw extruder (SZW20GT-20MG-STD, manufactured by Technobel Co., Ltd.)
Diameter 20 mmφ, L / D = 20, screw full flight type Supply part / compression part / measuring part / die = 150/200/220/220 ° C
Die: 300mm width coat hanger die (manufactured by Plastic Engineering Laboratory)
Pick-up roll temperature: 80 ° C

The obtained multilayer structure is thermoformed into a cup shape (mold shape 70φ x 70 mm, drawing ratio S = 0.5) at a sheet temperature of 170 ° C. using a thermoforming machine (manufactured by Asano Seisakusho) (compressed air: 5 kg /). A cup-shaped packaging container was prepared by using cm ² , a plug: 45φ × 65 mm, a syntax foam, and a mold temperature: 40 ° C.). With respect to the obtained packaging container, the surface roughness, hardness and oxygen permeability of the packaging container were measured according to the above evaluation methods (2), (3) and (9). The results are shown in Table 1.

(Preparation of coating liquid (S-1))
The temperature was raised to 70 ° C. with stirring 230 parts by mass of distilled water. 88 parts by mass of triisopropoxyaluminum was added dropwise to the distilled water over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled off to carry out hydrolysis condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added, and the mixture was stirred at 95 ° C. for 3 hours to deflocce the aggregates of the particles of the hydrolyzed condensate. Then, the liquid was concentrated so that the solid content concentration was 10% by mass in terms of aluminum oxide. To 22.50 parts by mass of the dispersion liquid thus obtained, 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added and stirred so as to be uniform to obtain a dispersion liquid. Next, while stirring the dispersion while maintaining the liquid temperature at 15 ° C., 4.41 parts by mass of an 85% by mass phosphoric acid aqueous solution was added dropwise, and the mixture was stirred at 15 ° C. until the viscosity became 1,500 mPa · s. The desired coating liquid (S-1) was obtained. The molar ratio of aluminum atom to phosphorus atom in the coating liquid (S-1) was aluminum atom: phosphorus atom = 1.15: 1.00.

(Synthesis of Organophosphorus Compound (BO-1))
Under a nitrogen atmosphere, 10 g of vinyl phosphonic acid and 0.025 g of 2,2'-azobis (2-amidinopropane) dihydrochloride were dissolved in 5 g of water and stirred at 80 ° C. for 3 hours. After cooling, 15 g of water was added to the polymerization solution to dilute the solution, and the mixture was filtered using a cellulose membrane (Spectra / Por (registered trademark) manufactured by Spectrum Laboratories). After distilling off the water in the filtrate, it was vacuum dried at 50 ° C. for 24 hours to obtain an organic phosphorus compound (BO-1; poly (vinyl sulfonic acid)). According to the result of GPC analysis, the number average molecular weight of the organic phosphorus compound (BO-1) was 10,000 in terms of polyethylene glycol.

(Manufacturing of coating liquid (T-1))
67% by mass of the organophosphorus compound (BO-1) obtained above and 33% by mass of polyethylene oxide (“Alcox® L-6” manufactured by Meisei Chemical Works, Ltd.) having a weight average molecular weight of 60,000. A mixture containing the above was prepared. This mixture was dissolved in a mixed solvent of water and methanol (water: methanol = 7: 3 in terms of mass ratio) to obtain a coating liquid (T-1) having a solid content concentration of 1% by mass.

