JP2019206175A - Laminate for molding container, molding container, and package - Google Patents

Abstract

To provide a container with good appearance by molding a laminate having a metal foil layer and an external appearance resin film layer at low cost.SOLUTION: There is provided a laminate 10 for molding container in which an external resin film layer 12 has at least a first resin film layer 12B containing a random copolymer containing propylene or a polymer of propylene element as one of a copolymer component of 50 mass% or more, and a second resin film layer 12A consisting of a resin composition containing a first elastomer modified olefin resin having melting point of 155°C or higher and crystalline melting energy of 50 J/g or more, and a second elastomer modified olefin resin having melting point of 135°C or higher and crystalline melting energy of 30 J/g or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate used as a material for a molded container for hermetically packaging foods, a molded container formed by molding the laminated body, and a package formed by covering the molded container filled with the contents More specifically, the present invention relates to a molded container laminate, molded container, and package having excellent long-term storage and good appearance.

For example, as a container for wrapping chicken poultry, jelly, baby food, food for nursing care, etc. so that it can be stored for a long period of time, it is laminated on the inner surface of the metal foil layer made of aluminum foil and the like, and on both sides of the metal foil layer There is known a molded container formed by molding a laminated body including a sealant layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer into a cup shape. (See Patent Document 1 below).
The outer resin film layer is for preventing scratches or molds on the surface of the container or corroding the metal foil layer, and for imparting moldability to the laminate, and includes a polyethylene terephthalate resin, It is composed of a single layer or a plurality of films made of nylon resin, polypropylene resin or the like.
And a package is obtained by heat-sealing the lid | cover which has a heat-fusible resin layer in the innermost layer to the flange of the shaping | molding container filled with the contents, such as foodstuffs.

JP-A-6-345123

In the above molded container, the design of the appearance is enhanced, the moldability is improved by adding appropriate flexibility to the resin composition, or the impact resistance of the outer layer of the container in the frozen state is improved. Therefore, it is conceivable to use a film formed by blending an elastomer with polypropylene resin or the like as the outer resin film layer of the molded container laminate.
However, when a molded container is molded using such a laminate, whitening may occur on the surface of the resulting molded container, which may impair the appearance.

  The present invention has been made in view of the above problems, and includes a molded container laminate including a metal foil layer and an outer resin film layer, a molded container formed by molding the laminate, and the molded container. An object of the present invention is to provide a package having a long-term storage stability and a good appearance at a low cost as a package formed by hermetically packaging the contents.

  In order to achieve the above object, the present invention comprises the following aspects.

1) A laminated body for a molded container comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each made of an elastomer-modified homopolypropylene resin,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more.

2) A laminated body for a molded container comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each made of an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of copolymer components,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more.

3) A molded container laminate comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are respectively composed of an elastomer-modified homopolypropylene resin and an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of copolymer components,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more.

4) The said 2nd resin film layer WHEREIN: The laminated body for molded containers any one of said 1) -3) whose content rate of said 2nd elastomer modified olefin resin is 1-50 mass%.

5) The laminate for a molded container according to any one of 1) to 4), wherein in the second resin film layer, the content of the first elastomer-modified olefin resin is 49 to 99% by mass.

6) The elastomer component of the first elastomer-modified olefin resin and the second elastomer-modified olefin resin is at least any one of ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer, respectively. Any one of said 1) -5 laminated body for molded containers.

7) The outer resin film layer includes at least one of inorganic fine particles, organic fine particles, and a slip agent in a layer constituting an outer surface of the molded container laminate. 6) Any one of the laminated bodies for molded containers.

8) Said 2nd elastomer modified olefin resin is a laminated body for molded containers any one of said 1) -7) which has a 2 or more crystallization peak in a differential scanning calorimetry graph.

9) The outer resin film layer includes the second resin film layer, the first resin film layer interposed between the second resin film layer and the metal foil layer, and one of the copolymer components. A third copolymer film layer containing at least 50% by mass of a random copolymer containing propylene or a polymer of propylene alone and laminated on the surface of the second resin film layer opposite to the metal foil layer; The laminated body for molded containers according to any one of 1) to 8), which has a multilayer structure of three or more layers.

10) A printing layer is formed between the metal foil layer and the outer resin film layer, or a coloring component is added to the outer resin film layer, whereby a predetermined surface is formed on the surface of the outer resin film layer. The laminate for molded containers according to any one of 1) to 9) above, wherein the display or decoration is shown.

11) A molded container obtained by molding the laminate for molded containers according to any one of 1) to 10) into a cup shape and having a flange at the periphery of the opening.

12) A package formed by joining a lid to the flange of the molded container of 11) filled with the contents so as to cover the opening of the molded container.

In this specification and claims, “melting point” is a melting peak temperature (Tmp) measured by differential scanning calorimetry (DSC) in accordance with JIS K7121-1987.
Similarly, “crystal melting energy” is the heat of fusion (crystal melting energy, ΔH) measured by differential scanning calorimetry (DSC) in accordance with JIS K7122-1987. In addition, when two or more crystal melting peak curves exist and two or more crystal melting energies (ΔH1, ΔH2) or three or more exist, the highest crystal melting energy value is indicated. .

In the molded container laminate of the above 1) to 3), the second resin film layer of the plurality of outer resin film layers has a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. Since it consists of a resin composition that combines a first elastomer-modified olefin resin and a second elastomer-modified olefin resin having a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g or less, The molded container formed by molding has good compatibility between the elastomer component and the olefin resin in the first and second elastomer-modified olefin resins of the resin composition, and the dispersibility of the elastomer component is also good. The bonding strength at the interface between the resin phase and the elastomer component is increased. Therefore, during the molding of the laminates 1) to 3), it is possible to prevent the interface between the olefin-based resin phase and the elastomer component from peeling off due to stress and to generate voids called voids, and the refractive index of the resin and voids can be reduced. The transparency deterioration due to the difference, that is, the whitening phenomenon is prevented.
Therefore, according to the molded container laminates 1) to 3), a molded container having an outer surface with a good appearance can be obtained at a low cost.
In addition, according to the molded container laminate of 1) to 3) above, the melting point of the first elastomer-modified olefin resin in the resin composition constituting the second resin film layer is 155 ° C. or higher. When the lid is heat-sealed to the flange of the container formed from the laminate, the outer resin film layer is not easily crushed, and sufficient shape retention is ensured.

