TWI770360B - Laminates, shaped containers, and packages for shaped containers - Google Patents

Abstract

[Problem] As a container for molding a laminate having a metal foil layer and an outer resin film layer, it is possible to inexpensively provide an outer surface having a matte state with a favorable appearance. [Solution] The outer resin film layers 12 and 12A of the outer surface layer 120 in the matte state of the laminated body 2 for forming a container are formed of a resin composition containing crystals having a melting point of 155° C. or higher A first elastomer-modified olefin-based resin having a melting energy of 50 J/g or more, a second elastomer-modified olefin-based resin having a melting point of 135° C. or higher and a crystal melting energy of 30 J/g or less, and an olefin-based elastomer. The first and second elastomer-modified olefin resins are elastomer-modified random copolymers of elastomer-modified homogeneous polypropylene resins and/or elastomer-modified bodies of random copolymers containing propylene as a copolymerization component, respectively. formed by things. The total value of the content of the first and second elastomer-modified olefin resins is 50% by mass or more.

Description

Laminates, shaped containers, and packages for shaped containers

The present invention relates to a laminate used as a material for a molded container for sealing and packaging foods, etc., a molded container for molding the laminate, and a package in which the molded container filled with the contents is covered, and more More specifically, it relates to a laminated body for a shaped container, a shaped container, and a package having an outer surface in a matt state.

As a container that can be stored for a long time, for example, water yokan, jelly, weaned food, nursing food, etc., there is known a molded container including a metal foil layer formed of aluminum foil or the like, and a metal foil layer laminated on the metal foil layer. A laminated body of a single layer or a plurality of layers of the outer resin film layer which becomes the outer surface of the container among the two sides of the container is molded into a cup shape (refer to the following Patent Document 1, etc.).

Here, in the packaging field, in order to give a high-quality appearance, a container having a matte outer surface is sometimes used.

For example, Patent Document 2 described below discloses the production of a stationery file or the like having an outer surface in a matte state by using an embossed polypropylene resin film.

The following Patent Document 3 discloses a hard coat film for molding in which a hard coat layer is formed on the outer surface of the outermost layer having a matte state.

In addition, the following patent document 4 discloses a polypropylene-based sheet having a matte surface obtained by blending a polypropylene resin, a polyethylene resin, and an elastomer.

[Prior Art Literature] [Patent Literature]

[Patent Document 1]] Japanese Patent Application Laid-Open No. 6-345123

[Patent Document 2] Japanese Patent Application Laid-Open No. 5-320376

[Patent Document 3] Japanese Patent Laid-Open No. 2011-148301

[Patent Document 4] Japanese Patent Application Laid-Open No. 2-92944

However, when the laminated body in which the outer resin film layer is formed by the embossed film as shown in the above-mentioned Patent Document 2 is molded into a cup shape, the embossed film is stretched at the time of molding and occurs on the outer surface of the matte state. Spots may detract from appearance. In addition, when an embossed film is used, there is a problem of high cost.

In addition, when a laminate having an outer resin film layer formed of a film having a coating layer in a matte state as shown in the above-mentioned Patent Document 3 is molded into a cup shape, cracks occur in the coating layer or the coating layer peels off. . In addition, there is also a problem of high cost when forming a coating layer in a matte state.

In addition, when a laminated body in which a sheet in a matte state constitutes a surface layer as described in Patent Document 4 above is molded into a cup shape, since the compatibility of the polyethylene resin and the elastomer with the polypropylene resin is low, there is a problem in the molded body. The problem of whitening occurs on the surface.

The present invention was made in view of the above-mentioned problems, and an object of the present invention is to provide, at low cost, an outer surface having a good appearance in a matte state as a container formed by molding a laminate having a metal foil layer and an outer resin film layer.

The present invention has been accomplished by the following aspects in order to achieve the above-mentioned object.

1) A laminate for forming a container, comprising: a metal foil layer; and an outer resin film layer that is laminated on the surface that becomes the outer surface of the container among both sides of the metal foil layer and constitutes an outer surface layer in a matte state the outer resin film layer is formed of a resin composition comprising a first elastomer-modified olefin resin having a melting point of 155°C or more and a crystal melting energy of 50 J/g or more, a melting point of 135°C or more and a crystal A second elastomer-modified olefin-based resin having a melting energy of 30 J/g or less, and an olefin-based elastomer, wherein the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are each composed of an elastomer A modified homogeneous polypropylene resin, wherein in the outer resin film layer, the total value of the content of the first elastomer-modified olefin resin and the content of the second elastomer-modified olefin resin is 50 mass %above.

2) A laminate for forming a container, comprising: a metal foil layer; and an outer resin film layer that is laminated on the surface that becomes the outer surface of the container among both sides of the metal foil layer and constitutes an outer surface layer in a matte state the outer resin film layer is formed of a resin composition comprising a first elastomer-modified olefin resin having a melting point of 155°C or more and a crystal melting energy of 50 J/g or more, a melting point of 135°C or more and a crystal A second elastomer-modified olefin-based resin having a melting energy of 30 J/g or less, and an olefin-based elastomer, wherein the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are each composed of an elastomer The modified random copolymer is formed, The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of the copolymerization components, and in the outer resin film layer, the content of the first elastomer-modified olefin-based resin is The total value with the content of the second elastomer-modified olefin-based resin is 50% by mass or more.

3) A laminate for forming a container, comprising: a metal foil layer; and an outer resin film layer that is laminated on the surface that becomes the outer surface of the container among both sides of the metal foil layer and constitutes an outer surface layer in a matte state the outer resin film layer is formed of a resin composition comprising a first elastomer-modified olefin resin having a melting point of 155°C or more and a crystal melting energy of 50 J/g or more, a melting point of 135°C or more and a crystal A second elastomer-modified olefin-based resin having a melting energy of 30 J/g or less, and an olefin-based elastomer, wherein the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are each composed of an elastomer It is formed of a modified homogeneous polypropylene 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 the copolymerization components. In the resin film layer, the total value of the content of the first elastomer-modified olefin resin and the content of the second elastomer-modified olefin resin is 50% by mass or more.

4) The laminate for forming a container according to any one of 1) to 3) above, wherein the content of the second elastomer-modified olefin resin in the outer resin film layer is 1 to 50 mass % .

5) The laminate for forming a container according to any one of the above 1) to 4), wherein the content of the first elastomer-modified olefin resin in the outer resin film layer is 49 to 98% by mass .

6) The laminate for forming a container according to any one of 1) to 5) above, wherein the content of the olefin-based elastomer in the outer resin film layer is 1 to 30% by mass.

7) The laminate for forming a container according to any one of 1) to 6) above, wherein the glossiness of the surface of the outer resin film layer is 0.5 to 12%.

8) The laminate for forming a container according to any one of 1) to 7) above, wherein the elastomer components of the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are respectively At least one of ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer.

9) The laminate for forming a container according to any one of the above 1) to 8), wherein the olefin-based elastomer is an ethylene-propylene elastomer, an ethylene-1-butene elastomer, an ethylene-propylene-1- At least one of butene elastomers.

