KR20190115414A - Laminate body for molding container, molding container and packaging body - Google Patents

Abstract

The present invention relates to a container which is configured by molding a lamination having a metal foil layer and an outer resin film layer, and provides an outer surface of matte touch having an excellent appearance. To this end, in a lamination (2) for a molded container, an outer resin film layer (12, 12A) constituting an outer surface layer (120) of matte touch is composed of 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 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 a resin composition including an olefin-based elastomer. Here, the first and second elastomer modified olefin-based resins are individually made of an elastomer modified homo-polypropylene resin and/or an elastomer modified random copolymer, which is an elastomer modified body of a random copolymer including propylene as a copolymerization component. The total value of the content of the first and second elastomer modified olefin-based resins is 50 mass% or more.

Description

Laminated body for molding container, molding container and package {LAMINATE BODY FOR MOLDING CONTAINER, MOLDING CONTAINER AND PACKAGING BODY}

The present invention relates to a laminate used as a material of a molding container for sealing packaging food, etc., a molding container formed by molding the copper laminate, and a package formed by covering a lid on a copper molding container filled with contents. More specifically, the present invention relates to a laminate for a molded container, a molded container, and a package having an outer surface of a mat tank.

For example, as a container for packaging long-term storage of yokan, jelly, baby food, nursing food, and the like, a single layer laminated on a metal foil layer made of aluminum foil or the like, and the outer surface of the container among both surfaces of the metal foil layer, or The molding container which shape | molds the laminated body provided with multiple outer side resin film layers in cup shape is known (refer patent document 1 etc. which are mentioned below).

Here, in the packaging field, a container having an outer surface of a matte (matte) may be used in order to give a sense of quality to the appearance.

For example, in Patent Literature 2 described below, producing a stationery file having a mat-like outer surface by using an embossed polypropylene resin film is disclosed.

The following patent document 3 discloses the hard coat film for shaping | molding which provided the hard-coat layer which has an outer surface of mat form in outermost layer.

Moreover, the following patent document 4 discloses the polypropylene sheet of the matte state of the surface which mix | blends a polypropylene resin, a polyethylene resin, and an elastomer.

Japanese Patent Laid-Open No. 6-345123 Japanese Patent Laid-Open No. 5-320376 Japanese Patent Application Laid-Open No. 2011-148301 Japanese Patent Laid-Open No. 2-92944

However, when the laminated body which consists of an outer side resin film layer by the embossed film like patent document 2 is shape | molded in cup shape, the embossed film will increase at the time of shaping | molding, a stain may arise on the outer surface of mat-like, and an appearance may be damaged. There is. Moreover, when an embossed film is used, there exists a problem that cost increases.

Moreover, when shape | molding the laminated body which consisted of an outer side resin film layer by the film which has a mat-like coat layer like the said patent document 3 in cup shape, the problem that a crack generate | occur | produces in a coat layer or a coating layer peels off have. In addition, also when forming a mat-like coat layer, there exists a problem that cost increases.

In addition, in the case where the laminate formed of the surface layer from the sheet in the matte state as described in Patent Document 4 is formed into a cup shape, since the compatibility of the polyethylene resin and the elastomer with respect to the polypropylene resin is low, There is a problem that whitening occurs on the surface.

This invention is made | formed in view of the said subject, Comprising: It aims at providing inexpensively the thing which has the external surface of the mat-like thing with favorable external appearance as a container formed by shape | molding the laminated body provided with the metal foil layer and the outer side resin film layer. have.

MEANS TO SOLVE THE PROBLEM This invention consists of the following aspects, in order to achieve the said objective.

1) A laminate for a molded container, comprising a metal foil layer and an outer resin film layer laminated on a surface of the both sides of the metal foil layer, which is an outer surface of the container, to form a mat-like outer surface layer.

The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,

The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified homopolypropylene resin,

The laminated body for molding containers in the said outer side resin film layer whose total value of the content rate of the said 1st elastomer modified olefin resin and the content rate of the 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 a surface of the both sides of the metal foil layer, which is an outer surface of the container, to form a mat-like outer surface layer,

The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,

The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified random copolymer,

The elastomer-modified random copolymer is an elastomer-modified product of a random copolymer containing propylene as one of the copolymerization components,

The laminated body for molding containers in the said outer side resin film layer whose total value of the content rate of the said 1st elastomer modified olefin resin and the content rate of the said 2nd elastomer modified olefin resin is 50 mass% or more.

3) A laminate for a molding container, comprising a metal foil layer and an outer resin film layer laminated on a surface of the both sides of the metal foil layer, which is an outer surface of the container, to form a mat-like outer surface layer.

The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,

The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified homopolypropylene resin and an elastomer-modified random copolymer,

The elastomer-modified random copolymer is an elastomer-modified product of a random copolymer containing propylene as one of the copolymerization components,

The laminated body for molding containers in the said outer side resin film layer whose total value of the content rate of the said 1st elastomer modified olefin resin and the content rate of the said 2nd elastomer modified olefin resin is 50 mass% or more.

4) The laminated body for any one of said 1) -3) whose said content of the said 2nd elastomer modified olefin resin is 1-50 mass% in the said outer side resin film layer.

5) The laminated body for any one of said 1) -4) whose said content of the said 1st elastomer-modified olefin resin is 49-98 mass% in the said outer side resin film layer.

6) The laminated body for any one of said 1) -5) whose said content of the said olefin elastomer is 1-30 mass% in the said outer side resin film layer.

7) The laminated body for any one of said 1) -6) whose glossiness of the surface of the said outer side resin film layer is 0.5 to 12%.

8) The elastomer components of the first elastomer-modified olefin resin and the second elastomer-modified olefin resin are ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-, respectively. The laminated body for any one of said 1) -7) molding containers which is at least any one of propylene-1-butene elastomer.

9) Any one of the above 1) to 8), wherein the olefin elastomer is at least one of ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer. Laminate for molded containers.

10) The laminated body for any one of said 1) -9) which the said outer side resin film layer contains at least any one of inorganic type microparticles | fine-particles, organic type microparticles | fine-particles, and a slip agent.