  According to the laminated body for molded containers of 4), the effects described above for the laminated bodies of 1) to 3) can be sufficiently ensured. In particular, for example, a flange of a container formed by molding the laminated body When the lid is heat-sealed, the outer resin film layer is more difficult to be crushed, and the whitening phenomenon can be more reliably suppressed.

  According to the molded container laminate of 5), the effects described above for the laminates of 1) to 3) can be more sufficiently ensured.

  According to the laminate for molded containers of 6), the effects described above for the laminates of 1) to 3) can be more sufficiently ensured.

  According to the molded container laminate of the above 7), excellent slipperiness is imparted to the outer surface of the laminate, molding with a deeper molding depth can be performed satisfactorily, and whitening during molding is also sufficient. To be suppressed.

  According to the molded container laminate of 8), the effects described above for the laminates of 1) to 3) can be more sufficiently ensured.

  According to the laminate for molded containers of 9), the effects described above for the laminates of 1) to 3) can be more sufficiently ensured.

  According to the laminate for molded containers of 10) above, a printed layer is formed between the metal foil layer and the outer resin film layer, or a colored component is added to the outer resin film layer, thereby Since a predetermined display or decoration appears on the surface of the resin film layer, a molded container formed by molding the laminate has a more excellent appearance.

  According to the molded container of the above 11), a good appearance can be given.

  According to the packaging body of the above 12), the productivity is good and the cost can be suppressed, and a high-class feeling can be given by a container that is suppressed in whitening during molding and has a good appearance.

It is a partial expanded sectional view which shows the layer structure of the two aspects of the laminated body for molded containers which concerns on embodiment of this invention. It is a vertical sectional view which shows the manufacturing method of the package which concerns on embodiment of this invention in order of a process. It is a perspective view of the package manufactured by the same method.

  Embodiments of the present invention will be described below with reference to FIGS.

  FIG. 1 shows the layer structure of a molded container laminate according to an embodiment of the present invention. The illustrated laminate (10) includes a metal foil layer (11) and an outer resin film layer (12) laminated on the outer surface of the container (2) of both surfaces of the metal foil layer (11). I have. In addition, the laminate (10) of this embodiment includes an inner resin layer (13) that is laminated on the inner surface of the container (2) out of both surfaces of the metal foil layer (11).

More specifically, in the laminate (10) shown in FIG. 1 (a), the outer resin film layer (12) includes the second resin film layer (12A) constituting the outer surface of the laminate (10), and the second resin film layer (12A). It has a two-layer structure comprising a first resin film layer (12B) interposed between a two resin film layer (12A) and a metal foil layer (11).
Moreover, in the laminated body (10) shown in FIG.1 (b), an outer side resin film layer (12) is a 2nd resin film layer (12A), a 2nd resin film layer (12A), and a metal foil layer (11). The outer surface of the laminate (10) is laminated on the surface opposite to the metal foil layer (11) of the first resin film layer (12B) interposed between and the second resin film layer (12A). It has a three-layer structure composed of a third resin film layer (12C) to be formed.

The metal foil layer (11) plays a role of imparting barrier properties to prevent oxygen and moisture from entering the laminated body for molded containers (10).
As the metal foil constituting the metal foil layer (11), aluminum foil, iron foil, stainless steel foil, copper foil and the like can be used, and aluminum foil is preferably used. In the case of an aluminum foil, it may be either a pure aluminum foil or an aluminum alloy foil, and may be either soft or hard. For example, it is classified according to JIS H4160 with an iron content of 0.3 to 1.5% by mass. Any soft material (O material) that has been annealed in the A8000 series (particularly A8079H or A8021H) is excellent in moldability and can be suitably used.
One side or both sides of the metal foil layer (11) is subjected to a base treatment such as chemical conversion treatment, if necessary. Specifically, for example, on the surface of the metal foil that has been degreased,
1) phosphoric acid;
Chromic acid,
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride; 2) phosphoric acid;
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of chromic acid and a chromium (III) salt, 3) phosphoric acid,
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
At least one compound selected from the group consisting of chromic acid and a chromium (III) salt;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a metal salt of fluoride and a non-metal salt of fluoride; By performing chemical conversion treatment, a film is formed.
Film formed on the surface of the metal foil layer (11) by the chemical treatment, the chromium coating weight is preferably 0.1mg ^{/ m 2} ~50mg ^/ m 2 as a (per one surface), in particular ^2mg / m ^{2 ~20mg} / m ² is preferred.
The thickness of the metal foil layer (11) is preferably 30 to 200 μm, and more preferably 50 to 150 μm. By setting it as the above range, sufficient barrier properties and moldability can be obtained.

  The outer resin film layer (12) has a design property on the outer surface of the molded container (2), and the surface of the molded container (2) is scratched or molded, or the metal foil layer (11) is corroded. In addition, it plays a role of imparting deep drawability and stretchability to the molded container laminate (10).

The second resin film layer (12A) of the outer resin film layer (12) is a first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔH) of 50 J / g or higher. And a second elastomer-modified olefin resin having a melting point (Tmp) of 135 ° C. or more and a crystal melting energy (ΔH) of 30 J / g or less.
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer. The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer (random polypropylene) containing propylene and a monomer other than propylene as a copolymer component. The copolymer component (monomer) other than propylene is not particularly limited. For example, in addition to olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene, Examples include butadiene. The elastomer component is not particularly limited, but at least one of ethylene-propylene elastomer (EPR), ethylene-1-butene elastomer (EBR), and ethylene-propylene-1-butene elastomer (EPBR). Is preferably used.