10) The laminate for forming a container according to any one of 1) to 9) above, wherein the aforementioned outer resin film layer further comprises at least any one of inorganic fine particles, organic fine particles and a lubricant.

11) The layered product for forming a container according to any one of 1) to 10) above, wherein the second elastomer-modified olefin-based resin has two or more crystallization peaks in a differential scanning calorimetry chart.

12) The laminate for forming a container according to any one of the above 1) to 11), wherein a plurality of outer resin film layers are formed in the area layer which becomes the outer side of the container on both sides of the aforementioned metal foil layers, The outermost surface layer is constituted by the outermost one of the outer resin film layers of the plurality of layers.

13) The laminate for forming a container according to any one of the above 1) to 12), wherein a printed layer is formed between the metal foil layer and the outer resin film layer, or the outer resin film layer is added The coloring component exhibits a predetermined display or decoration on the surface of the outer resin film layer.

14) A molded container in which the laminated body for a molded container according to any one of the above 1) to 13) is molded into a cup shape, and has a flange on the periphery of an opening.

15) A package attached to the flange of a shaped container as in 14) above filled with contents, engaging a lid to cover the opening of the shaped container.

However, in the present specification and the scope of the patent application, "melting point" is the melting peak temperature (Tmp) measured by differential scanning calorimetry (DSC) in accordance with JIS K7121-1987.

Similarly, the "crystal melting energy" is the heat of fusion (crystal melting energy, ΔH) measured by differential scanning calorimetry (DSC) in accordance with JIS K7122-1987. Among them, if there are two or more crystal melting peak curves and two or more crystal melting energy (ΔH1, ΔH2) or three or more, it refers to the value of the highest crystal melting energy.

In the above-mentioned 1) to 3) in the laminated body for forming the container, the outer resin film layer constituting the outer surface layer of the matte state is formed by a resin composition, and the resin composition is formed by melting the melting point at 155° C. or more and melting the crystals. A combination of a first elastomer-modified olefin-based resin having an energy of 50 J/g or more, a second elastomer-modified olefin-based resin having a melting point of 135° C. or higher and a crystal melting energy of 30 J/g or less, and an olefin-based elastomer, Therefore, the first and second elastomer-modified olefin-based resins of the above-mentioned resin compositions have good compatibility with the olefin-based resin and good dispersibility of the elastomer-based component, and the olefin-based resin phase and the elastomeric component have good compatibility. The bonding strength of the interface increases. Therefore, when the laminates of the above 1) to 3) are formed, the interface between the olefin-based resin phase and the elastomer component is peeled off due to stress to prevent the generation of voids called voids. And prevent the deterioration of transparency, that is, the phenomenon of whitening, due to the difference in the refractive index between the resin and the hole. Next, in the case of the laminates of the above 1) to 3), as in the laminates in which the outer surface of the matte state is formed by embossing the film, there is no possibility that the outer surface is stretched during molding, and spots are not generated on the outer surface, and Even if the laminate on the outer surface of the outer resin film layer is composed of a film having a coating layer in a matte state, the coating layer does not have cracks or the coating layer is peeled off, and it is not cost-intensive.

Therefore, by the above-mentioned 1)-3) laminated body for a molded container, the molded container which has the outer surface of the matte state favorable in appearance can be obtained at low cost.

In addition, with the above-mentioned 1) to 3) laminates for molding containers, since the melting point of the first elastomer-modified olefin resin in the resin composition constituting the outer surface layer is 155° C. or higher, for example, the lid is heated. When sealing the flange of the container formed with the laminated body, the outer surface layer is not easily damaged by pressure, and sufficient shape retention can be ensured.

With the laminate for forming a container according to 4) above, the above effects can be sufficiently ensured with respect to the laminates 1) to 3) above, especially when, for example, a lid is heat-sealed on the flange of a container in which the laminate is to be formed. When the outer surface layer is further less susceptible to pressure loss, the whitening phenomenon can be suppressed more reliably.

With the layered product for forming a container according to the above 5), the above-mentioned effects can be more sufficiently ensured with respect to the layered product of the above-mentioned 1) to 3).

With the layered product for forming a container according to the above-mentioned 6), the above-mentioned effects can be more sufficiently ensured with respect to the layered product of the above-mentioned 1) to 3).

With the layered product for forming a container according to the above 7), the above-mentioned effects can be more sufficiently ensured with respect to the layered product of the above-mentioned 1) to 3).

With the layered product for forming a container according to the above 8), the above-mentioned effects can be more sufficiently ensured with respect to the layered product of the above-mentioned 1) to 3).

With the layered product for forming a container according to the above 9), the above-mentioned effects can be more sufficiently ensured with respect to the layered product of the above-mentioned 1) to 3).

According to the above-mentioned layered product for forming a container in 10), the matte state (unevenness) of the outer surface of the layered product can be finely adjusted to obtain more excellent design properties. Forming with a deeper forming depth is favorably performed, and even whitening at the time of forming is sufficiently suppressed.

The above-mentioned effects can be more sufficiently ensured with the above-mentioned layered product of 1) to 3) by the layered product for forming a container according to 11) above.

The above-mentioned effects can be more sufficiently ensured by the above-mentioned layered product of 12) for forming a container and the above-mentioned layered product of 1) to 3).

With the above-mentioned 13) laminate for forming a container, by forming a printed layer between the metal foil layer and the outer resin film layer, or by adding a coloring component to the outer resin film layer, a predetermined display is displayed on the surface of the outer surface layer. or decoration, so that the appearance of the formed container formed with the laminated body becomes more excellent.

According to the above-mentioned molded container of 14), since the outer surface has a matte state with good appearance, it can be given a high-quality feeling.

According to the package of 15) above, the productivity is good and the cost can be suppressed. Therefore, the container having the outer surface in a matte state with good appearance can be provided with a high-quality feeling by suppressing whitening at the time of molding.

2: Forming container

23: Flange

3: cover

4: Packaging body

5: Sterilization device for sterilizer

10: Laminates for forming containers

11: Metal foil layer

12: Outer resin film layer

12A: 1st outer resin film layer

12B: Second outer resin film layer

120: outer surface layer

120a: Surface of the outer surface layer

13: Inner resin layer

14: Adhesive layer

15: Printing layer

16: Adhesive layer

21: Bottom wall

22: Zhou Wall

31: Tabs for opening

C: Contents

FIG. 1 is a partially enlarged cross-sectional view showing the layer structure of two aspects of the layered product for forming a container according to the embodiment of the present invention.

The second figure is a vertical cross-sectional view showing the manufacturing method of the package according to the embodiment of the present invention in the order of the steps.

The third figure is a perspective view of a package manufactured by the same method.

Embodiments of the present invention will be described below with reference to the first to third figures.

The first figure shows the layer structure of the layered product for forming the container according to the embodiment of the present invention. The layered body (10) in the drawing has: a metal foil layer (11); and an outer resin film layer (12) laminated on the outer surface of the molding container (2) on both sides of the metal foil layer (11): (12A)(12B). Moreover, the laminated body (10) of this embodiment has the inner resin layer (13) laminated|stacked on the surface which becomes the inner side of the container (2) among both surfaces of the metal foil layer (11).

