JP2007190876A - Multilayered film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayered film for a skin-pack packaging which is formed from a non-halogen type resin material, suitable for a skin-pack packaging and which can resist the heating by a microwave oven. <P>SOLUTION: The multilayered film comprises: an outermost layer 8 consisting of an oxygen gas barrier resin; an intermediate layer 10 consisting of an ionomer resin; an intermediate layer 11 consisting of an ethylene-vinyl acetate copolymer; and the innermost layer 13 consisting of a ethylene based heat sealing resin, and, optionally further comprises an adhesive layer among the above layers. The multilayer film is a completely new multilayer film which is rich in a soft nature and has a great elastic recoverability and is free from the occurrence of a crease or the like on the surface of a package and excellent in transparency, gloss and appearance, and has oxygen gas barrier properties and heat resistance in a skin-pack packaging. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a multilayer film for packaging, and more particularly to a multilayer film for skin pack packaging excellent in glossiness, transparency, hygiene, oxygen gas barrier properties and low-temperature sealing properties.

  In recent years, the demand for food packaging materials has come to be favored especially in the form of packaging with good appearance, in addition to the conventional good storability and openability. Examples of such packaging forms include deep drawing vacuum packaging and inert gas replacement packaging. In addition, since the packaging with skin packs has not been prone to wrinkles and has a good appearance, it has been used for packaging meat-storing foods such as ham, sausage, bacon and the like.

  An example of the form of skin pack packaging is shown in FIG. A package body or contents 3 such as various foods are placed between the lid material 1 and the bottom material 2, the space between the lid material 1 and the bottom material 2 is evacuated, and the lid material 1 follows the shape of the content 3. And the cover material 1 and the bottom material 2 at the periphery of the package are heat sealed. The bottom material 2 is often printed with information such as the expiration date, raw materials used, etc. as necessary, or printed on a separate sheet with a sticker attached. The bottom material may be a film or may be formed into a rectangular parallelepiped container, for example. Recently, there has been an increasing demand for liquids to be included in the contents. An example of the skin pack packaging in that case is shown in FIG. As shown here, since the liquid 7 is contained in the contents, the one in which the bottom material is previously formed into a tray shape or a cup shape is used to prevent spillage. The contents 6 such as various foods are placed between the lid 4 and the bottom 5, and the gap between the lid 4 and the bottom 5 is degassed to make the lid 4 into the shape of the contents 6. It is formed by closely adhering along, and further heat-sealing the lid 4 and the bottom 5 in the periphery of the package. Since several kinds of contents can be enclosed and commercialized as a set menu, this type of skin pack packaging is expected to increase in the future.

  Various techniques have been proposed as skin pack packaging methods. Among them, the skin film is drawn with a vacuum mold equipped with a heater, and then the object to be packaged on the base film is covered with a recess of the skin film formed by drawing, and then a vacuum is formed between the two films. The heating vacuum packaging method in which the material is brought into close contact with the object to be packaged by the elastic recovery stress of the skin film has an advantage that the original shape of the object to be packaged is maintained and automation is easy. (For example, see Patent Documents 1 and 2.)

  Various proposals have also been made on packaging materials for skin pack packaging. For example, a surface layer composed of a saponified ethylene-vinyl alcohol copolymer, acetic acid, which can be drawn, has a high elastic recovery rate at the molding temperature, a low elastic recovery stress, and good transparency, gloss, etc. A core layer made of an ethylene-vinyl acetate copolymer having a vinyl content of 2 to 7% by mass, an ethylene homopolymer, and an ethylene copolymer (provided that the ethylene copolymer is an ethylene-vinyl acetate copolymer) Is an inner layer made of at least one material selected from the group consisting of a vinyl acetate content of 5% by mass or less) and, if necessary, an adhesive layer between each of the layers, and at least a core layer Proposed multilayer film characterized by being crosslinked by radiation and, if necessary, stretched within a range of 5 to 40% area ratio upon crosslinking Proposal of the multi-layer film have been made to be. (For example, see Patent Documents 3 and 4.)

In another proposal, in the multilayer film for skin pack packaging having a thermoplastic resin layer having a large elastic recovery rate in the outermost layer, a gas barrier resin layer in the core layer, and a heat-sealable resin layer in the innermost layer, the innermost layer The heat-sealable resin layer was obtained using a constrained geometric catalyst, and the 1-octene content was 1% by weight or more and less than 20% by weight, and the density exceeded 0.885 g / cm ³ or 0.960 g / cm. There is a proposal of a multilayer film for skin pack packaging characterized by being a layer made of a resin containing 50% by weight or more of a substantially linear ethylene-1-octene copolymer of ³ or less. (For example, see Patent Document 5)

    Some proposals have been made to impart heat resistance to skin pack packaging materials. For example, an outermost layer (a) made of a heat-resistant gas barrier resin, a core layer (b) made of a composition containing 10 to 70% by weight of a thermoplastic elastomer in addition to a polypropylene resin, an ethylene (co) polymer, etc. There is a proposal of an innermost layer (c) made of a heat-sealable resin and, if necessary, a multilayer film having an adhesive layer between the layers. According to the present invention, it is proposed that recovery elasticity can be imparted by adding a thermoplastic elastomer to a polypropylene resin which is generally considered to have good heat resistance. (For example, see Patent Document 6.)