11) The laminate according to any one of the above-mentioned 1) to 10), wherein the second elastomer-modified olefin resin has two or more crystallization peaks in a differential scanning calorimetry graph.

12) A plurality of outer resin film layers are laminated on a surface of the both sides of the metal foil layer that is the outer side of the container, and the outer surface layer is formed by the outermost one of the outer resin film layers of the plurality of layers. The laminated body for molding container in any one of said 1) -11).

13) A printing layer is formed between the metal foil layer and the outer side resin film layer, or a coloring component is added to the outer side resin film layer so that a predetermined mark or decoration appears on the surface of the outer side resin film layer. The said laminated body for molded containers in any one of 1) -12).

14) A molding container formed by molding the laminate for any one of the molding containers according to 1) to 13) in a cup shape, and having a flange at the periphery of the opening.

15) A package, in which a cover is joined to a flange of the molding container of 14), wherein the lid is covered with the contents to cover the opening of the molding container.

In addition, in this specification and a claim, "melting point" is melting peak temperature Tmp measured by differential scanning calorimetry (DSC) based on JISK7121-1987.

Similarly, "crystal melting energy" is 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 ((DELTA) H1, (DELTA) H2) exist, it is assumed that the value of the highest crystal melting energy is indicated.

In the laminated body for shaping | molding container of said 1) -3), 1st elastomer modified olefin resin whose outer side resin film layer which comprises a mat-like outer surface layer is 155 degreeC or more of melting | fusing point, and crystal melting energy is 50 J / g or more. And a resin composition obtained by combining 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, and an olefin elastomer. 2 The compatibility of the elastomer component and the olefin resin in the elastomer-modified olefin resin is good, the dispersibility of the elastomer component is also good, and the olefin resin phase and the elastomer component Bonding strength of the interface is increased. Therefore, at the time of forming the laminate of 1) to 3), the interface between the olefinic resin phase and the elastomer component is peeled off by the stress and voids called voids are prevented from occurring, and the difference in the refractive index between the resin and the void is prevented. The deterioration of transparency due to, that is, whitening phenomenon is prevented. And in the case of the laminated body of said 1) -3), like the laminated body which the mat surface of the mat surface was comprised by the embossed film, it extends at the time of shaping | molding and a stain does not generate | occur | produce on the outer surface, and also the coat layer of a mat structure Like the laminated body in which the outer surface of the outer side resin film layer was comprised by the film which has, the crack does not generate | occur | produce in a coat layer, or a coat layer peels off, and it costs no cost.

Therefore, according to the laminated body for shaping | molding container of said 1) -3), the shaping | molding container which has the external surface of the mat-like thing with favorable external appearance is obtained in low cost.

In addition, according to the laminate for molding containers of 1) to 3), the melting point of the first elastomer-modified olefin resin in the resin composition constituting the outer surface layer is 155 ° C or higher. When the lid is heat-sealed on the flange of the container formed, the outer surface layer is less likely to be crushed, and sufficient shape retention is secured.

According to the molded container laminate of 4), various effects described above with respect to the laminate of 1) to 3) can be sufficiently secured, and in particular, the flange of the container formed by molding the laminate, for example. When the lid is heat-sealed, the outer surface layer is less likely to be crushed, and the whitening phenomenon can be suppressed more reliably.

According to the laminated body for shaping | molding container of said 5), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the laminated body for shaping | molding of said 6), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the laminated body for shaping | molding container of said 7), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the molded container laminate of 8), various effects described above with respect to the laminate of 1) to 3) can be more sufficiently secured.

According to the laminated body for molding container of said 9), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the laminate for molding container according to the above 10, fine adjustment of the mat roughness (unevenness) of the outer surface of the laminate can be performed, and more excellent design can be obtained, and excellent activity on the outer surface of the laminate The imparting property is imparted, and molding with a deeper molding depth can be performed satisfactorily, and whitening at the time of molding is also sufficiently suppressed.

According to the laminated body for molding container of said 11), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the laminated body for shaping | molding container of said 12), the various effects mentioned above regarding the laminated body of said 1) -3) can be ensured more fully.

According to the laminate for molding container according to the above 13), 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, so that a predetermined mark or Since decoration is shown, the molding container formed by shape | molding the copper laminated body becomes a thing of the outstanding external appearance.

According to the shaping | molding container of said 14), since it has a mat-like outer surface with a favorable external appearance, high quality can be provided.

According to the package of (15), the productivity is good, the cost can be suppressed, and the whitening at the time of molding is suppressed, and the container having a mat-like outer surface having a good appearance can provide a sense of quality.

BRIEF DESCRIPTION OF THE DRAWINGS The partially expanded sectional drawing which shows the layer structure of two states of the laminated body for molded containers which concerns on embodiment of this invention.
2 is a vertical sectional view showing a method for manufacturing a package according to an embodiment of the present invention in the order of steps.
3 is a perspective view of a package produced by the same method;

Embodiment of this invention is described below with reference to FIGS.

1 illustrates a layer structure of a laminate for molding containers according to an embodiment of the present invention. The laminated body 10 shown is the metal foil layer 11 and the outer side resin film layer 12 laminated | stacked on the surface which becomes the outer side of the container 2 among the both surfaces of the metal foil layer 11: 12A (12B) ). Moreover, the laminated body 10 of this embodiment is equipped with the inner side resin layer 13 laminated | stacked on the surface used as the inside of the container 2 among the both surfaces of the metal foil layer 11. As shown in FIG.

In more detail, in the laminated body 10 shown to Fig.1 (a), the outer side resin film layer 12 is a single layer structure, and the outer surface layer (mat-like outer surface layer of the laminated body 10 is formed by the copper layer 12). 120) is configured. In addition, in the laminated body 10 shown to FIG. 1 (b), the outer side resin film layer comprises the 1st outer side resin film layer 12A which comprises the mat outer surface layer 120 of the laminated body 10, It is a two-layered structure made of the second outer side resin film layer 12B interposed between the first outer side resin film layer 12A and the metal foil layer 11.

The metal foil layer 11 plays the role of providing the barrier property which prevents invasion of oxygen and moisture with respect to the laminated body 10 for molding containers.