(Preparation of lid material (B1) (composite structure containing phosphorus and multivalent metal element))
First, on a stretched polyethylene terephthalate film (Toray Industries, Inc. Lumirror (registered trademark) P60; thickness 12 μm), which is a base material, a bar coater was used so that the thickness after drying was 0.3 μm. The prepared coating liquid (S-1) was applied. The coated film was dried at 110 ° C. for 5 minutes and then heat-treated at 160 ° C. for 1 minute to form a precursor layer of the layer on the substrate. Next, a coating liquid (T-1) was used with a bar coater so that the ratio of the mass WBI of the inorganic phosphorus compound (BI) to the mass WBO of the organic phosphorus compound (BO) was WBO / WBI = 1.10 / 98.90. ) Was applied and dried at 110 ° C. for 3 minutes. Then, the layer (Y1-1) was formed by heat-treating at 220 ° C. for 1 minute. In this way, a composite structure (b1) containing phosphorus and a polyvalent metal element was obtained. A two-component adhesive ("Takelac ™ A-520" / "Takenate A-" on one side of the stretched nylon film "Emblem ™ ONBC-15" (ONY) on one side of the obtained composite structure (b1). 50 ") was applied with a solid content of 2.5 g / m2, and then a stretched nylon film" Emblem ™ ONBC-15 "(ONY) was laminated. Next, a two-component adhesive (“Takelac ™ A-520” / “Takenate A-50”) is applied to the ONY with a basis weight of 2.5 g / m ² , and then the unstretched polypropylene film “RXC” is applied. -22 "(CPP) was laminated by a dry laminating method to prepare a lid material (B1) (thickness 77 μm) having a composite structure (b1) / ONY / CPP structure. The oxygen permeability of the obtained lid material was measured according to (9) above, and the oxygen permeability per unit volume was calculated. The evaluation results are shown in Table 1.

(Making filled tofu)
Delicious unadjusted soymilk (manufactured by Kikkoman Co., Ltd.) and Amami bittern (manufactured by Ako Kasei Co., Ltd.) were mixed at a volume ratio of 100: 3 and filled in the obtained packaging container. Then, the packaging container filled with the contents was heat-sealed so that the CPP layer side of the lid material (B1) was in contact with the container to obtain a product in which the contents were sealed. The obtained product was boiled in hot water at 90 ° C. for 40 minutes, cooled with water after the boil treatment, and the water adhering to the container was wiped off and stored in a refrigerator.

Regarding the obtained product, according to the evaluation methods (4) to (7) and (11) described above, the hardness of the content, the lipid content, the quantification of the aldehyde-based aroma component, the ease of removal from the container and the content. The flavor was evaluated. The evaluation results are shown in Table 1. In the quantification of the aldehyde-based aroma component, aldehyde (f) was hexanal, and propanal was detected as another aldehyde-based aroma component.

<Examples 2 to 6, 8 to 10>
Implementation except that the layer structure, type of gas barrier layer, hardness of contents, and die surface roughness were changed as shown in Table 1, and the thickness of each layer was changed as shown in Table 1 by changing the screw rotation speed of the extruder. Multilayer structures, packaging containers and products were prepared and evaluated in the same manner as in Example 1. The hardness of the contents was adjusted by appropriately changing the amount of bittern added. The evaluation results are shown in Table 1.

<Example 7>
An air knife with a gap of 0.3 mm in the air outlet was placed at a height of 3 cm from the casting roll, and at the same time it was pushed out from the die onto the roll, air was blown at 0.1 MPa by the air knife. A multilayer structure, a packaging container and a product were produced and evaluated in the same manner as in Example 1 except that the die surface roughness was changed as shown in Table 1. The evaluation results are shown in Table 1.

<Example 11>
A multilayer structure, a packaging container, and a product were prepared and evaluated in the same manner as in Example 7 except that the strength of blowing air from the air knife and the surface roughness of the die were changed as shown in Table 1. The evaluation results are shown in Table 1.

<Comparative example 1>
Change the layer structure, type of gas barrier layer, hardness of contents, and die surface roughness as shown in Table 1, and change the thickness of each layer as shown in Table 1 by changing the screw rotation speed of the extruder. A multilayer structure, a packaging container, and a product were produced and evaluated in the same manner as in Example 1 except that the lid material (B2) described later was used. The evaluation results are shown in Table 1.