In another proposal, as a method for imparting a low-temperature sealing property to a skin pack packaging material, at least an outermost layer, an intermediate layer, and a sealing layer are used, and (a) ethylene having a density of 0.895 to 0.912 g / cm ³ . A blend of α-olefin copolymer resin and (b) polybutene 1 having a density of 0.895 to 0.918 g / cm ³ in a mass ratio of (a) :( b) 40:60 to 80:20. There is a disclosure of a packaging material characterized in that a sealing layer is used. (For example, see Patent Document 7)

Japanese Patent Publication No. 56-49206 Japanese Patent Publication No.57-23607 Japanese Patent Laid-Open No. 07-256830 JP 09-08652 A JP 09-216319 A JP 11-310265 A JP-A-2001-232735

  An object of the present invention is to provide a multilayer film for skin pack packaging that is formed from a non-halogen resin material, is suitable for skin pack packaging, and can withstand heating by a microwave oven. More specifically, the object of the present invention is to provide skin pack packaging with high flexibility, high elastic recovery, no wrinkles on the surface of the package, excellent transparency and gloss, and good appearance. Another object of the present invention is to provide a completely new multilayer film having oxygen gas barrier properties and heat resistance.

Such an object is achieved by the present invention described in the following (1) to (6). That is, the present invention
(1) Outermost layer (A) made of oxygen gas barrier resin, intermediate layer (B) made of ionomer resin, intermediate layer (C) made of ethylene-vinyl acetate copolymer, innermost layer made of ethylene heat seal resin ( D) are sequentially laminated, and a multilayer film characterized by having an adhesive layer between each of the layers as necessary,
(2) Outermost layer (A) made of oxygen gas barrier resin, intermediate layer (C) made of ethylene-vinyl acetate copolymer, intermediate layer (B) made of ionomer resin, innermost layer made of ethylene heat seal resin ( D) are sequentially laminated, and a multilayer film characterized by having an adhesive layer between each of the layers as necessary,
(3) The outermost layer (A) made of an oxygen gas barrier resin is made of an ethylene-vinyl alcohol copolymer saponified product, and the ethylene content copolymerized with the saponified product is between 32 mol and 44 mol, Is a multilayer film according to the above (1) or (2), wherein the stretched area ratio is 10 times or more,
(4) The multilayer film according to any one of (1) to (3) above, wherein the intermediate layer (C) made of an ethylene-vinyl acetate copolymer has a vinyl acetate concentration of 5 to 30% by weight,
(5) The innermost layer (D) made of an ethylene-based heat-sealable resin has a density measured by the method specified in JIS K7112 in the range of 0.890 to 0.910, and is measured by the method specified in JIS K7206. The multilayer film according to any one of the above (1) to (4), which is a linear low density polyethylene having a Vicat softening point of 90 ° C. or less,
(6) The multilayer film according to any one of (1) to (5), which constitutes a skin pack packaging lid material,
It is.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the multilayer film for skin pack packaging excellent in glossiness, transparency, hygiene, oxygen gas barrier property, and low temperature sealing property. The multilayer film of the present invention has been developed to achieve the above object, and more specifically, the outermost layer (A) made of an oxygen gas barrier resin, the intermediate layer (B) made of an ionomer resin, and ethylene-vinyl acetate. It is a multilayer film comprising an intermediate layer (C) made of a copolymer and an innermost layer (D) made of an ethylene-based heat sealable resin, and having an adhesive layer between the respective layers as necessary. It is characterized by.

  An example of the multilayer film form of the present invention is shown in FIG. 3 and will be described in detail. That is, this multilayer film is composed of an outermost layer (A) made of an oxygen gas barrier resin, an intermediate layer (B) made of an ionomer resin, an intermediate layer (C) made of an ethylene-vinyl acetate copolymer, and an ethylene heat seal resin. The innermost layer (D) is formed and has a layer structure in which these are sequentially laminated. The adhesive layers (E) and (F) are inserted as necessary in order to improve the adhesion between the layers, and can be omitted.

  First, how the present inventor arrived at the present invention will be described below.