As metal foil which comprises the metal foil layer 11, although aluminum foil, iron foil, stainless steel foil, copper foil etc. can be used, aluminum foil is used suitably. In the case of aluminum foil, any of pure aluminum foil and aluminum alloy foil may be used, and any of soft and hard may be used. For example, A8000 series (classified in JIS H4160 whose iron content is 0.3-1.5 mass%) In particular, if the soft material (O material) of the annealing treatment completed of A8079H or A8021H is excellent in moldability, it can be suitably used.

On one side or both sides of the metal foil layer 11, base treatment such as chemical conversion treatment is performed as necessary. Specifically, on the surface of the metal foil which performed the degreasing process, for example,

1) phosphoric acid;

Chromic acid,

Aqueous solution of a mixture comprising at least one compound selected from the group consisting of metal salts of fluoride and nonmetal salts 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 chromium (III) salts

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 chromium (III) salt,

Aqueous solution of a mixture comprising at least one compound selected from the group consisting of metal salts of fluoride and nonmetal salts of fluoride

After coating the aqueous solution in any one of 1) to 3) above, drying is performed to form a coating film.

As for the film formed on the surface of the metal foil layer 11 by the said chemical conversion treatment, it is preferable to make chromium adhesion amount (per single side) into 0.1 mg / m <2> -50 mg / m <2>, and especially 2 mg / m <2> -20 mg / m <2>. It is preferable to set it as.

It is preferable to set it as 30-200 micrometers, and, as for the thickness of the metal foil layer 11, it is more preferable to set it as 50-150 micrometers. By setting it as the said range, sufficient barrier property and moldability can be obtained.

Outer side resin film layer 12: (12A) (12B) has a mat-like design property on the outer surface of the molding container 1, and the deep drawing moldability and elongation to the laminated body 10 for molding containers. (張 出) plays a role in imparting moldability.

As for the outer side resin film layer 12 or the 1st outer side resin film layer 12A which comprises the mat outer surface layer 120, melting | fusing point (Tmp) is 155 degreeC or more and crystal melting energy ((DELTA) H) is 50 J / g or more. 1st elastomer-modified olefin resin, melting | fusing point (Tmp) is 135 degreeC or more, 2nd elastomer modified olefin resin whose crystal melting energy ((DELTA) H) is 30 J / g or less, and an olefin elastomer It consists of a resin composition. And the outer surface layer 120 comprised by said layer 12: 12A has the glossiness (gross value) of the surface 120a of 0.5-30%, Preferably it is 0.5-12%, More The preferable one is 0.5 to 9%. Here, "glossiness" is glossiness (gross value) measured based on JISZ8741-1997 (mirror surface glossiness-measuring method, method 3 (incidence angle 60 degree)).

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 above-mentioned elastomer-modified random copolymer is an elastomer-modified product of a random copolymer (random polypropylene) containing propylene and monomers other than propylene as a copolymerization component. Although it does not specifically limit as copolymerization component (monomer) other than propylene, For example, butadiene etc. are mentioned besides olefin components, such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4methyl-1- pentene. Can be. The elastomer component is not particularly limited, but at least any one of ethylene-propylene elastomer (EPR), ethylene-1-butene elastomer (EBR), and ethylene-propylene-1-butene elastomer (EPBR) It is preferable to use one.

Although it does not specifically limit as said olefin elastomer, It is an ethylene propylene elastomer (EPR), an ethylene-1-butene elastomer (EBR), and an ethylene propylene-1- butene elastomer (EPBR) It is preferable to use at least one of them.

The outer surface layer 120 has 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 ° C or higher. It is for the following reasons to comprise with the resin composition containing 2nd elastomer modified olefin resin whose energy ((DELTA) H) is 30 J / g or less.

That is, when melting | fusing point of 1st elastomer modified olefin resin is less than 155 degreeC, when whitening the laminated body 10 is shape | molded, whitening arises remarkably, and the cover 3 is attached to the flange 23 of the container 2 The outer surface layer 120 tends to be crushed when the heat seal is performed (see Comparative Example 5).

Moreover, when melting | fusing point of 2nd elastomer modified olefin resin is less than 135 degreeC, whitening arises remarkably at the time of shaping | molding of the laminated body 10 (refer 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 is likely to be crushed during the heat treatment (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 some extent during molding of the laminate 10 (see Comparative Example 8).

Moreover, when melting | fusing point (Tmp) is 155 degreeC or more and crystal melting energy ((DELTA) H) is 50 J / g or more of 1st elastomer-modified olefin resin which is non-containing, to some extent whitening will arise at the time of shaping | molding. In addition, the outer surface layer 120 tends to be crushed, and the shape retainability tends to be insufficient (see Comparative Example 3).

Moreover, when melting | fusing point (Tmp) is 135 degreeC or more and crystal melting energy ((DELTA) H) is 30 J / g or less of 2nd elastomer modified olefin resin, whitening will arise remarkably at the time of shaping | molding (comparative example 4 Reference).

It is preferable that melting | fusing point of the said 1st elastomer modified olefin resin is 185 degreeC or less, while being 155 degreeC or more. 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.

It is preferable that melting | fusing point of the said 2nd elastomer modified olefin resin is 135 degrees C or more, and is 175 degrees C or less. 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, more preferably 10 J / g or more and 20 J It is especially preferable that it is / g or less.

Although graft polymerization is mentioned as an elastomer modified aspect about a 1st elastomer modified olefin resin and a 2nd elastomer modified olefin resin, Other modified modes may be sufficient as it.

The first elastomer-modified olefin resin and the second elastomer-modified olefin resin can be produced by, for example, the following reactor made method.

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

Subsequently, the obtained homopolypropylene is transferred to the second reactor in a state containing unreacted propylene and a Ziegler-Natta catalyst. In the second reactor, propylene and hydrogen are added again to polymerize the homopolypropylene.

And the homopolypropylene obtained is moved to the 3rd reactor in the state containing unreacted propylene and a Ziegler-Natta catalyst. In the third reactor, ethylene, propylene and hydrogen are added again to polymerize the ethylene-propylene elastomer (EPR) copolymerized with ethylene and propylene.