The second resin film layer (12A) is composed of a first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔH) of 50 J / g or higher, and a melting point (Tmp) of 135. The reason why the resin composition containing the second elastomer-modified olefin resin having a crystal melting energy (ΔH) of 30 J / g or less and not lower than ° C. is as follows.
That is, when the melting point of the first elastomer-modified olefin resin is less than 155 ° C., whitening occurs remarkably over a wide area in the R portion at the bottom of the molded container (2) when the laminate (10) is molded (Comparative Example). 4).
In addition, when the melting point of the second elastomer-modified olefin resin is less than 135 ° C., streaky whitening occurs along the circumferential direction in the R portion at the bottom of the molded container (2) when the laminate (10) is molded (Comparative Example). 5).
Further, when the crystal melting energy (ΔH) of the first elastomer-modified olefin resin is less than 50 J / g, the outer resin film layer (12) is crushed to some extent during the heat sealing (see Comparative Example 6).
Further, when the crystal melting energy (ΔH) of the second elastomer-modified olefin resin exceeds 30 J / g, a streak is formed along the circumferential direction in the R portion at the bottom of the molded container (2) when the laminate (10) is molded. Whitening occurs (see Comparative Example 7).
Further, when the first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔH) of 50 J / g or more is not contained, a molded container is formed at the time of molding the laminate (10). In addition, streaky whitening occurs along the circumferential direction in the R portion at the bottom of (2), and the outer resin film layer (12) is liable to be crushed and the shape retainability tends to be insufficient (see Comparative Example 2).
Further, when the second elastomer-modified olefin resin having a melting point (Tmp) of 135 ° C. or higher and a crystal melting energy (ΔH) of 30 J / g or less is not contained, a molded container is formed at the time of molding the laminate (10). Whitening occurs remarkably over a wide area of the R portion at the bottom of (2) (see Comparative Example 1).

The melting point of the first elastomer-modified olefin resin is preferably 155 ° C. or more and 185 ° C. or less. The crystal melting energy of the first elastomer-modified olefin resin is preferably 50 J / g or more and 75 J / g or less, and more preferably 53 J / g or more and 70 J / g or less.
The melting point of the second elastomer-modified olefin resin is preferably 135 ° C. or higher and 175 ° C. or lower. The crystal melting energy of the second elastomer-modified olefin resin is preferably 5 J / g or more and 30 J / g or less, more preferably 10 J / g or more and 25 J / g or less, and more preferably 10 J / g or more. And it is especially preferable that it is 20 J / g or less.

  Regarding the first elastomer-modified olefin resin and the second elastomer-modified olefin resin, the elastomer modification mode includes graft polymerization, but other modification modes may be used.

The first elastomer-modified olefin resin and the second elastomer-modified olefin resin can be produced, for example, by the following reactor-made method.
That is, first, Ziegler-Natta catalyst, co-catalyst, propylene and hydrogen are supplied to the first reactor to polymerize homopolypropylene.
Next, the obtained homopolypropylene is moved to the second reactor in a state containing unreacted propylene and a Ziegler-Natta catalyst. In the second reactor, further propylene and hydrogen are added to polymerize the homopolypropylene.
And the obtained homopolypropylene is moved to a 3rd reactor in the state containing unreacted propylene and a Ziegler-Natta catalyst. In the third reactor, ethylene, propylene and hydrogen are further added to polymerize an ethylene-propylene elastomer (EPR) obtained by copolymerizing ethylene and propylene.
Thus, the first elastomer-modified olefin resin or the second elastomer-modified olefin resin is produced.
The first elastomer-modified olefin resin can be produced in a liquid phase by adding a solvent, for example. The second elastomer-modified olefin resin can be produced by, for example, performing a reaction in a gas phase without using a solvent.
However, the above is merely an example of the production method, and the first elastomer-modified olefin resin and the second elastomer-modified olefin resin are not limited to those produced by such a production method.

In the second resin film layer (12A) of the laminate (10), the content of the second elastomer-modified olefin resin is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. 10 to 25% by mass is particularly preferable. If the content of the second elastomer-modified olefin resin is less than 1% by mass, whitening may occur when the laminate (10) is molded. On the other hand, when the content rate of the second elastomer-modified olefin resin exceeds 50% by mass, the heat resistance decreases.
In the second resin film layer (12A), the content of the first elastomer-modified olefin resin is preferably 49 to 99% by mass, more preferably 70 to 95% by mass, and 75 to 90%. A mass% is particularly preferred. If the content of the first elastomer-modified olefin resin exceeds 99% by mass, whitening may occur when the laminate (10) is molded. On the other hand, heat resistance falls that the content rate of 1st elastomer modified olefin resin is less than 49 mass%.

  The second resin film layer (12A) preferably has a sea-island structure. With such a sea-island structure, it is possible to cause the second resin film layer (12A) to exhibit properties that conflict with heat resistance and flexibility. In the sea-island structure, it is preferable that the elastomer component of the first elastomer-modified olefin resin and the second elastomer-modified olefin resin form a fine island.

  The second elastomer-modified olefin-based resin preferably has two or more crystallization peaks in a suggested scanning calorimetry (DSC) measurement graph. In the case of having two crystallization peaks, the crystallization peak on the high temperature side (crystallization temperature) is 90 ° C. or higher, and the crystallization peak on the low temperature side (crystallization temperature) is 80 ° C. or less. Is preferred. In the case of having three or more crystallization peaks, the crystallization peak on the highest temperature side (crystallization temperature) is 90 ° C. or higher, and the crystallization peak on the lowest temperature side (crystallization temperature) is It is preferable that it is 80 degrees C or less.