(Making lid material)
A two-component adhesive ("Takelac ™ A-520" / "Takenate A-50") with a solid content of 2.5 g / m2 is applied to one side of the stretched nylon film "Emblem ™ ONBC-15" (ONY). After coating with a texture, the unstretched polypylene film "RXC-22" (CPP) was laminated by a dry laminating method to prepare a lid material (B2) (thickness 65 μm) having an ONY / CPP configuration. The oxygen permeability of the obtained lid material was measured according to (9) above, and the oxygen permeability per unit volume was calculated. The evaluation results are shown in Table 1.

<Comparative example 2>
Except that the layer structure, the type of gas barrier layer, the hardness of the contents, and the die surface roughness were changed as shown in Table 1, and the thickness of each layer was changed as shown in Table 1 by changing the screw rotation speed of the extruder. Packaging containers and products were prepared and evaluated in the same manner as in Example 1.

<Comparative example 3>
(Making a packaging container)
Using EVOH "EVOH (trademark) SP521B" as the gas barrier layer, polyester "PIFG5 (product number)" (PET) as the thermoplastic resin layer, and adhesive polyolefin "Admer (trademark) NF911E" (Ad2) as the adhesive layer, the following Under the conditions, a multilayer structure of 3 types and 5 layers (PET / Ad2 / EVOH / Ad2 / PET = 552 μm / 24 μm / 48 μm / 24 μm / 552 μm) was obtained. As the film-forming equipment, an extruder having a film-forming die was followed by a take-up roll whose temperature could be controlled, and the multilayer structure obtained by the winder was wound. For the film-forming die used, the roughness of the inner surface of the die was measured according to the above evaluation method (1). In addition, the thickness unevenness at the time of recovery was measured for the obtained multilayer structure according to the above evaluation method (8). The results are shown in Table 1.
<Film formation conditions>
Extruder for EVOH: Single-screw extruder (Lab machine ME type CO-EXT, manufactured by Toyo Seiki Co., Ltd.)
Diameter 20 mmφ, L / D = 20, screw full flight type Supply part / compression part / measuring part / die = 175/210/220/230 ℃
Extruder for PET: Single-screw extruder (GT-32-A, manufactured by Plastic Engineering Laboratory Co., Ltd.)
Caliber 32 mmφ, L / D = 28, screw full flight type Supply part / compression part / measuring part / die = 280/280/280/280 ° C
Extruder for Ad2: Single-screw extruder (SZW20GT-20MG-STD, manufactured by Technobel Co., Ltd.)
Diameter 20 mmφ, L / D = 20, screw full flight type Supply part / compression part / measuring part / die = 280/280/280/280 ° C
Die: 300mm width coat hanger die (manufactured by Plastic Engineering Laboratory)
Pick-up roll temperature: 80 ° C

The obtained multilayer structure is thermoformed into a cup shape (mold shape 70φ x 70 mm, drawing ratio S = 0.5) at a sheet temperature of 110 ° C. using a thermoforming machine (manufactured by Asano Seisakusho) (compressed air: 5 kg /). A cup-shaped packaging container was prepared by using cm ² , a plug: 45φ × 65 mm, a syntax foam, and a mold temperature: 40 ° C.). With respect to the obtained packaging container, the surface roughness, hardness and oxygen permeability of the packaging container were measured according to the above evaluation methods (2), (3) and (9). The results are shown in Table 1. In addition, a product was prepared and evaluated in the same manner as in Example 1 except that the obtained packaging container was used. The results are shown in Table 1.

<Comparative Examples 4 and 5>
A multilayer structure, a packaging container and a product were prepared and evaluated in the same manner as in Example 1 except that the contents were changed to the agar jelly having the hardness shown in Table 1. The evaluation results are shown in Table 1. The agar jelly was prepared as shown below. Immerse an appropriate amount of agar in 384 g of tap water for 1 hour and then heat it. After the agar has melted, add 96 g of sugar, continue heating to 400 g, and fill the packaging container so that it is tightly packed. The lid material (B2) was heat-sealed, solidified at room temperature, and then stored in a refrigerator. The amount of agar jelly added was appropriately adjusted according to the hardness shown in Table 1.