As a result of intensive studies by the present inventors, first, a gas barrier resin other than polyvinylidene chloride (hereinafter abbreviated as PVDC) typified by a saponified ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH), Although it is inferior in flexibility, it is generally known that it is used for the outermost layer because it has good heat resistance. As a result, I found out that it was the main cause of pinholes. This can be said to be completely different from the point of view that, in the past, oxygen barrier resins have not been discussed at all for stretch processability. More specifically, the EVOH resin used in the present invention is one having a stretch area ratio of 10 times or more which is better than that of the conventional EVOH resin. The stretched area magnification here means that the 150 μm EVOH resin single layer sheet is heated at 100 ° C. for 30 seconds and then stretched by the simultaneous tenter method, and the stretched sheet is torn or uneven. It is the magnification of the stretched area (stretching limit area) before being in a crushed state and the area before stretching.
By using this EVOH resin as the oxygen gas barrier resin in the outermost layer (A), the inventor has not only a gloss and transparency that does not deteriorate even when it comes into contact with the hot plate, but is also distorted due to its stretchability. The present inventors have newly found that excellent conformability is achieved without breaking the shape contents.

  However, skin pack packaging often requires toughness like other multilayer films. Generally, polyamide resin or polybutylene terephthalate resin is used to give toughness to the film, but these resins should be used from the viewpoint of adhesion to the contents and shape followability, especially in skin pack packaging. Is already known to be inappropriate. For this reason, in this invention, in order to provide toughness to a multilayer film, ionomer resin was used as an intermediate | middle layer (B).

  In addition to the requirement for conventional non-halogen resin materials, the demand for skin pack packaging has increased the need for so-called range-up suitability that allows the whole package to be heated in a microwave oven. Therefore, in addition to the conventional skin pack properties, heat resistance is required, and in particular, it is assumed that the use temperature exceeds 100 ° C. Therefore, special consideration is required for food hygiene. More specifically, various hygiene standards are specified by the test method based on the Ministry of Health and Welfare Notification No. 370 (according to the third standard equipment and containers and packaging D of foods, food additives, etc.). When oily or oily ingredients are used, it is necessary to consider the amount of n-heptane extraction residue. The present inventors have verified that, in the case of an ethylene-based copolymer such as an ethylene-vinyl acetate copolymer, which is generally considered to have good sealing properties during skin pack packaging, the weight ratio of the copolymer component The amount of extraction residue by n-heptane tended to increase as the value increased. This is thought to be because the crystal part of the resin decreases and the non-crystal part increases as the copolymerization component ratio increases, so that additives such as lubricants and antiblocking agents are easily eluted. However, on the other hand, it is essential to impart flexibility to the film in order to improve skin packability. For this reason, it is common to ensure flexibility by using a composition obtained by mixing a thermoplastic elastomer with these ethylene copolymer resins or polyolefin resins. For this reason, in the present invention, an ethylene-vinyl acetate copolymer is used as the intermediate layer (C). However, since this causes a problem in hygiene, there is no problem in hygiene and good heat sealability is achieved. By providing the innermost layer (D) with an ethylene-based heat-sealable resin, it is possible to obtain a flexible multilayer film suitable as a packaging material for skin pack packaging having heat resistance and hygiene that can be applied to a microwave oven. As a result, the present invention has been realized.

Furthermore, as a method of using the multilayer film of the present invention, there is no problem even if it is used on the bottom material side where the molding is not performed in the skin pack package. In this case, although it is already known, if the multilayer film of the present invention is used as the lid material film, the top and bottom layers are nearly symmetrical, and the occurrence of curling that tends to occur after heat sealing can be reduced.
Hereafter, each layer which comprises the multilayer film of this invention is demonstrated in detail.

  As the oxygen gas barrier resin constituting the outermost layer (A), among the saponified ethylene-vinyl alcohol copolymer, the ethylene content to be copolymerized is 27 to 44 mol%, and the stretched area ratio is 10 times or more. Use what you have. Conventionally, the stretch processability of EVOH resin has not been discussed as a method for enhancing the function of skin pack packaging. However, in the present invention, the stretch processability of EVOH resin is easily broken during conventional skin pack packaging. It has been found that there is a great effect in improving pinhole generation. This is a new function that is not recognized at all by other EVOH resins and polymetaxylene adipamide (hereinafter referred to as nylon MXD6) not defined in the present invention.

  As an ionomer resin constituting the intermediate layer (B), the metal ion to be cross-linked may be either zinc (Zn) or sodium (Na), and may be potassium (K) for the purpose of antistatic. The physical properties do not need to be particularly limited, but due to the processing characteristics of the resin, the melting point (based on JIS K-7121, measured by DSC method) is 100 ° C. or less, and tensile fracture stress (based on JIS K-7162) (Measurement) is more preferably 40 MPa or less.