In the laminate (10) shown in FIG. 1 (a), the second resin film layer (12A) constituting the outer surface of the laminate (10) is composed of a first elastomer-modified olefin resin and a second elastomer-modified olefin resin. In addition, it is preferable to contain at least one of inorganic fine particles, organic fine particles, and a slip agent. By adding inorganic fine particles, organic fine particles, and slip agent to the second resin film layer (12A), fine irregularities are formed on the outer surface of the laminate (10), and the area in contact with the mold during molding is reduced. Since it becomes small, slipperiness improves, shaping | molding with a larger shaping | molding depth can be performed favorably, and also the effect that whitening at the time of shaping | molding is fully suppressed is acquired.
The inorganic fine particles are not particularly limited, and examples thereof include silica, aluminum silicate, barium sulfate and the like. Although it does not specifically limit as said organic type microparticles | fine-particles, For example, an acrylic resin bead, a polystyrene resin bead, etc. are mentioned. The slip agent is not particularly limited, and examples thereof include fatty acid amides such as erucic acid amide, stearic acid amide, and oleic acid amide, and waxes such as crystallin wax and polyethylene wax. Further, instead of or in addition to the addition of the slip agent, a lubricating oil such as silicone oil or rapeseed oil may be applied to the surface of the laminate (10) during molding.

As shown in FIGS. 1 (a) and 1 (b), in a laminate (10) having an outer resin film layer (12) having a two-layer or three-layer structure, a first resin film disposed on the metal foil layer (11) side The layer (12B) is made of a resin composition containing 50% by mass or more of a random copolymer containing propylene as one of the copolymer components or a polymer of propylene alone (homopolypropylene). In the random copolymer, the copolymer component (monomer) other than propylene is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene. In addition to olefin components such as butadiene, butadiene and the like can be mentioned. When the lid (3) is heat-sealed to the flange (23) of the container (2) formed by molding the laminate (10) because the content of the random copolymer or homopolypropylene is 50% by mass or more. In addition (see FIG. 2), the first resin film layer (12B) is not easily crushed, and sufficient shape retention of the container (2) can be secured, and sufficient retort resistance can be secured. More preferably, the content of the random copolymer or homopolypropylene in the first resin film layer (12B) is set to 70% by mass or more. The random copolymer containing propylene as one of the copolymer components is preferably a random copolymer having two or more melting points. In this case, the low melting point random copolymer component can further increase the adhesive strength with the metal foil layer (11), further improve the adhesion performance, and the high melting point random copolymer component. When the lid (3) is heat sealed to the flange (23) of the container (2) formed from the laminate (10) (see FIG. 2), the first resin film layer (12B) is less likely to be crushed. Sufficient shape retention of the container (2) can be ensured.
The first resin film layer (12B) preferably has a structure that does not have a sea-island structure. With such a configuration, when the laminate (10) is deep-drawn to form the molded container (2), the first resin film layer (12B) has an interface between the olefin resin phase and the elastomer phase. There exists an advantage which can fully suppress that a void (space) arises. In particular, when the first resin film layer (12B) is disposed at a position adjacent to the metal foil layer (11), the above-described effect becomes remarkable.

In the laminate (10) having the outer resin film layer (12) having a three-layer structure as shown in FIG. 1 (b), a third resin film layer (12C) constituting the outer surface of the laminate (10). ) Has the same structure as the first resin film layer (12B), that is, contains 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone (homopolypropylene). It consists of a resin composition. By disposing the third resin film layer (12C) on the outer surface of the laminate (10), a container having a more glossy appearance can be obtained. Further, when the content of the random copolymer or homopolypropylene is 50% by mass or more, the lid (3) is heat sealed to the flange (23) of the container (2) formed from the laminate (10). When it is done (see FIG. 2), the third resin film layer (12C) is less likely to be crushed, and sufficient shape retention of the container (2) can be ensured and sufficient retort resistance can be ensured. . More preferably, the content of the random copolymer or homopolypropylene in the third resin film layer (12C) is set to 70% by mass or more. The random copolymer containing propylene as one of the copolymer components is preferably a random copolymer having two or more melting points. In this case, when the lid (3) is heat sealed (see FIG. 2) to the flange (23) of the container (2) formed from the laminated body (10) by the random copolymer component having a high melting point (see FIG. 2). The resin film layer (12C) is less likely to be crushed, and more sufficient shape retention of the container (2) can be ensured.
Since the third resin film layer (12C) also constitutes the outer surface of the laminate (10), it is preferable to add at least one of inorganic fine particles, organic fine particles, and a slip agent. In addition, excellent slipperiness is imparted to the outer surface of the laminate (10), molding with a deeper molding depth can be performed satisfactorily, and whitening during molding is sufficiently suppressed. It is done.

The film constituting the outer resin film layer (12) is preferably produced by a molding method such as multilayer extrusion molding, inflation molding or T-die cast film molding.
The overall thickness of the outer resin film layer (12) is preferably set to 20 to 80 μm. By setting the thickness to 20 μm or more, pinholes can be sufficiently prevented, and by setting the thickness to 80 μm or less, the amount of resin used can be reduced and the cost can be reduced. Can do. More preferably, the overall thickness of the outer resin film layer (12) is set to 30 to 50 μm.
When the outer resin film layer has a two-layer structure including the second resin film layer (12A) and the first resin film layer (12B) (see FIG. 1A), the second resin film layer (12A) The ratio of the thickness to the thickness of the first resin film layer (12B) is preferably in the range of 9: 1 to 4: 6. If the thickness ratio of the second resin film layer (12A) exceeds 9, the laminate strength between the two layers (12A) and (12B) may be reduced and peeling may occur. On the other hand, when the thickness ratio of the second resin film layer (12A) is less than 4, the outer resin film layer is not easily crushed during heat sealing. When the outer resin film layer has a three-layer structure including the second resin film layer (12A), the first resin film layer (12B), and the third resin film layer (12C) (see FIG. 1B). The ratio of the thickness of the second resin film layer (12A) to the thickness of the first resin film layer (12B) and the thickness of the third resin film layer (12C) is 0.5: 9: 0.5-3. Is preferably in the range of 4: 3.