More specifically, in the laminate (10) shown in the first figure (a), the outer resin film layer (12) has a single-layer structure, and this layer (12) constitutes the extinction of the laminate (10). state of the outer surface layer (120). In addition, in the laminate (10) shown in the first figure (b), the outer resin film layer is composed of the first outer resin film layer (12A) that constitutes the outer surface layer (120) of the laminate (10) in a matte state. ), and a two-layer structure formed by a second outer resin film layer (12B) interposed between the first outer resin film layer (12A) and the metal foil layer (11).

The metal foil layer (11) plays a role of providing a barrier property for preventing the intrusion of oxygen or moisture to the laminated body (10) for forming the container.

As the metal foil constituting the metal foil layer (11), aluminum foil, iron foil, stainless steel foil, copper foil, etc. can be used, but it is preferable to use aluminum foil. In the case of aluminum foil, either pure aluminum foil or aluminum alloy foil may be used. In addition, any one of soft and hard may be used. For example, if the iron content is 0.3 to 1.5 mass %, it is divided by JIS H4160. The annealed soft material (O material) of the A8000 series (especially A8079H or A8021H) is suitable for use because of its excellent formability.

On one side or both sides of the metal foil layer (11), base treatment such as chemical conversion treatment is performed as required. Specifically, for example, on the surface of the degreasing metal foil, any one of the following aqueous solutions 1) to 3) is applied:

1) An aqueous solution of a mixture comprising: phosphoric acid; chromic acid; and at least one compound selected from the group consisting of a metal salt of fluoride and a non-metallic salt of fluoride.

2) An aqueous solution of the mixture, comprising: phosphoric acid; at least one resin selected from the group consisting of acrylic resin, chitosan derivative resin, and phenol-based resin; and selected from chromic acid and chromium (III) At least one compound of the group consisting of salts.

3) An aqueous solution of the mixture, comprising: phosphoric acid; at least one resin selected from the group consisting of acrylic resins, chitosan derivative resins, and phenol-based resins; selected from chromic acid and chromium (III) salts at least one compound from the group consisting of; and At least one compound selected from the group consisting of metal salts of fluorides and non-metallic salts of fluorides.

After that, by drying, chemical conversion treatment is performed to form a film.

The film formed on the surface of the metal foil layer (11) by the above-mentioned chemical conversion treatment is preferably formed with a chromium adhesion amount (average single side) of 0.1 mg/m ² to 50 mg/m ² , especially 2 mg/m 2 . m ² ~20mg/m ² is better.

The thickness of the metal foil layer (11) is preferably 30 to 200 μm, preferably 50 to 150 μm. By forming it in the said range, sufficient barrier property and formability are obtained.

The outer resin film layer (12): (12A) (12B) exerts the design property of making the outer surface of the molding container (2) a matte state, and imparts deep drawing moldability or convexity to the laminated body (10) for the molding container. A formative role.

The outer resin film layer (12) or the first outer resin film layer (12A) constituting the outer surface layer (120) in the matte state is formed of a resin composition comprising: a melting point (Tmp) of 155° C. A first elastomer-modified olefin resin having a crystal melting energy (ΔH) of 50 J/g or more and a second elasticity having a melting point (Tmp) of 135° C. or higher and a crystal melting energy (ΔH) of 30 J/g or less Body-modified olefin resin and olefin elastomer. Next, in the outer surface layer (120) formed by the layers (12): (12A), the glossiness (gloss value) of the surface (120a) is 0.5-30%, preferably 0.5-12%, 0.5~9% is better. Here, the "gloss" is the gloss (gloss value) measured according to JIS Z8741-1997 (specular gloss - measuring method, method 3 (incidence angle 60 degrees)).

The first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are composed of an elastomer-modified homogeneous polypropylene and/or an elastomer-modified random copolymer, respectively. The above-mentioned elastomer-modified random copolymer is a random copolymer (random polypropylene) containing propylene and monomers other than propylene as copolymerization components elastomer modifier. Copolymerization components (monomers) other than propylene are not particularly limited, for example, olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene are not included. In addition, butadiene etc. are mentioned. As for the elastomer component, it is not particularly limited, but only one of ethylene-propylene elastomer (EPR), ethylene-1-butene elastomer (EBR), and ethylene-propylene-1-butene elastomer (EPBR) is used. At least one of them is preferred.

The above-mentioned olefin-based elastomers are not particularly limited, but ethylene-propylene elastomers (EPR), ethylene-1-butene elastomers (EBR), ethylene-propylene-1-butene elastomers ( At least one of EPBR) is preferred.

The olefin-based resin is modified by including a first elastomer having a melting point (Tmp) of 155°C or more and a crystal melting energy (ΔH) of 50 J/g or more, and a melting point (Tmp) of 135°C or more and a crystal melting energy (ΔH). H) is a resin composition of 30 J/g or less of the second elastomer-modified olefin-based resin to constitute the outer surface layer (120) for the following reasons.

That is, if the melting point of the first elastomer-modified olefin resin is less than 155° C., the laminate (10) will be significantly whitened during molding, and the lid (3) will be heat-sealed on the flange (2) of the container (2). 23), the outer surface layer (120) tends to be damaged by pressure (refer to Comparative Example 5).

In addition, when the melting point of the second elastomer-modified olefin resin was less than 135° C., whitening remarkably occurred during molding of the layered body (10) (refer to Comparative Example 6).

In addition, when the crystal melting energy (ΔH) of the first elastomer-modified olefin resin is less than 50 J/g, the outer surface layer ( 120 ) tends to be damaged by pressure during the above heat sealing (see Comparative Example 7).

In addition, when the crystal melting energy (ΔH) of the second elastomer-modified olefin resin exceeds 30 J/g, whitening occurs to a certain extent when the layered body (10) is molded (refer to Comparative Example 8).

In addition, unless the first elastomer-modified olefin-based resin having a melting point (Tmp) of 155°C or more and a crystal melting energy (ΔH) of 50 J/g or more is not contained, whitening occurs to a certain extent during molding, and the outer surface layer ( 120) Pressure loss is easy, and shape retention is easy to become insufficient (refer to Comparative Example 3).

In addition, if 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, whitening occurs remarkably during molding (see Comparative Example 4).

The melting point of the first elastomer-modified olefin resin is preferably 155°C or higher and 185°C or lower. The crystal melting energy of the first elastomer-modified olefin resin is preferably 50 J/g or more and 75 J/g or less, 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 10 J/g or more and 10 J/g or more. Below 20J/g is particularly good.

Regarding the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin, as an elastomer-modified aspect, graft polymerization is exemplified, but other modified aspects may be used.

The first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin can be produced, for example, by the reactor production method shown below.

That is, first, a Ziegler-Natta catalyst, a cocatalyst, propylene, and hydrogen are supplied to the first reactor to polymerize homogeneous polypropylene.