  The ethylene-vinyl acetate copolymer constituting the intermediate layer (C) preferably has a copolymerized VA content of 5 to 30% by weight or less. If it is 5% or less, sufficient flexibility and transparency cannot be obtained. Conversely, if it exceeds 30% by weight, the Ministry of Health and Welfare Notification No. 370 (such as food and food additives) has the innermost layer (D) of the present invention. There is a risk that the extraction residue amount of n-heptane specified in Standard Standard Third Apparatus and Container Packaging D.) exceeds the standard of 30 ppm. Moreover, since the melting point is lowered, there is a problem that heat resistance is not excellent.

  As the ethylene-based heat seal layer resin constituting the innermost layer (D), the density measured by the method defined in JIS K7112 is in the range of 0.890 to 0.910, and measured by the method defined in JIS K7206. A linear low density polyethylene resin having a Vicat softening point of 90 ° C. or lower is used. The innermost layer (D) is a layer that is in close contact with an object to be packaged in skin pack packaging, and is a layer for heat-sealing the multilayer film to the base film (bottom material).

  The innermost layer (D) is desirably used alone, but may be added along a known formulation technique such as polypropylene resin to facilitate the opening of the skin pack package.

  In addition, a lubricant may be appropriately added to the ethylene heat seal layer resin constituting the innermost layer (D) for the purpose of preventing slipping and blocking. In that case, preferred examples include organic lubricants such as behenic acid amide, oleic acid amide, and erucic acid amide, and inorganic lubricants such as silica, zeolite, and calcium carbonate. The addition amount is preferably 0.1 to 5% by weight, and is usually added in the form of a masterbatch.

  In the multilayer film of the present invention, as shown in FIG. 3 as an example, the outermost layer (A) made of an oxygen gas barrier resin, the intermediate layer (B) made of an ionomer resin, and the intermediate layer (B) made of an ionomer resin And an intermediate layer (C) made of an ethylene-vinyl acetate copolymer, an intermediate layer (C) made of an ethylene-vinyl acetate copolymer, and an innermost layer (D) made of an ethylene heat sealable resin. Adhesive layers E and / or F may be provided as necessary to impart or enhance adhesion. In particular, since the outermost layer (A) and the intermediate layer (B) or the intermediate layer (C) have weak adhesive strength even in film formation by coextrusion, it is preferable to dispose an adhesive resin layer between these two layers.

  Examples of the adhesive resin used for the adhesive layer include EVA, ethylene-maleic anhydride copolymer, EAA, EEA, ethylene-methacrylate-glycidyl acrylate terpolymer, or various polyolefins such as acrylic acid, methacrylic acid. Monobasic unsaturated fatty acids such as acids, dibasic unsaturated fatty acids such as maleic acid, fumaric acid, itaconic acid or the like grafted with these anhydrides, such as maleic acid grafted EVA, maleic acid grafted ethylene- A well-known thing, such as an alpha olefin copolymer, can be used suitably.

  The method for forming the multilayer film of the present invention is not particularly limited, and film formation and lamination can be performed by a known coextrusion method, dry lamination method, or the like.

  In the flexible multilayer film of the present invention, the outermost layer (A) made of an oxygen gas barrier resin has a thickness of 5 to 30 μm, the intermediate layer (B) made of an ionomer resin has a thickness of 5 to 80 μm, and consists of an ethylene-vinyl acetate copolymer. The thickness of the intermediate layer (C) is preferably in the range of 5 to 80 μm, and the thickness of the innermost layer (D) made of the ethylene-based heat sealable resin is preferably in the range of 5 to 80 μm.

  The multi-layer film of the present invention is preferably used as a multi-layer film for lid packaging for skin pack packaging, but there is no particular limitation on the structure of the bottom film or tray to be combined at this time, and it may be arbitrary. For example, a single-layer film of low-density polyethylene may be used, and a configuration such as a polypropylene resin / EVOH / ethylene-based resin seal layer and a polypropylene resin / EVOH / polypropylene resin seal layer is preferably used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these Examples.

The multilayer film was evaluated according to the following evaluation criteria.
Skin pack suitability: Using a skin pack packaging machine (HI-750 series) manufactured by Hipack Co., Ltd., a multilayer sheet for skin pack having the structure shown in FIG. 4 was formed to determine the state of the package. That is, a molding having a diameter of 200 mm × depth of 34 mm, a layer structure of polypropylene resin / adhesive / EVOH / adhesive / polypropylene, each layer thickness of 330/5/30/5/30 μm, total thickness of 400 μm). On the processed circular tray, hamburger 300 g, kidney beans 20 g, and pasta 85 g are placed as the contents, sandwiched between multilayer films for skin packs, and the packaging state in the package obtained by vacuum skin pack packaging, and The lid surface condition was evaluated according to the following criteria.