  Although it does not specifically limit as a method of laminating | stacking the film which comprises the 1st resin film layer (12B) of Fig.1 (a) (b) on the metal foil which comprises a metal foil layer (11), Examples thereof include a dry laminating method and a sandwich laminating method (a method in which an adhesive film made of an acid-modified polypropylene resin or the like is extruded, sand-laminated between the metal foil and the film and then heat-laminated by a hot roll). In the case of the dry laminating method, for example, it is performed through an adhesive layer (14) made of a two-component curable polyester-polyurethane resin adhesive, a polyether-polyurethane resin adhesive, or the like (see FIG. 1). The thickness of the adhesive layer (14) is preferably set to 1 to 5 μm, and more preferably set to 1 to 3 μm from the viewpoint of thinning and weight reduction of the laminate (10) for molded containers. .

On the inner surface of the outer resin film layer (12), the printing layer (15) is formed entirely or partially by gravure printing or the like. With this printed layer (15), a predetermined display or decoration appears on the outer surface of the molded container (2). The printing layer (15) is not particularly limited, but it is preferable that the background color is a light color such as yellow (gold) in order to give a high-class feeling. Thereby, a metallic luster color tone is obtained.
Instead of the printing layer (15), a coloring component such as a pigment may be added to the outer resin film layer (12).

The inner resin layer (13) constitutes the inner surface of the molded container (2) (including the upper surface of the flange portion (23)). For example, a polypropylene resin (PP) film or polyethylene having heat-fusibility It is composed of a versatile film such as a resin (PE) film, or a composite sheet obtained by bonding them together. Above all, when opening the lid of the package by configuring the inner resin layer (13) with a composite sheet in which a versatile film such as a polypropylene resin (PP) film and a polyethylene resin (PE) film is bonded. In addition, it can be easily peeled between a polypropylene resin (PP) film and a polyethylene resin (PE) film, and can be opened with a relatively small force.
The thickness of the film or composite sheet constituting the inner resin layer (13) is preferably 100 to 500 μm, and more preferably 200 to 400 μm.

Lamination of the metal foil constituting the metal foil layer (11) and the film or composite sheet constituting the inner resin layer (13) is performed, for example, by a dry lamination method via the adhesive layer (16). For the adhesive layer (16), for example, a two-component curable polyester-polyurethane resin adhesive or a polyether-polyurethane resin adhesive is used. The thickness of the adhesive layer (16) is preferably set to 1 to 5 μm, and more preferably set to 1 to 3 μm from the viewpoint of thinning and weight reduction of the laminate (10) for molded containers. .
The inner resin layer (13) may be formed of a coat layer such as an epoxy resin or a shellac resin instead of the film or the composite sheet.

  FIG. 2 shows a package (4) formed by hermetically packaging contents (C) such as food using a molded container (2) molded from the laminate (10) and a lid (3). The manufacturing method is shown in the order of steps.

First, the laminate (10) is cut into a predetermined shape and dimensions, and formed into a cup shape. The laminate (10) is formed by cold forming such as deep drawing or stretch forming. Thus, a molded container (2) as shown in FIG. 2 (a) is obtained.
The forming container (2) includes a bottom wall (21), a peripheral wall (22) rising from the periphery of the bottom wall (21), and a horizontal annular flange (23) extending radially outward from the upper end edge of the peripheral wall (22). ).
The shape of the molded container (2) has a cross-sectional shape such as a circle, an ellipse, an oval, a substantially square, a substantially rectangular shape, etc., and a tapered tubular shape whose diameter gradually increases toward the top, or a vertical tubular shape And the like.
The depth of the molded container (2) is usually 15 to 50 mm.
Almost no whitening is observed in the outer surface portion of the molded container (2) formed from the laminate (10), that is, the outer resin film layer (12). This is because when the resin composition of the second resin film layer (12A) of the laminate (10) is as described above, the interface between the olefinic resin phase and the elastomer component peels off due to the stress during molding and voids ( This is because the generation of voids is effectively suppressed.

Next, as shown in FIG. 2 (b), after the molded container (2) is filled with the contents (C) such as food, the lid (3) is placed on the upper surface of the flange (23) of the molded container (2). Heat sealing (thermal fusion) is performed on the peripheral edge of the lower surface.
Here, as the lid (3), for example, a metal foil layer made of an aluminum foil or the like, and a heat made of a polypropylene resin (PP) film or a polyethylene resin (PE) film and laminated on the lower surface of the metal foil layer. A material having a fusible resin film layer and an outer resin film layer made of a polyester resin (PEs) film, a polyamide resin (PA) film or the like and laminated on the upper surface of the metal foil layer is used. Further, the lid (3) is integrally formed with an opening tab (31) at a part of its outer peripheral edge so as to protrude outward from the flange (23) of the molded container (2). (See FIG. 3).
The means for heat-sealing (heat-sealing) the lid (3) to the flange (23) of the molded container (2) is not particularly limited. For example, the lower surface peripheral portion of the lid (3) is overlapped on the upper surface of the flange (23). In addition, these polymerization portions are performed by heating for a predetermined time while applying a predetermined pressure with a hot plate heated to a predetermined temperature (for example, about 180 ° C.).

Next, the package (4) obtained in the above step is introduced into the retort sterilizer (5), and a retort sterilization process is performed.
This retort sterilization treatment step can also serve as a heat treatment step for eliminating whitening that has occurred in a part of the outer resin film layer (12) of the molded container (2). That is, in the molded container (2) formed by molding the laminate (10) according to the present invention into a cup shape, as described above, depending on the specific resin composition of the second resin film layer (12A) of the laminate (10), Although the occurrence of whitening in the outer resin film layer (12) is suppressed, in the unlikely event, a part of the outer resin film layer (12), in particular, the bottom wall (21) and the peripheral wall (22 having a large degree of deformation due to molding) By performing this heat treatment even if slight whitening occurs due to voids (voids) generated at the interface between the olefin resin matrix and the olefin elastomer at the corners of the boundary with Whitening can be completely eliminated.
The heating temperature of the package (4) in this step is set to a temperature equal to or higher than the softening point of the resin of the second resin film layer (12A) of the laminate (10). More preferably, the heating temperature is not less than the softening point and less than the melting point of the resin. By setting the heating temperature to a temperature equal to or higher than the softening point of the resin, the distortion of the laminate (10) due to molding is relaxed, and voids are easily filled. Further, by setting the heating temperature to a temperature lower than the melting point of the resin, the shape of the molded container (2) can be maintained even after heating. Specifically, the temperature is about 80 ° C. or higher, preferably about 100 to 180 ° C. The heating time is about 5 minutes to 3 hours.
Of course, the heat treatment step may be other than the retort sterilization treatment, and may be performed by, for example, an oven heat treatment, a hot water immersion treatment, or the like. In the case of a heat treatment other than the retort sterilization treatment, only the molded container (2) may be heat-treated in the step before forming the package (4).