In this way, 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, for example, adding a solvent. Moreover, the said 2nd elastomer modified olefin resin can be manufactured by making it react in a gaseous phase, for example 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 outer surface layer 120 of the laminated body 10, it is preferable that the content rate of the said 2nd elastomer modified olefin resin is 1-50 mass%, Especially, it is more preferable that it is 5-30 mass%, 10-10 It is especially preferable that it is 25 mass%. When 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 2nd elastomer modified olefin resin exceeds 50 mass%, heat resistance will fall.

In the outer surface layer 120, the content of the first elastomer-modified olefin resin is preferably 49 to 98% by mass, more preferably 70 to 95% by mass, more preferably 75 to 90% by mass. Particularly preferred. When the content rate of 1st elastomer-modified olefin resin exceeds 98 mass%, when forming the laminated body 10, there exists a possibility that whitening may arise. On the other hand, if the content rate of 1st elastomer-modified olefin resin is less than 49 mass%, heat resistance will fall.

In the outer surface layer 120, the content of the olefin elastomer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, particularly preferably 5 to 15% by mass. . If the content of the olefin-based elastomer is less than 1% by mass, there is a possibility that the appearance of the mat bath may not be obtained. On the other hand, if the content of the olefin-based elastomer exceeds 30% by mass, the heat resistance is insufficient, and when the lid 3 is heat-sealed to the flange 23 of the molding container 2, the outside of the flange 23 There is a fear that the surface layer 120 is crushed.

The outer surface layer 120 is preferably in the form of a sea island structure. By having such an island-in-the-sea structure, irregularities are appropriately formed on the surface of the outer surface layer 120, and the gloss is suppressed due to the diffuse reflection of light, and an excellent matte appearance can be obtained. In the island-in-sea structure, a form in which the elastomer component forms an island is preferable.

It is preferable that the said 2nd elastomer modified olefin resin has a 2 or more crystallization peak in a differential scanning calorimetry (DSC) measurement graph. When it has two crystallization peaks, it is preferable that the crystallization peak (crystallization temperature) on the high temperature side is 90 degreeC or more, and the crystallization peak (crystallization temperature) on the low temperature side is 80 degrees C or less. Moreover, when it has three or more crystallization peaks, it is preferable that the crystallization peak (crystallization temperature) of the highest temperature side is 90 degreeC or more, and the crystallization peak (crystallization temperature) of the lowest temperature side is 80 degrees C or less.

In addition to the first elastomer-modified olefin resin, the second elastomer-modified olefin resin, and the olefin-based elastomer, the outer surface layer 120 contains at least one of inorganic particles, organic particles, and a slip agent. It is preferable. By the addition of the inorganic fine particles or the organic fine particles to the outer surface layer 120, fine adjustment of the mat roughness (concave-convex) of the outer surface of the laminate 10 can be performed, and more excellent designability can be obtained. In addition, by adding the slip agent to the outer surface layer 120, excellent activity is imparted to the outer surface of the laminate 10, and molding with a deeper molding depth can be performed satisfactorily, and the whitening at the time of molding is also sufficient. The effect of being suppressed can be obtained.

Although it does not specifically limit as said inorganic type microparticles | fine-particles, For example, silica, aluminum silicate, barium sulfate, etc. are mentioned. Although it does not specifically limit as said organic type microparticles | fine-particles, Acrylic resin beads, polystyrene resin beads, etc. are mentioned, for example. Although it does not specifically limit as said slip agent, For example, waxes, such as fatty acid amides, such as an erucamide, a stearic acid amide, and an oleic acid amide, a crystalline wax, a polyethylene wax, etc. are mentioned. Instead of or in addition to the addition of the slip agent, lubricating oils such as silicone oil and rapeseed oil may be applied to the surface of the laminate 10 during molding.

As shown to Fig.1 (b), in the laminated body 10 which has the outer side resin film layers 12A and 12B of a two-layer structure, the 2nd outer side resin film layer 12B arrange | positioned at the metal foil layer 11 side. ) Is preferably made of a resin composition containing 50% by mass or more of a random copolymer containing propylene as one of the copolymerization components. Although it does not specifically limit as copolymerization component (monomer) other than propylene, For example, butadiene etc. are mentioned besides olefin components, such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4methyl-1- pentene. Can be. When the content rate of the said random copolymer is 50 mass% or more, sufficient heat seal strength can be ensured. More preferably, the content rate of the said random copolymer in 2nd outer side resin film layer 12B is set to 70 mass% or more. Moreover, it is preferable that the said random copolymer containing propylene as one of the copolymerization components is a random copolymer which has 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 to further improve the adhesive performance, while laminating with the high melting point random copolymer component. When the lid 3 is heat-sealed to the flange 23 of the container 2 formed by forming the sieve 10 (see FIG. 2), the second outer resin film layer 12B is less likely to be crushed, which is more sufficient. The shape retention of the container 2 can be ensured.

Moreover, it is preferable that the 2nd outer side resin film layer 12B is a structure which is not made into the form of an island-in-sea structure. With such a configuration, when the laminate 10 is deep-drawn and the molding container 2 is formed, the olefin resin phase and the elastomer phase in the second outer resin film layer 12B There is an advantage that it is possible to sufficiently suppress the occurrence of voids (space) at the interface of. Especially when the 2nd outer side resin film layer 12B is arrange | positioned in the position adjacent to the metal foil layer 11, the said effect becomes remarkable.

Outer side resin film layer 12: It is preferable that the film which comprises (12A) (12B) is manufactured by shaping | molding methods, such as multilayer extrusion molding, inflation molding, and T die cast film molding. Outside resin film layer 12: It is preferable that thickness (total thickness in the case of two or more layers) of (12A) (12B) is set to 20-80 micrometers. By the said thickness being 20 micrometers or more, generation | occurrence | production of a pinhole can fully be prevented, and also by setting the said thickness to 80 micrometers or less, resin usage amount can be reduced and cost reduction can be attained. More preferably, the thickness of the outer side resin film layers 12 and 12A and 12B is set to 30-50 micrometers.