-Followability ○: The followability of the skin film is good with respect to the unevenness of the filling, and there is no gap.
(Triangle | delta): The convex part of a filler is crushed or the adhesiveness to a recessed part is small.
X: The filling is greatly deformed, and the gravy is squeezed out or accumulated.
・ Wrinkle ○: There is no wrinkle on the entire surface of the package.
Δ: Short and shallow wrinkles occur at the corners of the filling section.
X: Long and deep wrinkles are generated on the entire surface of the package.
-Heat resistance ○: No fusing to a hot plate and tearing of the film when heated in a microwave oven.
Δ: No roughening of the film surface due to adhesion to the hot plate, but generation of pinholes with a diameter of 5 mm or less was observed when heated in a microwave oven.
X: Roughening of the film surface due to adhesion to the hot plate was observed, and the occurrence of pinholes with a diameter of 5 mm or more was observed when heated in a microwave oven.
-Sealability ○: The state of close contact with the bottom material of the lid is good and there is no fear of bag breaking.
Δ: In some cases, the state of close contact with the bottom material of the lid is unstable, and there is a risk of bag breakage due to external impact.
X: Adhesion of the lid material is poor and a part is peeled off.

  The dissolution test with n-heptane is a sanitary test based on Ministry of Health and Welfare Notification No. 370 (according to the third standard equipment such as food and food additives and container packaging D). The sample is left in contact with heptane at 25 ° C. for 1 hour, and the extraction residue in the solvent is measured. According to the standard stipulated in the Food Sanitation Law, it is stipulated that the amount of the sample used at 100 ° C. or higher must be 30 ppm or less.

  About the transparent molded multilayer film, the haze (Haze) was measured according to JIS K-7015. The unit is%.

The oxygen gas permeability was measured according to JIS K-7126 under conditions of a temperature of 25 ° C. and a relative humidity of 65% RH. The unit of the measured value is cm ³ / m ² · 24 hr · atm.

Example 1
Using the following four types of resin materials, a multilayer film having a four-layer structure (sequentially corresponding to layers 5 to 9 in FIG. 3) was formed. The layer structure was laminated in the order of outermost layer A / intermediate layer B / intermediate layer C / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP295) density 1.13 g / cm ³ , melt index 5.5 g / 10 min (measured at 190 ° C.), melting point 163 ° C., ethylene content 44 mol%, stretched area 20x magnification.
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1601) density 0.940 kg / m ³ , MFR 1.3 g / 10 min (measured at 190 ° C.), melting point 97 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5716RC) density 0.930 kg / m ³ , MFR 2.6 g / 10 min (measured at 190 ° C.), melting point 93 ° C., vinyl acetate content 10% by weight
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (micrometer) of the obtained film was 135 micrometers in total of 30/5/80/20 from the outermost layer.

(Example 2)
Except for changing the layer structure as described below, the following five types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer structure (in order, layers 5 to 9 in FIG. 3). Corresponding to the above). The layer structure was laminated in the order of outermost layer A / adhesive layer E / intermediate layer B / intermediate layer C / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP295) density 1.13 g / cm ³ , melt index 5.5 g / 10 min (measured at 190 ° C.), melting point 163 ° C., ethylene content 44 mol%, stretched area 20x magnification.
Adhesive layer E: acid-modified L-LDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1601) density 0.940 kg / m ³ , MFR 1.3 g / 10 min (measured at 190 ° C.), melting point 97 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5716RC) density 0.930 kg / m ³ , MFR 2.6 g / 10 min (measured at 190 ° C.), melting point 93 ° C., vinyl acetate content 10% by weight
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (μm) of the obtained film was 80 μm in total, 20/10/10/20/20, from the outermost layer.

(Example 3)
Except for changing the layer structure as follows, a multilayer film having a four-layer structure (in order of layers 5 to 9 in FIG. 3) using the following four types of resin materials by the same extrusion film forming method as in Example 1. Equivalent). In addition, the layer structure was made into order of outermost layer A / intermediate layer C / intermediate layer B / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP295) density 1.13 g / cm ³ , melt index 5.5 g / 10 min (measured at 190 ° C.), melting point 163 ° C., ethylene content 44 mol%, stretched area 20x magnification.
Adhesive layer E: acid-modified L-LDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5716RC) density 0.930 kg / m ³ , MFR 2.6 g / 10 min (measured at 190 ° C.), melting point 93 ° C., vinyl acetate content 10% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1601) density 0.940 kg / m ³ , MFR 1.3 g / 10 min (measured at 190 ° C.), melting point 97 ° C.
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (micrometer) of the obtained film was 200 micrometers in total of 25/10/80/30/55 from the outermost layer.