Next, the obtained homogeneous polypropylene was moved to the second reactor in a state containing unreacted propylene and the Ziegler-Natta catalyst. In the second reactor, propylene and hydrogen were additionally added to polymerize homogeneous polypropylene.

Next, the obtained homogeneous polypropylene was moved to the third reactor in a state containing unreacted propylene and the Ziegler-Natta catalyst. In the third reactor, ethylene, propylene, and hydrogen are additionally added to polymerize an ethylene-propylene elastomer (EPR) in which ethylene and propylene are copolymerized.

As a result, the first elastomer-modified olefin-based resin or the second elastomer-modified olefin-based resin is produced.

The aforementioned first elastomer-modified olefin-based resin can be produced in a liquid phase by adding a solvent, for example. Moreover, the said 2nd elastomer-modified olefin resin system can be manufactured by making a reaction in a gas phase, for example, without using a solvent.

However, the above only shows an example of the production method, and the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are not limited to those produced by the above-described production method.

In the outer surface layer (120) of the layered body (10), the content of the second elastomer-modified olefin resin is preferably 1 to 50% by mass, preferably 5 to 30% by mass, and 10 to 25 mass % is particularly preferred. If the content of the second elastomer-modified olefin resin is less than 1% by mass, whitening may occur when the layered body (10) is molded. On the other hand, when the content of the second elastomer-modified olefin-based resin exceeds 50 mass %, heat resistance decreases.

In the outer surface layer (120), the content of the first elastomer-modified olefin resin is preferably 49 to 98% by mass, preferably 70 to 95% by mass, and preferably 75 to 90% by mass Excellent. When the content of the first elastomer-modified olefin-based resin exceeds 98% by mass, whitening may occur when the layered body (10) is molded. On the other hand, if the content of the first elastomer-modified olefin resin is less than 49% by mass, the heat resistance will decrease.

In the outer surface layer (120), the content of the olefin-based elastomer is preferably 1 to 30% by mass, preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass. If the content of the olefin-based elastomer is less than 1 mass %, there is a possibility that the appearance of the matt state cannot be obtained. On the other hand, if the olefin-based elastomer If the content exceeds 30% by mass, the heat resistance is insufficient, and when the lid (3) is heat-sealed to the flange (23) of the molded container (2), the outer surface layer (120) of the flange (23) may be formed. Danger of pressure loss.

The outer surface layer (120) is preferably formed in a sea-island structure. By forming the sea-island structure as described above, the surface of the outer surface layer ( 120 ) is appropriately formed with irregularities, so that light is randomly reflected, gloss is suppressed, and an excellent appearance in a matte state is obtained. In the above-mentioned sea-island structure, it is preferable that the elastomer component forms islands.

It is preferable that the second elastomer-modified olefin-based resin has two or more crystallization peaks in a differential scanning calorimetry (DSC) measurement chart. In the case of having two crystallization peaks, the crystallization peak (crystallization temperature) on the high temperature side is preferably 90°C or higher, and the crystallization peak (crystallization temperature) on the low temperature side is preferably 80°C or lower. In addition, if there are three or more crystallization peaks, the crystallization peak (crystallization temperature) on the highest temperature side is preferably 90°C or higher, and the crystallization peak (crystallization temperature) on the lowest temperature side is preferably 80°C or lower. .

The outer surface layer (120) preferably contains inorganic fine particles, organic fine particles, and lubricants in addition to the first elastomer-modified olefin-based resin, the second elastomer-modified olefin-based resin, and the olefin-based elastomer. At least one of them. By adding inorganic fine particles or organic fine particles to the outer surface layer ( 120 ), the matte state (unevenness) of the outer surface of the layered body ( 10 ) can be finely adjusted, and more excellent design properties can be obtained. In addition, by adding a lubricant to the outer surface layer (120), excellent sliding properties are imparted to the outer surface of the layered body (10), forming with a deeper forming depth can be performed well, and whitening during forming is also sufficiently suppressed. .

The inorganic fine particles are not particularly limited, and examples thereof include silicon oxide, aluminum silicate, barium sulfate, and the like. Although it does not specifically limit about the said organic microparticles|fine-particles, For example, an acrylic resin particle, a polystyrene resin particle, etc. are mentioned. The aforementioned lubricant is not particularly limited, and examples thereof include fatty acid amides such as erucamide, stearic acid amide, and oleic acid amide, and waxes such as crystal wax and polyethylene wax. In addition, it is also possible to take Instead of adding a lubricant or removing lubricant, a lubricant such as silicone oil or rapeseed oil is coated on the surface of the layered body (10) during forming.

In the laminate (10) having the outer resin film layers (12A) and (12B) having a two-layer structure as shown in FIG. 1 (b), the second outer resin film layer is disposed on the metal foil layer (11) side. (12B) is preferably formed from a resin composition containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components. Copolymerization components (monomers) other than propylene are not particularly limited. For example, olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene are excluded. Butadiene etc. are mentioned. Sufficient heat sealing strength can be ensured by the content rate of the said random copolymer being 50 mass % or more. It is preferable to set the content rate of the said random copolymer in a 2nd outer resin film layer (12B) to 70 mass % or more. Further, the random copolymer containing propylene as one of the copolymerization components is preferably a random copolymer having two or more melting points. At this time, the bonding strength with the metal foil layer (11) can be further increased by the random copolymer component with a low melting point, and the bonding performance can be further improved, and the random copolymer component with a high melting point can be used. When the lid (3) is heat-sealed on the flange (23) of the container (2) formed by the laminated body (10) (refer to the second figure), the second outer resin film layer (12B) is less likely to be damaged by pressure, which can ensure better performance. For sufficient shape retention of the container (2).

Further, the second outer resin film layer (12B) is preferably configured not to have a sea-island structure. With the above-described configuration, when the laminated body (10) is deep-drawn molded to form the molding container (2), the olefin resin phase and the elastomer can be sufficiently suppressed in the second outer resin film layer (12B) The advantage of the situation where voids (spaces) occur at the interface of the phases. In particular, when the second outer resin film layer ( 12B ) is arranged at a position adjacent to the metal foil layer ( 11 ), the above-mentioned effect is remarkable.

The film constituting the outer resin film layer (12): (12A) (12B) is preferably produced by a molding method such as multilayer extrusion molding, inflation molding, and T-die casting film molding.

The thickness of the outer resin film layer (12): (12A) (12B) (if it is two or more layers, the total thickness) is preferably set to 20 to 80 μm. By making the said thickness 20 micrometers or more, generation|occurrence|production of pinholes can fully be prevented, and by setting said thickness to 80 micrometers or less, the resin usage-amount can be reduced, and cost reduction can be achieved. Preferably, the thicknesses of the outer resin film layers (12), (12A) and (12B) are set to 30 to 50 μm.