In the case where the outer side resin film layer is a two-layer structure composed of the first outer side resin film layer 12A and the second outer side resin film layer 12B (see FIG. 1 (b)), the first outer side resin film layer 12A It is preferable that ratio of the thickness of) and the thickness of the 2nd outer side resin film layer 12B is the range of 9: 1-4: 6. When the ratio of the thickness of the 1st outer side resin film layer 12A exceeds 9, the lamination strength between both layers 12A and 12B may fall and peeling may occur. On the other hand, if the ratio of the thickness of the 1st outer side resin film layer 12A is less than 4, there exists a possibility that the outer surface layer of a mat-like may not be obtained.

It is especially limited as a method of laminating | stacking the film which comprises the 2nd outer side resin film layer 12B located inside in the single side outer resin film layer 12 or two layers to the metal foil which comprises the metal foil layer 11. Although not, it is a dry lamination method, a sandwich lamination method (method of extruding an adhesive film made of an acid-modified polypropylene resin and the like, followed by sand lamination between the metal foil and the film and then heat laminating with a heat roll). Can be. In the case of the dry lamination method, it is performed through the adhesive bond layer 14 which consists of a 2-component hardening type polyester-polyurethane resin adhesive, a polyether polyurethane resin adhesive, etc. (refer FIG. 1). It is preferable that the thickness of the adhesive bond layer 14 is set to 1-5 micrometers, More preferably, it is set to 1-3 micrometers from a viewpoint of thinning and weight reduction of the laminated body 10 for molding containers.

On the inner surface of the outer side resin film layer 12 or the second outer side resin film layer 12B, the printing layer 15 is formed in whole or in part by gravure printing or the like. By this printing layer 15, predetermined marks or decorations appear on the outer surface of the molding container 2. Although the printing layer 15 is not specifically limited, In the meaning which emphasizes the outer surface 12a of a mat-like, and gives a high quality, it is preferable to make a ground color deep colors, such as black. In addition, instead of the printing layer 15, you may add coloring components, such as a pigment, to the outer side resin film layers 12 and 12A, 12B.

The inner resin layer 13 constitutes the inner surface of the molding container 2 (including the upper surface of the flange portion 23), and is, for example, a polypropylene resin (PP) film or polyethylene having heat sealability. It is comprised by general-purpose films, such as a resin (PE) film, or the composite sheet which bonded these.

It is preferable to set it as 100-500 micrometers, and, as for the thickness of the film or composite sheet which comprise the inner side resin layer 13, 200-400 micrometers is more preferable.

Lamination | stacking of the metal foil which comprises the metal foil layer 11, and the film or composite sheet which comprises the inner side resin layer 13 is performed by the dry lamination method through the adhesive bond layer 16, for example. As the adhesive layer 16, for example, a two-component curable polyester-polyurethane resin adhesive or a polyether-polyurethane resin adhesive is used. It is preferable that the thickness of the adhesive bond layer 16 is set to 1-5 micrometers, More preferably, it is set to 1-3 micrometers from a viewpoint of thinning and weight reduction of the laminated body 10 for molding containers.

In addition, the inner side resin layer 13 may be formed of coat layers, such as an epoxy resin and a shellac resin, instead of the said film or a composite sheet.

FIG. 2 is a step of manufacturing a package 4 formed by sealing and packaging contents C, such as food, using the molding container 2 molded from the laminate 10 and a lid 3. It is shown in order.

First, the above-mentioned laminated body 10 is cut into predetermined shape and dimension, and this is shape | molded in cup shape. Molding of the laminate 10 is performed by cold forming such as deep drawing molding or elongated molding. In this way, the shaping | molding container 2 as shown to Fig.2 (a) can be obtained.

The shaping | molding container 2 is a horizontal annular shape extended in the radial direction outward from the bottom wall 21, the circumferential wall 22 erected from the periphery of the bottom wall 21, and the upper edge of the circumferential wall 22. The flange 23 is provided.

As the shape of the shaping | molding container 2, it has a cross section, such as a circle, an ellipse, an oblong shape, an approximate square, an outline rectangle, etc., and the thing of the taper cylindrical shape of which a diameter grows gradually upward and a vertical cylindrical shape, etc. are mentioned. Can be.

In addition, the depth of the shaping | molding container 2 is 15-50 mm normally.

Whitening is hardly seen on the outer surface of the shaping | molding container 2 formed from the laminated body 10 mentioned above. This is an olefin system by the stress at the time of shaping | molding by carrying out the resin composition of the outer side resin film layer 12 or the 1st outer side resin film layer 12A which comprises the outer surface layer 120 of the laminated body 10 as mentioned above. This is because the separation of the interface between the dendritic phase and the elastomer component and generation of voids (voids) are effectively suppressed.

Subsequently, as shown in FIG. 2 (b), after the contents C, such as food, are filled in the molding container 2, the lid 3 is placed on the upper surface of the flange 23 of the molding container 2. The periphery of the lower surface is heat-sealed.

Here, as the lid 3, for example, a heat sealability laminated on the lower surface of the metal foil layer while being made of a metal foil layer made of aluminum foil or the like, a polypropylene resin (PP) film, a polyethylene resin (PE) film, or the like The thing provided with the outer side resin film layer laminated | stacked on the upper surface of a metal foil layer, consisting of a resin film layer and a polyester resin (PEs) film, a polyamide resin (PA) film, etc. is used. Moreover, the opening part 31 is integrally formed in the cover 3 so that it may protrude outward from the flange 23 of the shaping | molding container 2 in a part of the outer periphery (refer FIG. 3).

The means for heat-sealing (heat-sealing) the lid 3 to the flange 23 of the molding container 2 is not particularly limited, but for example, the upper edge of the lid 3 is fitted to the upper surface of the flange 23. These overlapping portions are overlapped and heated by a predetermined time while applying a predetermined pressure by a hot plate heated at a predetermined temperature (for example, about 180 ° C.).

Subsequently, the package 4 obtained in the above step is introduced into the retort sterilization apparatus 5 to perform the retort sterilization treatment.