FIG. 3 shows the package (4) after the retort sterilization treatment.
The illustrated package (4) is provided with a molded container (2) that is not whitened by molding and has a good overall appearance, and can give a high-class feeling to consumers.

  Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.

<Example 1>
As a metal foil layer, it is made of A8021H-O classified according to JIS H4160, and a chemical conversion treatment solution consisting of polyacrylic acid, trivalent chromium compound, water and alcohol is applied on both sides, and dried at 180 ° C. An aluminum foil having a thickness of 120 μm on which a chemical conversion film having a chromium adhesion amount of 5 mg / m ² was formed was prepared.
An unstretched polypropylene resin film (CPP) having a three-layer structure with a thickness of 30 μm was prepared as the outer resin film layer. The film comprises a first resin film layer having a thickness of 4 μm made of an ethylene-propylene random copolymer (R-PP, melting points 152 ° C., 144 ° C., crystal melting energy 57 J / g), and a first elastomer-modified olefin resin. (B-PP1) 99% by mass of an ethylene-propylene elastomer-modified homopolypropylene resin copolymerized with ethylene and propylene having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin resin ( B-PP2) having a melting point of 144 ° C. and a crystal composition energy of 19 J / g, ethylene-propylene elastomer-modified random copolymer obtained by copolymerizing ethylene and propylene, and a thickness of 22 μm. Second resin film layer and ethylene-propylene run Using a T-die molding machine so that a 4 μm-thick third resin film layer made of a dam copolymer (R-PP, melting points 152 ° C., 144 ° C., crystal melting energy 57 J / g) is formed in this order. Formed by coextrusion. Further, 2000 ppm erucamide was added to the second resin film layer, and 1000 ppm erucamide and 5000 ppm silica were added to the first resin film layer and the third resin film layer, respectively.
Here, the melting point (Tmp) and the crystal melting energy (ΔH) of each resin are measured under the following measurement conditions.
・ Raising / lowering speed: Increase / decrease speed of 10 ℃ / min between 23 ℃ and 210 ℃ ・ Sample fee: 5mg metering ・ Container: Using aluminum pan ・ Equipment: “DSC-60A” manufactured by Shimadzu Corporation
Next, a plain print layer of yellow ink was formed on the entire surface of the unstretched polypropylene resin film on the metal foil layer side using a gravure printing machine.
Further, as the inner resin layer, a composite sheet (layer ratio: 50 μm / 250 μm) of a high-density polyethylene resin film (HDPE) and a polypropylene resin film (PP) having a thickness of 300 μm was prepared.
Then, on one side of the aluminum foil, a non-stretched polypropylene resin film (CPP) is dry-laminated using a two-component curable polyester-polyurethane resin adhesive so that the printed layer is on the inside, and the aluminum foil On the other side, the composite sheet is dry-laminated using a two-component curable polyester-polyurethane resin adhesive so that the high-density polyethylene resin film side is inside, and is cured in an environment of 40 ° C. for 5 days. Thereby, the laminated body for molded containers of Example 1 was produced.

<Example 2>
90 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g was 10% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Example 2.

<Example 3>
An ethylene-propylene elastomer-modified random copolymer 90 having a melting point of 155 ° C. and a crystal melting energy of 51 J / g using the resin composition of the second resin film layer as the first elastomer-modified olefin resin (B-PP1). The second elastomer-modified olefin resin (B-PP2) is 10% by mass except that the melting point is 144 ° C. and the crystal-melting energy is 19 J / g. In the same manner as in Example 1, a laminate for a molded container was produced, and this was designated as Example 3.

<Example 4>
90 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 136 ° C. and a crystal melting energy of 18 J / g was 10% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Example 4.

<Example 5>
80 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was carried out except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g was 20% by mass. In the same manner as in Example 1, a laminate for a molded container was produced, and this was designated as Example 5.

<Example 6>
70 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g was 30% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Example 6.

<Example 7>
80 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 166 ° C. and a crystal melting energy of 65 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was carried out except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g was 20% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Example 7.

<Example 8>
70 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 166 ° C. and a crystal melting energy of 65 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g was 30% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Example 8.

<Example 9>
As the outer resin film layer, an unstretched polypropylene resin film (CPP) having a two-layer structure with a thickness of 26 μm was used. The film comprises a first resin film layer having a thickness of 4 μm made of an ethylene-propylene random copolymer (R-PP, melting points 152 ° C., 144 ° C., crystal melting energy 57 J / g), and a first elastomer-modified olefin resin. (B-PP1) 90% by mass of an ethylene-propylene elastomer-modified homopolypropylene resin copolymerized with ethylene and propylene having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin resin ( B-PP2), a 22 μm thick second resin film layer comprising a resin composition of 10% by mass of an ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g, Are co-extruded using a T-die molding machine so that It is formed by doing.
Except for the above, a molded container laminate was produced in the same manner as in Example 1, and this was designated as Example 9.

<Example 10>
The first resin film layer and the third resin film layer were each 4 μm thick made of homopolypropylene (H-PP, melting point: 165 ° C., crystal melting energy 63 J / g). Moreover, erucic acid amide 1000ppm and silica 5000ppm were added to the 1st resin film layer and the 3rd resin film layer, respectively.
Except for the above, a molded container laminate was produced in the same manner as in Example 2, and this was designated as Example 10.