Example 4
Except for changing the layer structure as described below, the following five types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer structure (in order, layers 5 to 9 in FIG. 3). Corresponding to the above). In addition, the layer structure was made into the order of outermost layer A / adhesive material layer E / intermediate layer C / intermediate layer B / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP451) density 1.18 g / cm ³ , melt index 1.9 g / 10 min (measured at 190 ° C.), melting point 182 ° C., ethylene content 32 mol%, stretched area 16x magnification.
Adhesive layer E: acid-modified L-LDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5714RC) density 0.940 kg / m ³ , MFR 2.8 g / 10 min (190 ° C. measurement), melting point 89 ° C., vinyl acetate content 16% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1702) density 0.950 kg / m ³ , MFR 16 g / 10 min (190 ° C. measurement), melting point 90 ° C.
Heat seal layer D: LLDPE (Prime Polymer Co., Ltd., Evolution SP0510) density 0.903 g / cm ³ , MFR 1.2 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

Each layer thickness (μm) of the obtained film was 140 μm in total 20/20/30/30/40 from the outermost layer.

(Example 5)
Except for changing the layer configuration as follows, the following four types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer configuration (sequentially, layers 5 to 9 in FIG. 3). Corresponding to the above). In addition, the layer structure was made into order of outermost layer A / intermediate layer B / intermediate layer C / adhesive layer E / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP482) density 1.16 g / cm ³ , melt index 2.0 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol%, stretching Area magnification 18 times.
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1856) density 0.950 kg / m ³ , MFR 1.0 g / 10 min (measured at 190 ° C.), melting point 86 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5274) density 0.940 kg / m ³ , MFR 0.8 g / 10 min (190 ° C. measurement), melting point 89 ° C., vinyl acetate content 17% by weight
Adhesive layer E: acid-modified L-LDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (micrometer) of the obtained film was 255 micrometers in total of 5/80/80/30/60 from the outermost layer.

(Example 6)
Except for changing the layer structure as described below, the following five types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer structure (in order, layers 5 to 9 in FIG. 3). Corresponding to the above). In addition, the layer structure was made into order of outermost layer A / adhesive layer E / intermediate layer B / intermediate layer C / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP482) density 1.16 g / cm ³ , melt index 2.0 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol%, stretching Area magnification 18 times.
Adhesive layer E: acid-modified LLDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1856) density 0.950 kg / m ³ , MFR 1.0 g / 10 min (measured at 190 ° C.), melting point 86 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5274) density 0.940 kg / m ³ , MFR 0.8 g / 10 min (190 ° C. measurement), melting point 89 ° C., vinyl acetate content 17% by weight
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (μm) of the obtained film was 5 μm / 80/80/80 from the outermost layer, which was 255 μm in total.

(Example 7)
Except for changing the layer configuration as follows, the following four types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer configuration (sequentially, layers 5 to 9 in FIG. 3). Equivalent). In addition, the layer structure was made into the order of outermost layer A / adhesive material layer E / intermediate layer C / intermediate layer B / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP482) density 1.16 g / cm ³ , melt index 2.0 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol%, stretched area 18x magnification.
Adhesive layer E: acid-modified LLDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V5274) density 0.940 kg / m ³ , MFR 0.8 g / 10 min (190 ° C. measurement), melting point 89 ° C., vinyl acetate content 17% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1601) density 0.940 kg / m ³ , MFR 1.3 g / 10 min (measured at 190 ° C.), melting point 97 ° C.
Heat seal layer D: LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

  Each layer thickness (micrometer) of the obtained film was 145 micrometers in total of 20/15/30/40/40 from the outermost layer.

(Example 8)
Except for changing the layer structure as described below, the following five types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer structure (in order, layers 5 to 9 in FIG. 3). Corresponding to the above). In addition, the layer structure was made into the order of outermost layer A / adhesive material layer E / intermediate layer C / intermediate layer B / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP434) density 1.16 g / cm ³ , melt index 4.9 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol%, stretched area 16x magnification.
Adhesive layer E: acid-modified LLDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Mitsui DuPont Polychemical, Evaflex V961RC) density 0.930 kg / m ³ , MFR 2.0 g / 10 min (190 ° C. measurement), melting point 103 ° C., vinyl acetate content 5% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1702) density 0.950 kg / m ³ , MFR 16 g / 10 min (190 ° C. measurement), melting point 90 ° C.
Heat seal layer D: LLDPE (Prime Polymer Co., Ltd., Evolution SP0510) density 0.903 g / cm ³ , MFR 1.2 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

Each layer thickness (micrometer) of the obtained film was 145 micrometers in total of 25/10/40/30/40 from the outermost layer.