If the outer resin film layer has a two-layer structure formed by the first outer resin film layer (12A) and the second outer resin film layer (12B) (see Fig. 1 (b)), the first outer resin film layer (12A) ) and the thickness of the second outer resin film layer (12B) are preferably in the range of 9:1 to 4:6. If the thickness ratio of the first outer resin film layer (12A) exceeds 9, the lamination strength between the two layers (12A) and (12B) may be lowered and peeling may occur. On the other hand, when the thickness ratio of the 1st outer resin film layer (12A) is less than 4, there exists a possibility that the outer surface layer in a matte state may not be obtained.

In the method of laminating the film constituting the single-layer outer resin film layer (12) or the second outer resin film layer (12B) located on the inner side among the two layers on the metal foil constituting the metal foil layer (11), It is not particularly limited, and examples include dry lamination, sandwich lamination (extrusion of an adhesive film formed of an acid-modified polypropylene resin, etc., and sandwich lamination between a metal foil and the above-mentioned film, followed by a heated roll for lamination). method of thermal lamination), etc. In the case of the dry lamination method, for example, it is performed through an adhesive layer ( 14 ) formed of a two-part curing type polyester-polyurethane resin-based adhesive or a polyether-polyurethane resin-based adhesive (refer to the first figure). . The thickness of the adhesive layer ( 14 ) is preferably set to 1 to 5 μm, and is preferably set to 1 to 3 μm from the viewpoint of thinning and weight reduction of the laminate ( 10 ) for forming a container.

On the inner surface of the outer resin film layer (12) or the second outer resin film layer (12B), a printing layer (15) is formed entirely or partially by gravure printing or the like. By means of the printed layer (15), a predetermined display or decoration is presented on the outer surface of the shaped container (2). The printed layer (15) is not particularly limited, and in the sense of emphasizing the outer surface (12a) in a matt state to give it a sense of luxury, it is preferable that the background color is a dark color such as black.

Here, coloring components such as pigments may be added to the outer resin film layers (12), (12A) and (12B) instead of the printed layer (15).

The inner resin layer (13) constitutes the inner surface (including the upper surface of the flange portion (23)) of the molding container (2), and is made of, for example, a thermally fusible polypropylene resin (PP) film or a polyethylene resin (PE) film. It is composed of general-purpose films such as these, or composite sheets that are bonded together.

The thickness of the film or composite sheet constituting the inner resin layer (13) is preferably 100 to 500 μm, 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 by, for example, a dry lamination method through an adhesive layer (16). For the adhesive layer ( 16 ), for example, a two-pack curing type polyester-urethane resin-based adhesive or a polyether-polyurethane resin-based adhesive is used. The thickness of the adhesive layer ( 16 ) is preferably set to 1 to 5 μm, and is preferably set to 1 to 3 μm from the viewpoint of thinning and weight reduction of the laminate ( 10 ) for forming the container.

In addition, the inner resin layer (13) can also be formed by a coating layer such as epoxy resin or shellac resin instead of the above-mentioned film or composite sheet.

The second figure shows the production of a package (4) in which the contents (C) such as food are hermetically packaged using a molded container (2) formed from the above-mentioned laminate (10) and a lid (3) in order of steps method.

First, the above-mentioned laminated body (10) is cut into a predetermined shape and size, and this is formed into a cup shape. The layered body (10) is formed by cold forming such as deep draw forming and extrusion forming. Thereby, a shaped container (2) as shown in the second figure (a) can be obtained.

The forming container (2) has a bottom wall (21), a peripheral wall (22) erected from the peripheral edge of the bottom wall (21), and a horizontal annular protrusion extending radially outward from the upper end edge of the peripheral wall (22). Edge (23).

In terms of the shape of the shaped container (2), there are examples of circular, oval, oval, approximately square, approximately rectangular and other cross-sections, and the diameter of the conical cylindrical shape gradually increases as it goes upward, or vertical Cylindrical, etc.

Moreover, the depth of the shaping|molding container (2) is normally formed in 15-50 mm.

Almost no whitening was found on the outer surface of the shaped container (2) formed of the above-mentioned layered body (10). This is effective because the resin composition of the outer resin film layer ( 12 ) or the first outer resin film layer ( 12A) constituting the outer surface layer ( 120 ) of the laminate ( 10 ) is as described above. The occurrence of voids (voids) due to the interface between the olefin-based resin phase and the elastomer component due to stress during molding is suppressed.

Next, as shown in the second figure (b), after the molding container (2) is filled with contents (C) such as food, the lower surface of the lid (3) is placed on the upper surface of the flange (23) of the molding container (2). heat-sealing (heat-sealing) is performed on the peripheral edge of the .

Here, as the cover (3), for example, a metal foil layer made of aluminum foil or the like, a polypropylene resin (PP) film, a polyethylene resin (PE) film, or the like, which is laminated on the metal foil layer, is used. The lower heat-fusible resin film layer, and the outer resin film layer formed of polyester resin (PEs) film or polyamide resin (PA) film, etc. and laminated on the upper surface of the metal foil layer. In addition, the lid (3) is integrally formed with an unsealing tab (31) on a part of its outer peripheral edge so as to protrude outward from the flange (23) of the molding container (2) (see Figure 3).

The means for heat-sealing (heat-sealing) the lid (3) to the flange (23) of the shaped container (2) is not particularly limited. These superimposed portions are heated for a predetermined time while applying a predetermined pressure by a hot plate heated to a predetermined temperature (for example, about 180° C.).

Next, the package (4) obtained in the above-mentioned steps is introduced into a retort sterilization device (5), and a retort sterilization process is performed.

This autoclave sterilization treatment step can also be used as a heat treatment step for eliminating the whitening that occurred in a part of the outer surface of the molding container (2). That is, in the molding container (2) formed by molding the layered body (10) of the present invention into a cup shape, as described above, the unique resin composition of the outer surface layer (120) of the layered body (10) , to suppress whitening on the outer surface, but in case a part of the outer surface, especially in the corner of the boundary between the bottom wall and the peripheral wall, etc., where the degree of deformation due to molding is large, even if the matrix of the olefin-based resin and the olefin-based elastic When the voids (voids) generated at the interface of the body are slightly whitened, the whitening can be completely eliminated by performing the heat treatment.

The heating temperature of the packaging body (4) in this step is to form the outer surface layer (120) of the laminated body (10), that is, the single layer of the outer resin film layer (12) or the outer resin film layer of a plurality of layers. The temperature of the outermost layer (in the case of the first figure (b), the first outer resin film layer (12A)) is the temperature equal to or higher than the softening point of the resin. The heating temperature is more preferably a temperature that is equal to or higher than the softening point of the resin and less than the melting point. By setting the heating temperature to a temperature equal to or higher than the softening point of the resin, the deformation of the layered body (10) due to molding is alleviated, and the holes are easily filled. Moreover, by setting the heating temperature to a temperature lower than the melting point of the resin, the shape of the molding container (2) can also be maintained after heating. Specifically, it is about 80 degreeC or more, Preferably it is about 100-180 degreeC. The heating time is about 5 minutes to 3 hours.