<Comparative Example 1>
An ethylene-propylene elastomer-modified homopolypropylene resin (B-PP1) film having a melting point of 163 ° C. and a crystal melting energy of 58 J / g is used as the first resin film layer, the second resin film layer, and the third resin film layer. A laminated body for a molded container was produced in the same manner as in Example 1 except that a three-layer unstretched polypropylene resin film (CPP) having a thickness of 30 μm was used, and this was used as Comparative Example 1. .

<Comparative Example 2>
The second resin film layer is not added with the first elastomer-modified olefin resin (B-PP1), but as the second elastomer-modified olefin resin (B-PP2), the melting point is 144 ° C. and the crystal melting energy is 19 J / A laminate for a molded container was produced in the same manner as in Example 1 except that it was composed of 100% by mass of the ethylene-propylene elastomer-modified random copolymer g.

<Comparative Example 3>
The second resin film layer is made of the first elastomer-modified olefin resin (B-PP1) without adding the second elastomer-modified olefin resin (B-PP2), and has a melting point of 163 ° C. and a crystal melting energy of 58 J / A laminate for a molded container was produced in the same manner as in Example 1 except that it was composed of 100% by mass of the ethylene-propylene elastomer-modified homopolypropylene resin g.

<Comparative example 4>
An ethylene-propylene elastomer-modified random copolymer 90 having a melting point of 145 ° C. and a crystal melting energy of 50 J / g, using the resin composition of the second resin film layer as the first elastomer-modified olefin resin (B-PP1). The second elastomer-modified olefin resin (B-PP2) is 10% by mass except that the melting point is 144 ° C. and the crystal-melting energy is 19 J / g. A laminated body for a molded container was produced in the same manner as in Example 1, and this was designated as Comparative Example 4.

<Comparative Example 5>
90 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 130 ° C. and a crystal melting energy of 14 J / g was 10% by mass. In the same manner as in Example 1, a laminate for a molded container was produced, and this was designated as Comparative Example 5.

<Comparative Example 6>
An ethylene-propylene elastomer-modified random copolymer 90 having a melting point of 155 ° C. and a crystal melting energy of 49 J / g using the resin composition of the second resin film layer as the first elastomer-modified olefin resin (B-PP1). The second elastomer-modified olefin resin (B-PP2) is 10% by mass except that the melting point is 144 ° C. and the crystal-melting energy is 19 J / g. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Comparative Example 6.

<Comparative Example 7>
90 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer The second elastomer-modified olefin resin (B-PP2) was used except that the ethylene-propylene elastomer-modified random copolymer having a melting point of 158 ° C. and a crystal melting energy of 44 J / g was 10% by mass. In the same manner as in Example 1, a molded container laminate was produced, and this was designated as Comparative Example 7.

<Comparative Example 8>
99 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer A molded container in the same manner as in Example 1 except that 1% by mass of an ethylene-propylene elastomer (EPR) having a melting point of 40 to 70 ° C. and a crystal melting energy of 15 J / g was used as the olefin elastomer. A laminate for manufacturing was prepared, and this was designated as Comparative Example 8.

<Comparative Example 9>
90 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer A molded container in the same manner as in Example 1 except that the ethylene-propylene elastomer (EPR) having an olefin-based elastomer having a melting point of 40 to 70 ° C. and a crystal melting energy of 15 J / g was 10% by mass. A laminate for manufacturing was produced, and this was designated as Comparative Example 9.

<Comparative Example 10>
80 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer A molded container in the same manner as in Example 1, except that the ethylene-propylene elastomer (EPR) was 20% by mass as the olefin-based elastomer having a melting point of 40 to 70 ° C. and a crystal melting energy of 15 J / g. A laminate for manufacturing was prepared, and this was designated as Comparative Example 10.

<Comparative Example 11>
70 mass of ethylene-propylene elastomer-modified homopolypropylene resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g as the first elastomer-modified olefin resin (B-PP1) as the resin composition of the second resin film layer A molded container in the same manner as in Example 1, except that 30% by mass of an ethylene-propylene elastomer (EPR) having a melting point of 40 to 70 ° C. and a crystal melting energy of 15 J / g was used as the olefin elastomer. A laminate for manufacturing was prepared, and this was designated as Comparative Example 11.

[Production of container]
Next, each of the molded container laminates of Examples 1 to 10 and Comparative Examples 1 to 11 is cut into a predetermined shape and size to produce a blank, and a small amount of siloxane is applied to both sides of each blank. From a deep cup using a male mold and a female mold (manufactured by Amada Co., Ltd.), a round cup-shaped container having a flange (bottom diameter 52 mmφ, opening diameter 65 mmφ, height 30 mm, flange 8 mm in width) was produced.

[Production of lid]
On the other hand, a polyethylene terephthalate resin (PET) film having a thickness of 12 μm as an outer resin layer is formed on one side of an aluminum foil made of A1N30H-O classified according to JIS H4160 and having a thickness of 20 μm. A dry lamination using an adhesive, and a linear low density polyethylene resin (LLDPE) film having a thickness of 30 μm as a heat-fusible resin layer on the other surface of the aluminum foil is a two-component curing type polyester-polyurethane resin system. The laminated body for lid | covers was produced by carrying out dry lamination using the adhesive agent, and curing for 5 days in a 40 degreeC environment.
The obtained laminated body was cut into a required shape and size according to the flange, thereby producing a lid with an opening tab.

[Production of packaging body]
70 ml of water is put into each of the above containers, and then the lid is stacked on the top surface of the flange of the container so that the non-stretched polypropylene resin film (CPP) surface is in contact with each other. A heat plate (outer diameter 90 mmφ, inner diameter 74 mmφ) was pressed with a pressure of 150 kgf for 3 seconds to perform heat sealing (thermal fusion).
Thus, a package was obtained.