This retort sterilization process can also serve as a heat treatment process for dissipating whitening that has occurred on a part of the outer surface of the molding container 2. That is, in the shaping | molding container 2 formed by shape | molding the laminated body 10 which concerns on this invention in cup shape, as mentioned above, by the unique resin composition of the outer surface layer 120 of the laminated body 10, an outer surface Although whitening is suppressed, if a part of an outer surface, especially the corner part of the boundary between the bottom wall and the principal wall with a large degree of deformation | transformation by shaping | molding, etc., the matrix of an olefin resin and an olefin elastomer Even if some whitening occurs due to the voids (voids) generated at the interface, whitening can be completely lost by performing this heat treatment.

The heating temperature of the package 4 in this step is that of the outer surface layer 120 of the laminate 10, that is, the outermost layer of the outer resin film layer 12 of the single layer or the outer resin film layer of the plural layers. 1 (b), it is set to the temperature more than the softening point of resin of 1st outer side resin film layer 12A. More preferably, the heating temperature is a temperature below the melting point while being at least the softening point of the resin. By setting heating temperature to the temperature more than the softening point of the said resin, the deformation | transformation of the laminated body 10 by shaping | molding is alleviated and a void becomes easy to bury. Moreover, the shape of the shaping | molding container 2 can be maintained even after heating by making heating temperature into the temperature below the melting point of the said resin. Specifically, it is about 80 degreeC or more, and about 100-180 degreeC is preferable. The heating time is about 5 minutes to 3 hours.

Further, the heat treatment step may be of course other than the retort sterilization treatment. For example, the heat treatment step may also be performed by heat treatment by an oven, immersion treatment in hot water, or the like. In the case of heat treatment other than the retort sterilization treatment, only the molding container 2 may be heat treated in the step before the package 4 is formed.

3 shows the package 4 after the retort sterilization treatment.

The package 4 shown in the figure is provided with the molding container 2 which does not show the whitening by shaping | molding, and has the external surface of the mat-like thing with the favorable external appearance of the whole, and can bring a sense of quality to a consumer.

EXAMPLE

Next, the Example of this invention is described. However, this invention is not limited to the following example.

<Example 1>

As a metal foil layer, it consists of A8021H-O classified by JIS H4160, apply | coated the chemical conversion treatment liquid which consists of polyacrylic acid, a trivalent chromium compound, water, and alcohol on both surfaces, it is made to dry at 180 degreeC, and the amount of chromium adhesion per one side is carried out. An aluminum foil having a thickness of 120 μm was formed by forming a 5 mg / m 2 chemical conversion film.

As an outer side resin film layer, the unstretched polypropylene resin film (CPP) of the 2-layer structure of thickness 30micrometer was prepared. The film is a first elastomer-modified olefin resin (B-PP1), and is an ethylene-propylene elastomer-modified homopolypropylene resin obtained by copolymerizing ethylene and propylene having a melting point of 163 ° C and a crystal melting energy of 58 J / g. Ethylene-propylene elastomer-modified random copolymer 1 copolymerized with ethylene and propylene having a melting point of 144 ° C and a crystalline melting energy of 19 J / g as 94 mass% and the second elastomer-modified olefin resin (B-PP2). As a mass% and an olefin elastomer, the 1st resin film layer of 27 micrometers in thickness which consists of a resin composition of 5 weight% of ethylene-1-butene elastomers (EBR), and comprises an outer surface layer, and ethylene-propylene It is formed by co-extrusion using a T die so that a 2 μm-thick second resin film layer made of a random copolymer (R-PP, melting point of 155 ° C.) is formed. In addition, 1500 ppm of erucic acid amide and 5000 ppm of silica were added to the first resin film layer.

Here, melting | fusing point (Tmp) and crystal melting energy ((DELTA) H) of each said resin are measured on the following measurement conditions.

Lifting temperature speed: The lifting temperature of 10 ℃ / min between 23 ℃ 210 ℃

Sample rate: 5 mg

Container: use aluminum pan

Device: Shimadzu Corporation `` DSC-60A ''

Next, the plain paper by black ink (made by DIC Graphics, a product name: Panascia CVL-SP patent 805) using the gravure printing machine to the whole surface of the 2nd resin film layer side among the both sides of an unstretched polypropylene resin film. A printed layer of no land was formed.

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.

Then, on the one side of the aluminum foil, dry-laminated non-stretched polypropylene resin film (CPP) using a two-component curable polyester-polyurethane resin adhesive such that the printing layer is inside, and on the outer surface of the aluminum foil The composite sheet was dried in a two-component curable polyester-polyurethane resin adhesive so that the high-density polyethylene resin film side was inward, and cured in an environment at 40 ° C. for 5 days to form the mold of Example 1. The laminated body for containers was produced.

About the laminated body of Example 1, the glossiness (gross | gloss value) of the surface of an outer surface layer was measured with the glossiness meter (microtrigloss S by BYK Gardner) (the following example and a comparative example are also the same) , 28%.

<Example 2>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 85% by mass of homopolypropylene resin and second elastomer-modified olefin resin (B-PP2), 10% by mass of ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C and a crystal melting energy of 19 J / g. In the same manner as in Example 1, except that the olefin elastomer was changed to 5% by weight of ethylene-1-butene elastomer (EBR), a laminate for a molded container was produced, which was defined as Example 2.

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

<Example 3>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 155 ° C and a crystal melting energy of 51 J / g. 80 mass% of random copolymers, 2nd elastomer modified olefin resin (B-PP2), 10 mass% of ethylene-propylene elastomer modified random copolymers of 144 degreeC melting | fusing point and crystal melting energy of 19 J / g, Except having made into 10 weight% of ethylene-1-butene elastomers (EBR) as an olefin type elastomer, it carried out similarly to Example 1, and produced the laminated body for molded containers, and set it as Example 3.

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

<Example 4>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 75% by mass of homopolypropylene resin and second elastomer-modified olefin resin (B-PP2), 10% by mass of ethylene-propylene elastomer-modified random copolymer having a melting point of 136 ° C and a crystal melting energy of 18 J / g. In the same manner as in Example 1, except that the olefin elastomer was changed to 15% by weight of ethylene-1-butene elastomer (EBR), a laminate for a molded container was produced, which was defined as Example 4.