Among them, the heat treatment step may be performed by, for example, heat treatment in an oven, immersion treatment in warm water, or the like other than those sterilized by a sterilizer. In the case of heat treatment other than the autoclave sterilization treatment, only the molded container ( 2 ) may be subjected to heat treatment in the step before forming into the package body ( 4 ).

The third figure shows the package body (4) after sterilization in the autoclave.

The package ( 4 ) of the drawing has a molded container ( 2 ) having an outer surface in a matt state with good overall appearance, with no whitening observed due to molding, and can give a sense of luxury to the user.

[Example]

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

<Example 1>

As for the metal foil layer, it is prepared by A8021H-O classified according to JIS H4160, and the chemical conversion treatment liquid composed of polyacrylic acid, trivalent chromium compound, water and alcohol is coated on both sides at 180°C. It was dried to form an aluminum foil with a thickness of 120 μm of a chemical conversion-treated film with an average single-side chromium adhesion amount of 5 mg/m ² .

As the outer resin film layer, a non-stretch polypropylene resin film (CPP) having a thickness of 30 μm in two layers was prepared. The film was formed by co-extrusion using a T-die to form a co-polymer of ethylene and propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g as the first elastomer-modified olefin-based resin (B-PP1). The ethylene-propylene elastomer-modified homogeneous polypropylene resin after polymerization was 94% by mass, and the melting point of the second elastomer-modified olefin-based resin (B-PP2) was 144°C and the crystal melting energy was 19 J/g. 1 mass % of an ethylene-propylene elastomer modified random copolymer after propylene copolymerization, as an olefin-based elastomer, it is formed from a resin composition of 5 wt % of ethylene-1-butene elastomer (EBR), and is composed of A first resin film layer with a thickness of 27 μm in the outer surface layer; and a second resin film layer with a thickness of 3 μm formed of an ethylene-propylene random copolymer (R-PP, melting point of 155° C.). In addition, 1500 ppm of erucamide and 5000 ppm of silicon oxide were added to the first resin film layer.

Here, the melting point (Tmp) and crystal melting energy (ΔH) of each of the above-mentioned resins were measured under the following measurement conditions.

‧Heating and cooling rate: 10°C/min between 23°C and 210°C

‧Sample material: adjust the amount of 5mg

‧Container: Use aluminum pan

‧Installation: "DSC-60A" made by Shimadzu Corporation

Next, the entire surface on the side of the second resin film layer among the two sides of the unstretched polypropylene resin film was formed with black ink (manufactured by DIC Graphics, product name: PANACEA CVL-SP Special Ink 805) using a gravure printing machine. ) obtained plain color printing layer.

In addition, 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 as the inner resin layer.

Next, on one side of the aluminum foil, a non-stretch polypropylene resin film (CPP) was dry-laminated using a two-component curing polyester-urethane resin adhesive so that the printed layer was on the inside, and on the other side of the aluminum foil. On the one hand, the composite sheet was dry-laminated using a two-pack curing polyester-polyurethane resin adhesive so that the side of the high-density polyethylene resin film became the inner side, and maintained at a temperature of 40°C for 5 days. The laminated body for forming the container of Example 1.

Regarding the laminate of Example 1, the surface gloss (gloss value) of the outer surface layer was measured with a gloss meter (Micro Tri Gloss S manufactured by BYK Gardner) (the same applies to the following Examples and Comparative Examples). ), the result is 28%.

<Example 2>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Elastomer-modified homogeneous polypropylene resin 85% by mass, ethylene-propylene elastomer modified random having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin resin (B-PP2) common Except for 10 mass % of polymer and 5 wt % of ethylene-1-butene elastomer (EBR) as an olefin-based elastomer, a laminate for forming a container was produced in the same manner as in Example 1, and this was carried out Example 2.

In the laminate of Example 2, the surface glossiness of the outer surface layer was 12%.

<Example 3>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 155°C and a crystal melting energy of 51 J/g Elastomer-modified random copolymer 80% by mass, ethylene-propylene elastomer-modified random copolymer having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin resin (B-PP2) Except for 10% by mass of the copolymer and 10% by weight of the ethylene-1-butene elastomer (EBR) as the olefin-based elastomer, a laminate for forming a container was produced in the same manner as in Example 1, and this was implemented. Example 3.

In the laminate of Example 3, the surface glossiness of the outer surface layer was 8%.

<Example 4>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Elastomer-modified homogeneous polypropylene resin 75% by mass, ethylene-propylene elastomer modified random having a melting point of 136°C and a crystal melting energy of 18 J/g as the second elastomer-modified olefin resin (B-PP2) Except for 10 mass % of the copolymer and 15 wt % of ethylene-1-butene elastomer (EBR) as the olefin-based elastomer, a laminate for forming a container was produced in the same manner as in Example 1, and this was carried out Example 4.

In the laminate of Example 4, the surface glossiness of the outer surface layer was 9%.

<Example 5>

Except for the resin composition of the first resin film layer constituting the outer surface layer, the first elastomer-modified olefin-based resin (B-PP1) has a melting point of 163° C. and a crystal melting energy of ethyl acetate of 58 J/g. Ethylene-propylene elastomer modified 70 mass % of ethylene-propylene elastomer-modified homogeneous polypropylene resin, melting point of 144° C. and crystal melting energy of 19 J/g as second elastomer-modified olefin-based resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the mass random copolymer was 20% by mass, and the ethylene-1-butene elastomer (EBR), which is an olefin-based elastomer, was 10% by weight. Let it be Example 5.

In the laminate of Example 5, the surface glossiness of the outer surface layer was 7%.

<Example 6>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Elastomer-modified homogeneous polypropylene resin 60% by mass, ethylene-propylene elastomer modified random having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin-based resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the copolymer was 30% by mass and the ethylene-propylene elastomer (EPR), which is an olefin-based elastomer, was 10% by weight.

In the laminate of Example 6, the surface glossiness of the outer surface layer was 4%.

<Example 7>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 166° C. and a crystal melting energy of 65 J/g. Elastomer-modified homogeneous polypropylene resin 65% by mass, ethylene-propylene elastomer modified random having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the copolymer was 20% by mass and the ethylene-propylene elastomer (EPR), which is an olefin-based elastomer, was 15% by weight.

In the laminate of Example 7, the surface glossiness of the outer surface layer was 5%.

<Example 8>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 166° C. and a crystal melting energy of 65 J/g. Elastomer-modified homogeneous polypropylene resin 60% by mass, ethylene-propylene elastomer modified random having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin-based resin (B-PP2) A laminate for forming a container was produced in the same manner as in Example 1, except that the copolymer was 30% by mass and the ethylene-propylene elastomer (EPR) as the olefin-based elastomer was 10% by weight, and this was referred to as Example 8.

In the laminate of Example 8, the surface glossiness of the outer surface layer was 4%.