<Example 12>
A multilayer structure, a packaging container, and a product were produced in the same manner as in Example 1 except that the content was egg tofu and the surface roughness of the packaging container was changed as shown in Table 2. According to the methods described in the above evaluation methods (2) to (5) and (7) to (11), the surface roughness of the packaging container, the hardness of the packaging container, the hardness of the contents, the lipid content, and the content from the container Ease of removal, thickness unevenness at the time of recovery, oxygen permeability, content of carotenoid compounds in the contents, and flavor of the contents were evaluated. The results are shown in Table 2. In the quantification of carotenoid compounds, carotenoid (c) was lutein, and zeaxanthin was detected as another carotenoid compound.

(Making egg tofu)
4 eggs, 300 mL of soup stock, 2 teaspoons of soy sauce, and a pinch of salt were mixed, strained with a strainer, filled in a container, and the lid material (B1) was heat-sealed in the same manner as in Example 1 to prepare a product. After that, it was stored refrigerated.

<Comparative Example 6>
Change the layer structure, type of gas barrier layer, hardness of contents, and die surface roughness as shown in Table 1, and change the thickness of each layer as shown in Table 1 by changing the screw rotation speed of the extruder. A multilayer structure, a packaging container, and a product were prepared and evaluated in the same manner as in Example 12 except that B2) was used. The evaluation results are shown in Table 2.

In the first embodiment, the ratio T / U of the hardness T of the packaging container (A) having EVOH and the hardness (U) of the content (C) is adjusted to an appropriate range, and the content (C) It is easy to take out from the container. In addition, it shows good gas barrier properties and can maintain a high flavor (quality) of the contents. Furthermore, since the surface roughness of the packaging container is within an appropriate range, it can be seen that there is no thickness unevenness at the time of collection and the recyclability is good. When the thickness of each layer of the multilayer structure (a) is changed as in Examples 2 to 4, the hardness T of the packaging container (A) fluctuates, and the ratio T / U of the content (C) to the hardness U Will fluctuate, resulting in slightly inferior ease of removal. When the thickness of the gas barrier layer containing EVOH is reduced as in Examples 3 and 5, the rate of change of the aldehyde-based aroma component increases, resulting in a slightly inferior flavor evaluation. From Examples 6, 7, 10 and 11, the inner surface roughness of the die and the condition of the air knife affect the surface roughness of the packaging container, and affect the thickness unevenness at the time of recovery and the ease of taking out the content (C). I understand. From Example 8, even when the hardness U of the content (C) is changed and the ratio T / U to the hardness T of the packaging container (A) is adjusted, the hardness T of the packaging container (A) is adjusted. It can be seen that the ease of taking out is affected as in the case of changing. From Example 9, it can be seen that the decrease in the gas barrier property of the packaging container increases the rate of change of the aldehyde-based aroma component and affects the flavor.

On the other hand, in Comparative Example 1 which does not include the gas barrier layer, it can be seen that the rate of change of the aldehyde-based aroma component is very high and the flavor is also significantly reduced. Further, in Comparative Examples 2 and 3 in which the thickness and the layer structure of each layer are different, the hardness T of the packaging container (A) is a high value, and the hardness T of the packaging container (A) and the hardness U of the contents are It was confirmed that the ease of taking out the content (C) from the container deteriorates when the ratio T / U of is out of the preferable range. Further, in Comparative Examples 4 and 5 in which the hardness of the content (C) was adjusted, the ratio T / U of the hardness T of the packaging container (A) to the hardness U of the content U deviated from the preferable range. It was confirmed that the ease of taking out the contents (C) from the container deteriorated.

In Example 12, the ratio T / U of the hardness T of the packaging container (A) having EVOH to the hardness (U) of the content (C), the maximum height roughness (Rz) of the container surface, and the arithmetic average. Roughness (Ra) is adjusted to a suitable range, and while ensuring the ease of taking out the contents (C) from the container, the recyclability is good, and the quality of the egg tofu which is the contents (C). Was able to be held high. In Comparative Example 6, the hardness T of the packaging container (A) is low, the oxygen permeability is adjusted to be high, the ease of removal from the container is slightly inferior, and the quality retention of the egg tofu which is the content (C) is maintained. Was confirmed to worsen.