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

<Example 5>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 70 mass% of homopolypropylene resin and the second elastomer-modified olefin resin (B-PP2), 20 mass% of ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g. In the same manner as in Example 1, except that 10 wt% of ethylene-1-butene elastomer (EBR) was used as the olefin-based elastomer, a laminate for a molded container was produced, which was defined as Example 5.

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

<Example 6>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 30 mass% of ethylene-propylene elastomer modified random copolymers of 60 mass% of homopolypropylene resins, and the 2nd elastomer-modified olefin resin (B-PP2) which have a melting point of 144 ° C. and a crystal melting energy of 19 J / g. In the same manner as in Example 1, except that the olefin-based elastomer was 10% by weight of ethylene-propylene elastomer (EPR), a laminate for a molded container was produced, which was defined as Example 6.

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

<Example 7>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 166 ° C and a crystal melting energy of 65 J / g. 65 mass% of homopolypropylene resin and the second elastomer-modified olefin resin (B-PP2), 20 mass% of ethylene-propylene elastomer-modified random copolymer having a melting point of 144 ° C. and a crystal melting energy of 19 J / g. In the same manner as in Example 1, except that the olefin elastomer was changed to 15% by weight of ethylene-propylene elastomer (EPR), a laminate for a molded container was produced, which was defined as Example 7.

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

<Example 8>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 166 ° C and a crystal melting energy of 65 J / g. 30 mass% of ethylene-propylene elastomer modified random copolymers of 60 mass% of homopolypropylene resins, and the 2nd elastomer-modified olefin resin (B-PP2) which have a melting point of 144 ° C. and a crystal melting energy of 19 J / g. In the same manner as in Example 1, except that the olefin-based elastomer was 10% by weight of ethylene-propylene elastomer (EPR), a laminated body for a molding container was produced, which was set as Example 8.

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

<Example 9>

As an outer side resin film layer, the unstretched polypropylene resin film (CPP) of the single-layer structure of thickness 30micrometer was prepared. The copper film is a first elastomer-modified olefin resin (B-PP1), and is an ethylene-propylene elastomer-modified homopolypropylene resin obtained by copolymerizing ethylene and propylene having a melting point of 163 ° C and a crystal melting energy of 58 J / g. Ethylene-propylene elastomer-modified random copolymer 1 copolymerized with ethylene and propylene having a melting point of 144 ° C and a crystalline melting energy of 19 J / g as 94 mass% and the second elastomer-modified olefin resin (B-PP2). As a mass% and an olefin elastomer, it consists of a resin composition of 5 weight% of ethylene-1-butene elastomer (EBR), and is extrusion-molded using T-die. Furthermore, 1500 ppm of erucic acid amide and 5000 ppm of silica were added to the said outer side resin film layer.

And except having mentioned above, it carried out similarly to Example 1, and produced the laminated body for molded containers, and made this the Example 9.

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

<Comparative Example 1>

As the outer side resin film layer, an ethylene-propylene having a random polypropylene resin (R-PP) film (= outer surface layer, melting point of 155 ° C., crystal melting energy of 57 J / g) and crystal melting energy of 58 J / g while melting point of 163 ° C. 30 micrometers in thickness formed by laminating an elastomer-modified homopolypropylene resin (B-PP) film and a random polypropylene resin (R-PP) film (melting point 155 degreeC, crystal melting energy 57J / g) in this order Except having used the non-stretched polypropylene resin film (CPP) of 3 layer structure, it carried out similarly to Example 1, and produced the laminated body for molded containers, and made this the comparative example 1.

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

<Comparative Example 2>

As the first elastomer-modified olefin resin (B-PP1), an ethylene-propylene copolymerized with ethylene and propylene having a melting point of 163 DEG C and a crystal melting energy of 58 J / g was used as the first elastomer-modified olefin resin (B-PP1). Molding container was carried out in the same manner as in Example 1 except that it was made of a resin composition of 10% by mass of an ethylene-1-butene copolymer (EBR) as a stormer-modified homopolypropylene resin and 90% by mass of an olefin elastomer. The laminated body for metal was produced and it was set as the comparative example 2.

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

<Comparative Example 3>

As the second elastomer-modified olefin resin (B-PP2), the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified random air having a melting point of 144 ° C and a crystal melting energy of 19 J / g. A laminate for molding containers was produced in the same manner as in Example 1 except that 90% by weight of the copolymer and the olefin-based elastomer were made of a resin composition of 10% by weight of ethylene-propylene elastomer (EPR). This was set as Comparative Example 3.

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

<Comparative Example 4>

As the first elastomer-modified olefin resin (B-PP1), the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified homopolyol having a melting point of 163 ° C and a crystal melting energy of 58 J / g. Except having consisted of 100 mass% of propylene resin, it carried out similarly to Example 1, and produced the laminated body for molded containers, and made this the comparative example 4.

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

<Comparative Example 5>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 145 ° C and a crystal melting energy of 50 J / g. 80 mass% of random copolymers, 2nd elastomer modified olefin resin (B-PP2), 10 mass% of ethylene-propylene elastomer modified random copolymers of 144 degreeC melting | fusing point and crystal melting energy of 19 J / g, Except having made into 10 weight% of ethylene-propylene elastomers (EPR) as an olefin elastomer, the laminated body for molded containers was produced like Example 1, and it was set as the comparative example 5.

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

<Comparative Example 6>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 80% by mass of homopolypropylene resin and second elastomer-modified olefin resin (B-PP2), 10% by mass of ethylene-propylene elastomer-modified random copolymer having a melting point of 130 ° C. and a crystal melting energy of 14 J / g. In the same manner as in Example 1, except that 10 wt% of ethylene-propylene elastomer (EPR) was used as the olefin elastomer, a laminate for a molded container was produced, and this was set as Comparative Example 6.