<Example 9>

As the outer resin film layer, a non-stretch polypropylene resin film (CPP) having a single-layer structure of 30 μm in thickness was prepared. The film was formed by extrusion using a T-die, and obtained by copolymerizing ethylene and propylene with a melting point of 163° C. and a crystal melting energy of 58 J/g as the first elastomer-modified olefin resin (B-PP1). 94 mass % of the ethylene-propylene elastomer-modified homogeneous polypropylene resin, the melting point of the second elastomer-modified olefin resin (B-PP2) is 144°C, and the crystal melting energy is 19 J/g. Co-polymerization of ethylene and propylene The polymerized ethylene-propylene elastomer modified random copolymer was composed of 1 mass % of the ethylene-1-butene elastomer (EBR), which is an olefin-based elastomer, and 5 wt % of the resin composition. In addition, 1500 ppm of erucamide and 5000 ppm of silicon oxide were added to the outer resin film layer.

Next, except for the above, a laminate for forming a container was produced in the same manner as in Example 1, and this was referred to as Example 9.

In the laminate of Example 9, the surface glossiness of the outer surface layer was 28%.

<Comparative Example 1>

Except for using sequentially laminated random polypropylene resin (R-PP) film (= outer surface layer, melting point 155°C, crystal melting energy 57 J/g), ethylene- Propylene elastomer-modified homogeneous polypropylene resin (B-PP) film and random polypropylene resin (R-PP) film (melting point 155°C, crystal melting energy 57 J/g) with a 3-layer structure of 30 μm in thickness A stretched polypropylene resin film (CPP) was used as the outer resin film layer, and a laminate for forming a container was produced in the same manner as in Example 1, and this was referred to as Comparative Example 1.

In the laminate of Comparative Example 1, the surface glossiness of the outer surface layer was 102%.

<Comparative Example 2>

The outer resin film layer constituting the outer surface layer is formed by copolymerizing ethylene and propylene with a melting point of 163° C. and a crystal melting energy of 58 J/g as the first elastomer-modified olefin resin (B-PP1). Except for the resin composition formed by the ethylene-propylene elastomer modified homogeneous polypropylene resin at 90 mass % and ethylene-1-butene copolymer (EBR) as the olefin-based elastomer at 10 mass %, the same as the examples 1 In the same manner, a laminate for forming a container was produced, and this was referred to as Comparative Example 2.

In the laminate of Comparative Example 2, the surface glossiness of the outer surface layer was 10%.

<Comparative Example 3>

Except that the first resin film layer constituting the outer surface layer was formed of an ethylene-propylene elastomer having a melting point of 144° C. and a crystal melting energy of 19 J/g as the second elastomer-modified olefin-based resin (B-PP2) A resin composition for forming a container was prepared in the same manner as in Example 1, except that the resin composition was composed of 90% by weight of the modified random copolymer and 10% by weight of the ethylene-propylene elastomer (EPR) as the olefin-based elastomer. The layered body is referred to as Comparative Example 3.

In the laminate of Comparative Example 3, the surface glossiness of the outer surface layer was 22%.

<Comparative Example 4>

In addition to forming the first resin film layer constituting the outer surface layer, the first elastomer-modified olefin-based resin (B-PP1) was formed of an ethylene-propylene bomb having a melting point of 163° C. and a crystal melting energy of 58 J/g. A layered product for forming a container was produced in the same manner as in Example 1, except that the product was formed of 100% by mass of the property-modified homogeneous polypropylene resin, and this was referred to as Comparative Example 4.

In the laminate of Comparative Example 4, the surface glossiness of the outer surface layer was 72%.

<Comparative Example 5>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 145° C. and a crystal melting energy of 50 J/g. Elastomer-modified random copolymer 80% by mass, ethylene-propylene elastomer-modified random copolymer having a melting point of 144°C and a crystal melting energy of 19 J/g as the second elastomer-modified olefin resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the copolymer was 10% by mass and the ethylene-propylene elastomer (EPR) as the olefin-based elastomer was 10% by weight, and this was referred to as Comparative Example 5.

In the laminate of Comparative Example 5, the surface glossiness of the outer surface layer was 19%.

<Comparative Example 6>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Elastomer-modified homogeneous polypropylene resin 80% by mass, ethylene-propylene elastomer modified random having a melting point of 130°C and a crystal melting energy of 14 J/g as the second elastomer-modified olefin-based resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the copolymer was 10% by mass and the ethylene-propylene elastomer (EPR) as the olefin-based elastomer was 10% by weight, and this was referred to as Comparative Example 6.

In the laminate of Comparative Example 6, the surface glossiness of the outer surface layer was 13%.

<Comparative Example 7>

Except for the resin composition of the first resin film layer constituting the outer surface layer, the first elastomer-modified olefin-based resin (B-PP1) has a melting point of 155° C. and a crystal melting energy of ethyl acetate of 49 J/g. Ethylene-propylene elastomer modified 75% by mass of ethylene-propylene elastomer-modified random copolymer, melting point of 144° C. and crystal melting energy of 19 J/g as the second elastomer-modified olefin-based resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the mass random copolymer was 10% by mass and the ethylene-propylene elastomer (EPR), which is an olefin-based elastomer, was 15% by weight, and this was used as a comparison. Example 7.

In the laminate of Comparative Example 7, the surface glossiness of the outer surface layer was 12%.

<Comparative Example 8>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Elastomer-modified homogeneous polypropylene resin 80% by mass, ethylene-propylene elastomer modified random having a melting point of 158°C and a crystal melting energy of 44 J/g as the second elastomer-modified olefin resin (B-PP2) A layered product for forming a container was produced in the same manner as in Example 1, except that the copolymer was 10% by mass and the ethylene-propylene elastomer (EPR) as the olefin-based elastomer was 10% by weight, and this was referred to as Comparative Example 8.

In the laminate of Comparative Example 8, the surface glossiness of the outer surface layer was 15%.

<Comparative Example 9>

Except for the resin composition of the first resin film layer constituting the outer surface layer, as the first elastomer-modified olefin-based resin (B-PP1), the melting point of the first elastomer-modified olefin-based resin (B-PP1) is ethylene-propylene having a melting point of 163° C. and a crystal melting energy of 58 J/g. Other than 90% by mass of elastomer-modified homogeneous polypropylene resin, and 10% by weight of ethylene-propylene elastomer (EPR) having a melting point of 40 to 70° C. as an olefin-based elastomer and a crystal melting energy of 15 J/g, the same as the examples 1 A laminate for forming a container was produced in the same manner, and this was referred to as Comparative Example 9.

In the laminate of Comparative Example 9, the surface glossiness of the outer surface layer was 15%.

[Manufacture of the container]

Next, the laminates for forming containers of Examples 1 to 9 and Comparative Examples 1 to 9 were cut into predetermined shapes and sizes to prepare blanks, and after applying a small amount of siloxane to both sides of each blank, using The metal mold (manufactured by AMADA Co., Ltd.) formed by the male mold and the female mold is deeply drawn to produce a circular cup-shaped container with a flange (bottom diameter 52mmφ, opening diameter 65mmφ, height 30mm, flange width width 8mm).