Example 9
Except for changing the layer structure as described below, a multilayer film having a 6-layer structure (sequentially, layers 5 to 9 in FIG. Equivalent). In addition, the layer structure was made into order of outermost layer A / adhesive material layer E / intermediate layer C / intermediate layer B / adhesive material layer E / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP451) density 1.18 g / cm ³ , melt index 1.9 g / 10 min (measured at 190 ° C.), melting point 182 ° C., ethylene content 32 mol%, stretched area 16x magnification.
Adhesive layer E: acid-modified LLDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Evaflex EV260 manufactured by Mitsui DuPont Polychemical Co., Ltd.) Density 0.950 kg / m ³ , MFR 6.0 g / 10 min (190 ° C. measurement), melting point 72 ° C., vinyl acetate content 28% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1702) density 0.950 kg / m ³ , MFR 16 g / 10 min (measured at 190 ° C.), melting point 90 ° C.
Heat seal layer D: LLDPE (Prime Polymer Co., Ltd., Evolution SP0510) density 0.903 g / cm ³ , MFR 1.2 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

Each layer thickness (μm) of the obtained film is 160 μm, which is 30/20/5/5/20/80 from the outermost layer.

(Example 10)
Except for changing the layer structure as described below, the following five types of resin materials were used by the same extrusion film forming method as in Example 1 to form a multilayer film having a five-layer structure (in order, layers 5 to 9 in FIG. 3). Corresponding to the above). In addition, the layer structure was made into the order of outermost layer A / adhesive material layer E / intermediate layer C / intermediate layer B / heat seal layer D.
Outermost layer A: EVOH (manufactured by Kuraray Co., Ltd., Eval SP434) density 1.16 g / cm ³ , melt index 4.9 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol%, stretched area 16x magnification.
Adhesive layer E: acid-modified LLDPE (manufactured by Mitsui Chemicals, Admer NF528, density 0.906 kg / m ³ , MFR 2.2 g / 10 min (measured at 190 ° C.), melting point 120 ° C.
Intermediate layer C: ethylene-vinyl acetate copolymer resin (Evaflex EV260 manufactured by Mitsui DuPont Polychemical Co., Ltd.) Density 0.950 kg / m ³ , MFR 6.0 g / 10 min (190 ° C. measurement), melting point 72 ° C., vinyl acetate content 28% by weight
Intermediate layer B: ionomer resin (manufactured by Mitsui DuPont Polychemical Co., Ltd., Himiran 1702) density 0.950 kg / m ³ , MFR 16 g / 10 min (190 ° C. measurement), melting point 90 ° C.
Heat seal layer D: LLDPE (Prime Polymer Co., Ltd., Evolution SP0510) density 0.903 g / cm ³ , MFR 1.2 g / 10 min (measured at 190 ° C.), melting point 98 ° C.

Each layer thickness (micrometer) of the obtained film was 135 micrometers in total of 10/10/5/70/40 from the outermost layer.

(Comparative Example 1)
The outermost layer A of Example 1 is EVOH (manufactured by Kuraray Co., Ltd., EVAL F101) density 1.19 g / cm ³ , melt index 1.3 g / 10 min (190 ° C. measurement), melting point 183 ° C., ethylene content 32 mol%. The same configuration except that the stretched area magnification was 4 times.

  As a result, since the stretched area ratio of EVOH was small, the occurrence of pinholes was observed during skin pack packaging, and the skin pack properties were not excellent.

(Comparative Example 2)
The intermediate layer C of Example 2 was formed by using ethylene-vinyl acetate copolymer resin (Evaflex EV170, Mitsui DuPont Polychemical Co., Ltd.) density 0.960 kg / m ³ , MFR 1.0 g / 10 min (measured at 190 ° C.), melting point 62 ° C., acetic acid. The composition was the same except that the vinyl content was 33% by weight.

  As a result, since the vinyl acetate content of the ethylene-vinyl acetate copolymer resin exceeded 30% by weight, the extraction residue of n-heptane was 35 ppm, which was not compliant with the standards of the Food Sanitation Law.

(Comparative Example 3)
The heat seal layer D of Example 3 has the same configuration except that LLDPE (manufactured by Nippon Polyethylene Co., Ltd., Novatec LL UJ960) density 0.935 g / cm ³ , MFR 5.0 g / 10 min (measured at 190 ° C.), and melting point 126 ° C. did.

  As a result, the sealing property with the bottom material at the time of skin pack packaging was not good, and the sealing property was insufficient. Moreover, the followability of the cover material to the contents was insufficient.

(Comparative Example 4)
Outermost layer A of Example 4: EVOH (Kuraray Co., Ltd., Eval SP451) density 1.18 g / cm ³ , melt index 1.9 g / 10 min (measured at 190 ° C.), melting point 182 ° C., ethylene content 32 mol% The same configuration was adopted except that the thickness of the stretched area ratio 16 times was 60 μm.

  Each layer thickness (micrometer) of the obtained film was 180 micrometers in total of 60/20/30/30/40 from the outermost layer.

  As a result, although the oxygen shielding property was good, the EVOH resin layer was set to be thicker than a predetermined thickness, so that the mold following property at the time of skin pack packaging was insufficient.