The product of the present invention can maintain the quality of the gel-like contents at a high level, and at the same time, the contents can be easily taken out, and the shape of the contents can be kept good even after the contents are taken out. The product of the present invention is particularly useful when it contains gel-like foods such as tofu, egg tofu, pudding, almond tofu, milk pudding, and bavarois.

1 Cup-shaped container 2 Cup body 3 Flange part 4 Opening 5 Inner surface 6 Outer surface 7 Lid 50 Polymer (gas barrier layer)
60 polymer (thermoplastic resin layer)
70 Extrusion die 80 1st transfer roll 90 2nd transfer roll 100 Multi-layer structure 110 Air knife

Claims (13)

The packaging container (A) including the multilayer structure (a) including the gas barrier layer containing an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 mol% or more and 60 mol% or less is sealed with the packaging container (A). A product having a lid material (B) and a gel-like content (C) in the sealed space, and the hardness T of the packaging container (A) measured in accordance with ISO527-1 and the gel-like content. A product in which the ratio T / U of the hardness U of the product (C) is 1,000 or more and 100,000 or less. The product according to claim 1, wherein the gel-like content (C) is tightly packed. The product according to claim 1 or 2, wherein the maximum height roughness (Rz) on the surface of the packaging container (A) measured in accordance with JIS-B0601 (2001) is 1 μm or more and 30 μm or less. Any one of claims 1 to 3, wherein the arithmetic mean roughness (Ra) on the surface of the packaging container (A) measured in accordance with JIS-B0601 (2001) is 0.1 μm or more and 2.5 μm or less. Products listed in. The product according to any one of claims 1 to 4, wherein the hardness T of the packaging container (A) is 100 N or more and 100,000 N or less. The product according to any one of claims 1 to 5, wherein the hardness U of the gel-like content (C) is 0.3 N or more and 20 N or less. The product according to any one of claims 1 to 6, wherein the average thickness of the gas barrier layer in the average total thickness of the multilayer structure (a) is 1% or more and 20% or less. The product according to any one of claims 1 to 7, wherein the multilayer structure (a) includes a thermoplastic resin layer. Any one of claims 1 to 8, wherein the multilayer structure (a) includes at least two layers of the thermoplastic resin, and the gas barrier layer is arranged between the at least two layers of the thermoplastic resin. The products listed in the section. The product according to any one of claims 1 to 9, wherein the ratio of the average thickness of the thermoplastic resin layer to the average total thickness of the multilayer structure (a) is 80% or more. The product according to any one of claims 1 to 10, wherein the gel-like content (C) is a food containing 1.0% by mass or more of lipid. The food containing 1.0% by mass or more of the lipid contains an aldehyde-based aroma component having 3 to 7 carbon atoms, and the content of the aldehyde-based aroma component contained in the food after refrigerating for 10 days after the production of the product is high. When the most aldehyde-based aroma component is aldehyde (f), the content (F ₂ ) of aldehyde (f) contained in the food after being refrigerated for 2 days after the product is produced and the refrigerated storage for 10 days after the product is produced The product according to claim 11, wherein the rate of change ((F ₁₀ −F ₂ ) / F ₂ ) from the content (F ₁₀ ) of the aldehyde (f) contained in the subsequent food product is less than 0.5%. The carotenoid compound is contained in the food containing 1.0% by mass or more of the lipid, and the carotenoid compound having the highest content among the carotenoid compounds contained in the food after being refrigerated for 10 days after the production of the product is a carotenoid ( In the case of c), the content (C ₂ ) of the carotenoid (c) contained in the food after being refrigerated for 2 days after the product was produced and the carotenoid (c) contained in the food after being refrigerated for 10 days after the product was produced. the content of) (C ₁₀₎ and rate of change _{((C 2 -C 10) /} C 2) is less than 0.5%, product of claim 11.