[Production of the cover]

On the other hand, a polyethylene terephthalate resin (PET) film with a thickness of 12 μm as an outer resin layer was used on one side of an aluminum foil with a thickness of 20 μm made of A1N30H-O classified in JIS H4160. A two-component curable polyester-polyurethane resin adhesive was dry-laminated, and on the other side of the aluminum foil, a linear low-density polyethylene resin (LLDPE) film with a thickness of 30 μm as a heat-fusible resin layer was used. The liquid-curable polyester-polyurethane resin adhesive was dry-laminated and maintained in a 40° C. environment for 5 days, thereby producing a lid laminate.

The obtained laminated body was cut into a desired shape and size according to a flange, thereby producing a lid with a tab for opening.

[Production of the packaging body]

After placing 70 ml of water in each of the above-mentioned containers, the above-mentioned lid was placed on the flange of the container so as to be in contact with the non-stretched polypropylene resin film (CPP) surface, and a doughnut-shaped hot plate heated to 200°C was placed. (Outer diameter 90 mmφ, inner diameter 74 mmφ), heat sealing (heat welding) was performed by pushing against these polymerization surfaces with a pressing force of 150 kgf for 3 seconds.

Thereby, a package body is obtained.

[Verification of the appearance of the packaging body]

The container of each obtained package body was visually observed to verify whether whitening occurred on the outer surface thereof and whether or not pressure loss occurred in the outer surface layer of the flange. The verification results are shown in Table 1 below together with the composition and glossiness of the outer surface layer of the laminated body of the molding material of each container.

Among them, in the column of "whitening of the outer surface of the container" in Table 1, those with no whitening or almost no whitening on the outer surface of the container were set as "◎", and those with less whitening were set as "○", Those with a certain degree of whitening were designated as "△", and those with marked whitening were designated as "X". In addition, in the column of "pressure loss of flange" in Table 1, the outer surface layer of the flange of the container, which was not found to have pressure loss due to the heat sealing of the lid, was designated as "◎", and almost Those with no pressure loss were designated as "○", those with a certain degree of pressure loss were designated as "△", and those with significant pressure loss were designated as "×". In addition, in Table 1, the 1st elastomer-modified olefin resin is shown as "B-PP1", and the 2nd elastomer-modified olefin resin is shown as "B-PP2".

As can be seen from Table 1, the layered systems of Examples 1 to 9 had low glossiness, and the whitening phenomenon at the time of molding was improved. In addition, in Examples 1 to 9, no pressure loss occurred in the outer surface layer of the flange of the container after the lid was heat-sealed.

On the other hand, since the compositions of the outer surface layers of the series of Comparative Examples 1 and 4 were different from those of the present invention, the glossiness was not sufficiently lowered, and a laminated body in a matt state was not obtained.

In the laminated systems of Comparative Examples 2, 6, 8, and 9, the glossiness was sufficiently lowered, and a strong whitening phenomenon was observed in the R part of the bottom of the container after molding.

In the laminates of Comparative Examples 3, 5, and 7, whitening due to molding was suppressed, but the outer surface of the flange of the container after the lid was heat-sealed was damaged and the shape retention was insufficient.

From the above verification results, it is considered that the pressure loss of the outer surface layer of the flange of the container is affected by both the melting point of the resin component and the crystal melting energy. The melting point of the higher one) is 155°C or more, and the crystal melting energy (if B-PP1 and B-PP2 are contained, the value of the weighted average of the crystal melting energy of the two based on the content ratio) is 40 J/g or more ( It is preferable that it is 50 J/g or more), and it turns out that pressure loss is hard to generate|occur|produce.

[Industrial availability]

The present invention is used for sealing and packaging foods and the like, and can be suitably used for a molded container having an outer surface in a matte state with favorable appearance, and a laminate formed of its molding material.

10‧‧‧Laminates for forming containers

11‧‧‧Metal foil layer

12‧‧‧Outer resin film layer

12A‧‧‧First outer resin film layer

12B‧‧‧Second outer resin film layer

120‧‧‧Outer surface layer

120a‧‧‧Surface of the outer surface layer

13‧‧‧Inner resin layer

14‧‧‧Adhesive layer

15‧‧‧Printing layer

16‧‧‧Adhesive layer

Claims (13)

A laminate for forming a container, comprising: a metal foil layer; and an outer resin film layer laminated on both sides of the metal foil layer to be the outer surface of the container to constitute an outer surface layer in a matte state, the aforementioned The outer resin film layer is formed of a resin composition comprising: a first elastomer-modified olefin-based resin having a melting point of 155° C. or higher and a crystal melting energy of 50 J/g or more, a melting point of 135° C. or higher and a crystal-melted olefin resin A second elastomer-modified olefin-based resin and an olefin-based elastomer having an energy of 30 J/g or less, wherein the crystal melting energy is the heat of fusion measured by differential scanning calorimetry (DSC) in accordance with JIS K7122-1987 (Crystal melting energy, ΔH); The first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are made of elastomer-modified homogeneous polypropylene resin and/or elastomer-modified random resin, respectively The above-mentioned elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene as one of the copolymerization components, and in the above-mentioned outer resin film layer, the above-mentioned first elastomer-modified olefin is formed. The total value of the content of the system resin and the content of the second elastomer-modified olefin-based resin is 50% by mass or more. The laminate for forming a container according to claim 1, wherein the content of the second elastomer-modified olefin-based resin in the outer resin film layer is 1 to 50% by mass. The laminate for forming a container according to claim 1, wherein the content of the first elastomer-modified olefin-based resin in the outer resin film layer is 49 to 98% by mass. The laminate for forming a container according to claim 1, wherein the content of the olefin-based elastomer in the outer resin film layer is 1 to 30% by mass. The laminate for forming a container according to claim 1, wherein the glossiness of the surface of the outer resin film layer is 0.5 to 12%. The laminate for forming a container according to claim 1, wherein the elastomer components of the first elastomer-modified olefin-based resin and the second elastomer-modified olefin-based resin are ethylene-propylene elastomer, ethylene - At least one of 1-butene elastomer and ethylene-propylene-1-butene elastomer. The laminate for forming a container according to claim 1, wherein at least any one of the aforementioned olefin-based elastomers ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer 1. The laminate for forming a container according to claim 1, wherein the outer resin film layer further contains at least one of inorganic fine particles, organic fine particles, and a lubricant. The laminate for a molded container according to claim 1, wherein the second elastomer-modified olefin-based resin has two or more crystallization peaks in a differential scanning calorimetry chart. The laminated body for forming a container according to claim 1, wherein a plurality of layers of outer resin film layers are formed in the area layer that becomes the outer side of the container among both sides of the metal foil layers, and the outer resin film layers of the plurality of layers are formed by the plurality of layers of the outer resin film. The outermost one among the thin film layers constitutes the aforementioned outer surface layer. The laminate for forming a container according to claim 1, wherein a printed 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, and the outer resin film is added to the outer resin film layer. The surface of the film layer exhibits a predetermined display or decoration. A shaped container in which the laminated body for a shaped container according to claim 1 is shaped into a cup shape, and has a flange on the periphery of an opening. A package attached to the flange of a shaped container as claimed in claim 12 filled with contents, engaging a lid to cover the opening of the shaped container.

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