(Comparative Example 5)
Heat seal layer D of Example 5, LLDPE (manufactured by Prime Polymer Co., Ltd., Evolution SP0540) density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C., thickness changed to 120 μm The configuration.
Each layer thickness (micrometer) of the obtained film was 315 micrometers in total of 5/80/80/30/120 from the outermost layer.

  As a result, although the heat resistance was good, the LLDPE resin layer was set to be thicker than a predetermined thickness, so that the mold followability at the time of skin pack packaging was insufficient.

(Comparative Example 6)
Heat seal layer D of Example 6: LLDPE (Prime Polymer Co., Ltd., Evolution SP0540) Density 0.903 g / cm ³ , MFR 3.8 g / 10 min (measured at 190 ° C.), melting point 98 ° C. The configuration was as follows.
Each layer thickness (micrometer) of the obtained film was 177 micrometers in total of 5/10/80/80/2 from the outermost layer.

    As a result, although the heat resistance was good, since the LLDPE resin layer was set to be thinner than a predetermined thickness, the sealing property at the time of skin pack packaging was insufficient.

(Comparative Example 7)
Outermost layer A of Example 7: EVOH (manufactured by Kuraray Co., Ltd., Eval SP482) density 1.16 g / cm ³ , melt index 2.0 g / 10 min (measured at 190 ° C.), melting point 181 ° C., ethylene content 32 mol% The same configuration was adopted except that the thickness of the stretched area ratio 18 times was 3 μm.

  Each layer thickness (μm) of the obtained film was 3/15/30/40/40 of the total thickness of 128 μm from the outermost layer.

  As a result, although the oxygen shielding property was good, the EVOH resin layer was set to be thicker than a predetermined thickness, so that the mold following property at the time of skin pack packaging was insufficient.

  About the multilayer film obtained by said each Example and comparative example, the result of having evaluated the physical property is put together in Table 1 and Table 2, respectively. From the results shown in Tables 1 and 2, the following was found.

  By producing a package using the multilayer film of Examples 1 to 10, a skin pack package having good skin pack properties, heat resistance, hygiene, and transparency could be obtained.

  The multilayer film of the present invention can provide a package having good skin pack properties, heat resistance, hygiene and transparency by using the multilayer film in a skin pack package. Compared to conventional deep-drawn packages, it is possible to propose a product that does not generate wrinkles and has a good appearance.

The figure which shows embodiment of the skin pack package of this invention. The figure which shows another embodiment of the skin pack package of this invention. The figure which shows an example of the layer structure of the multilayer film of this invention. The figure which shows an example of the layer structure of the multilayer film of this invention.

Explanation of symbols

1 Skin Pack Lid Film 2 Skin Pack Bottom Film 3 Contents (Solid)
4 Skin pack lid material film 5 Skin pack bottom material tray 6 Contents (solid)
7 Contents (liquid)
8 Outermost layer (A)
9 Adhesive layer (E)
10 Middle layer (B)
11 Intermediate layer (C)
12 Adhesive layer (E)
13 Innermost layer (D)
14 Polypropylene resin layer 15 Adhesive layer 16 EVOH resin layer 17 Adhesive layer 18 Ethylene-based resin layer or polypropylene resin layer

Claims (6)

  An outermost layer (A) made of an oxygen gas barrier resin, an intermediate layer (B) made of an ionomer resin, an intermediate layer (C) made of an ethylene-vinyl acetate copolymer, and an innermost layer (D) made of an ethylene heat sealable resin A multilayer film characterized by being sequentially laminated and having an adhesive layer between the layers as necessary.   An outermost layer (A) made of an oxygen gas barrier resin, an intermediate layer (C) made of an ethylene-vinyl acetate copolymer, an intermediate layer (B) made of an ionomer resin, and an innermost layer (D) made of an ethylene heat seal resin A multilayer film characterized by being sequentially laminated and having an adhesive layer between the layers as necessary.   The outermost layer (A) made of an oxygen gas barrier resin is made of a saponified ethylene-vinyl alcohol copolymer, and the ethylene content copolymerized therewith is between 32 mol and 44 mol, and the stretched area The multilayer film according to claim 1 or 2, wherein the magnification is 10 times or more.   The multilayer film according to any one of claims 1 to 3, wherein the intermediate layer (C) made of an ethylene-vinyl acetate copolymer has a vinyl acetate concentration of 5 to 30% by weight.   The innermost layer (D) made of an ethylene heat sealable resin has a density measured by the method defined in JIS K7112 in the range of 0.890 to 0.910, and Vicat softening measured by the method defined in JIS K7206 The multilayer film according to any one of claims 1 to 4, which is a linear low-density polyethylene having a point of 90 ° C or lower.   The multilayer film in any one of Claims 1-5 which comprises the cover material for skin pack packaging.

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