[Verification of package appearance]
By visually observing the container of each obtained package, it was verified whether or not the outer resin film layer was whitened and whether or not the outer resin film layer of the flange was crushed. The verification results are shown in Tables 1 and 2 below together with the composition of the second resin film layer of the laminate that is the molding material of each container.
In Tables 1 and 2, in the column of “whitening during molding”, “◎” indicates that the outer resin film layer of the container is not whitened or hardly whitened, and “○” indicates that whitening is small. “△” indicates that whitening has occurred in a streak pattern along the circumferential direction in the R portion of the bottom of the container, and “White” indicates that whitening has occurred remarkably over a wide area in the R portion of the bottom of the container. × ”. Moreover, in the column of “Flange Crush” in Tables 1 and 2, the outer resin film layer of the flange of the container was “◎” when there was no occurrence of crush due to heat sealing of the lid, and there was almost no crush. “◯” indicates a case where crushing occurred to some extent, “△” indicates that crushing occurred to some extent, and “x” indicates that crushing occurred remarkably. In Tables 1 and 2, the ethylene-propylene random copolymer is “R-PP”, the homopolypropylene is “H-PP”, the first elastomer-modified olefin resin is “B-PP1”, and the second elastomer-modified olefin. The system resin is indicated as “B-PP2”, and the ethylene-propylene elastomer is indicated as “EPR”.

As is apparent from Table 1, it can be seen that the laminated bodies of Examples 1 to 10 have improved whitening phenomenon during molding. Moreover, in the case of Examples 1-10, the outer resin film layer of the flange of the container after heat-sealing the lid was not crushed.
On the other hand, as shown in Table 2, in the laminates of Comparative Examples 1, 3 and 8 to 11, a strong whitening phenomenon was observed over a wide area in the R part at the bottom of the molded container.
In the laminate of Comparative Example 2, the outer resin film layer of the flange of the container after the lid was heat-sealed was crushed, and the shape retainability was insufficient. Moreover, in the laminated body of the comparative example 2, stripe-like whitening had arisen along the circumferential direction in R part of the bottom of the container after shaping | molding.
In the laminate of Comparative Example 4, a strong whitening phenomenon was observed over a wide area in the R part at the bottom of the molded container, and the outer resin film layer of the flange of the container after the lid was heat-sealed to some extent. It was.
In the laminates of Comparative Examples 5 and 7, the outer resin film layer of the flange of the container after the lid was heat-sealed was not crushed, but the R portion at the bottom of the molded container was streaked along the circumferential direction. Whitening of the shape occurred.
In the case of the laminate of Comparative Example 6, whitening due to molding was substantially suppressed, but the outer resin film layer of the flange of the container after the lid was heat sealed was crushed to some extent.
From the above verification results, the collapse of the outer resin film layer of the flange of the container is considered to be affected by both the melting point of the resin component and the crystal melting energy, and the melting points (including B-PP1 and B-PP2) The higher melting point) is 155 ° C. or higher, and the crystal melting energy (in the case of containing B-PP1 and B-PP2 is a weighted average of the crystal melting energies of the two by the content ratio) is 40 J / It can be seen that crushing hardly occurs when it is g or more (more preferably 50 J / g or more).

  The present invention is used for hermetically packaging foods and the like, and can be suitably used for a molded container excellent in long-term storage stability and having a good appearance and a laminate as a molding material thereof.

(2): Molded container
(23): Flange
(3): Lid
(4): Packaging
(5): Retort sterilizer
(10): Molded container laminate
(11): Metal foil layer
(12): Outer resin film layer
(12A): Second resin film layer
(12B): First resin film layer
(12C): Third resin film layer
(15): Print layer
(C): Contents

Claims (12)

A laminated body for a molded container comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each made of an elastomer-modified homopolypropylene resin,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more. A laminated body for a molded container comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each made of an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of copolymer components,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more. A laminated body for a molded container comprising a metal foil layer and an outer resin film layer laminated on the outer surface of the container among both surfaces of the metal foil layer,
The outer resin film layer has a first resin film layer containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components or a polymer of propylene alone, a melting point of 155 ° C. or more, and A resin composition comprising a first elastomer-modified olefin resin having a crystal melting energy of 50 J / g or more and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It is a multilayer structure of two or more layers having at least a second resin film layer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are respectively composed of an elastomer-modified homopolypropylene resin and an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of copolymer components,
The said 2nd resin film layer WHEREIN: The laminated body for shaping | molding containers whose sum total value of the content rate of a said 1st elastomer modified olefin resin and the content rate of a said 2nd elastomer modified olefin resin is 50 mass% or more.   The laminated body for molded containers according to any one of claims 1 to 3, wherein in the second resin film layer, the content of the second elastomer-modified olefin resin is 1 to 50 mass%.   The laminated body for molded containers according to any one of claims 1 to 4, wherein in the second resin film layer, the content of the first elastomer-modified olefin resin is 49 to 99 mass%.   The elastomer component of the first elastomer-modified olefin resin and the second elastomer-modified olefin resin is at least one of ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer, respectively. The laminated body for molded containers according to any one of claims 1 to 5, wherein   The outer resin film layer includes at least one of inorganic fine particles, organic fine particles, and a slip agent in a layer constituting the outer surface of the laminate for a molded container. The laminated body for molded containers as described in any one.   The laminate for a molded container according to any one of claims 1 to 7, wherein the second elastomer-modified olefin-based resin has two or more crystallization peaks in a differential scanning calorimetry graph.   The outer resin film layer includes the second resin film layer, the first resin film layer interposed between the second resin film layer and the metal foil layer, and propylene as one of the copolymerization components. It has at least a third resin film layer containing 50% by mass or more of a random copolymer or a propylene single polymer and laminated on the surface of the second resin film layer opposite to the metal foil layer. The laminated body for molded containers according to any one of claims 1 to 8, which has a multilayer structure of three or more layers.   A printing layer is formed between the metal foil layer and the outer resin film layer, or a predetermined component is displayed on the surface of the outer resin film layer by adding a coloring component to the outer resin film layer. Or the decoration is showing, The laminated body for molded containers as described in any one of Claims 1-9.   A molded container formed by molding the laminated body for molded containers according to any one of claims 1 to 10 into a cup shape, and having a flange at the periphery of the opening.   The package body which a lid | cover is joined to the flange of the shaping | molding container of Claim 11 with which the content was filled so that the opening of a shaping | molding container might be covered.

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