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

<Comparative Example 7>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 155 ° C and a crystal melting energy of 49 J / g. 75 mass% random copolymers, 2nd elastomer-modified olefin resin (B-PP2), 10 mass% of ethylene-propylene elastomer modified random copolymers having a melting point of 144 ° C. and a crystal melting energy of 19 J / g, Except having made ethylene-propylene elastomer (EPR) 15 weight% as an olefin elastomer, it carried out similarly to Example 1, and produced the laminated body for molded containers, and made this the comparative example 7.

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

<Comparative Example 8>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 80% by mass of homopolypropylene resin and second elastomer-modified olefin resin (B-PP2), 10% by mass of ethylene-propylene elastomer-modified random copolymer having a melting point of 158 ° C and a crystal melting energy of 44 J / g. In the same manner as in Example 1, except that the olefin elastomer was changed to 10% by weight of ethylene-propylene elastomer (EPR), a laminate for molding containers was produced, and this was set as Comparative Example 8.

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

<Comparative Example 9>

As the first elastomer-modified olefin resin (B-PP1), the resin composition of the first resin film layer constituting the outer surface layer is an ethylene-propylene elastomer-modified resin having a melting point of 163 ° C and a crystal melting energy of 58 J / g. 90 mass% of homopolypropylene resin and an olefin-type elastomer except Example 10 except having made into 10 weight% of ethylene-propylene elastomers (EPR) whose crystal melting energy is 15 J / g while melting | fusing point is 40-70 degreeC. In the same manner as in the above, a laminated body for a molding container was produced, which was set as Comparative Example 9.

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

[Production of Courage]

Next, the laminates for molding containers of Examples 1 to 9 and Comparative Examples 1 to 9 were cut into predetermined shapes and sizes, respectively, to produce blanks, and after applying a small amount of siloxane to both sides of each blank, Deep drawing process using a die (made by AMADA Co., Ltd.) made of a mold and a shape of a die, thereby forming an annular cup-shaped container having a flange (bottom diameter 52 mmφ, opening diameter 65 mmφ, height 30). Mm, flange width 8 mm).

[Making of cover]

On the other hand, on one side of a 20-micrometer-thick aluminum foil consisting of A1N30H-O classified in JIS H4160, a 12-micrometer-thick polyethylene terephthalate resin (PET) film was used as a two-component curable polyester-polyurethane resin system as an outer resin layer. Dry lamination using an adhesive and dry a low-density linear low density polyethylene resin (LLDPE) film having a thickness of 30 µm on the other surface of the aluminum foil using a two-component curable polyester-polyurethane resin adhesive on the other surface of the aluminum foil. It laminated and cured for 5 days in 40 degreeC environment, and produced the laminated body for a cover.

The cover with a tab for opening was produced by cutting the obtained laminated body to the shape and size required according to a flange.

[Production of the package]

After putting 70 ml of water in each said container, the said cover was overlapped on the flange upper surface of a container so that a non-stretched polypropylene resin film (CPP) surface might contact, and these polymerized surfaces heated to 200 degreeC in the donut shape. The heat plate (heat-sealing) was performed by pressing the hot plate (outer diameter 90mm (phi), inner diameter 74mm (phi)) for 3 second by the pressing force of 150 kgf.

In this way, a package was obtained.

[Verification of Appearance of Package]

By visually observing the containers of the obtained packages, it was verified whether whitening occurred on the outer surface thereof and whether or not crushing occurred on the outer surface layer of the flange. The verification result is shown in the following Table 1 with the composition and glossiness of the outer surface layer of the laminated body which is the molding material of each container.

In addition, in the column of "whitening of the outer surface of a container" of Table 1, whether or not whitening is recognized on the outer surface of a container, or there is little whitening, "◎" and that there are few whitenings, and to what extent What had arisen was "(triangle | delta)" and what had whitening remarkably was made into "x". In addition, in the column of `` crushing of the flange '' of Table 1, the occurrence of crushing is not recognized in the outer surface layer of the flange of the container with the heat seal of the lid, `` ◎ '', almost no crushing. "" And the thing which dent generate | occur | produced to some extent were made into "(circle)", and the thing which dent produced remarkably was "x". In addition, in Table 1, "B-PP1" and the 1st elastomer-modified olefin resin were shown as "B-PP2".

TABLE 1

As is clear from Table 1, it is understood that the laminates of Examples 1 to 9 had low glossiness and improved whitening phenomenon during molding. In addition, in Examples 1-9, the dent did not generate | occur | produce in the outer surface layer of the flange of the container after heat-sealing the lid | cover.

On the other hand, in Comparative Examples 1 and 4, since the composition of the outer surface layer was different from the present invention, the glossiness did not sufficiently decrease, and a mat-like laminate could not be obtained.

Although the glossiness fell sufficiently in the laminated body of the comparative example 2, 6, 8, 9, the strong whitening phenomenon was recognized by the R part of the bottom of the container after shaping | molding.

Although the whitening by the shaping | molding of the laminated bodies of Comparative Examples 3, 5, and 7 was suppressed, the outer surface layer of the flange of the container after heat-sealing the lid was crushed, and shape retention was inadequate.

From the above verification results, it is thought that the crushing 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, and it contains the melting point (B-PP1 and B-PP2). The higher melting point is 155 ° C or higher, and when the crystal melting energy (B-PP1 and B-PP2 is contained, the weighted average of both crystal melting energies in the content ratio) is 40 J / g or more (more preferred. Is 50 J / g or more), it can be seen that the crushing is difficult to occur.

INDUSTRIAL APPLICABILITY The present invention is suitable for sealing packaging foods and the like, and can be suitably used for a molding container having an external surface having a good matte appearance and a laminate comprising the molding material.

2: forming container
23: flange
3: cover
4: package
5: retort sterilization apparatus
10: laminated body for molding container
11: metal foil layer
12: outer side resin film layer
12A: 1st outer side resin film layer
12B: 2nd outer side resin film layer
120: outer surface layer
120a: surface of outer surface layer
15: print layer
C: Contents

Claims (15)

As a laminated body for shaping | molding container provided with the metal foil layer and the outer side resin film layer laminated | stacked on the surface which becomes the outer side of a container among the both surfaces of the said metal foil layer, and comprises the mat-like outer surface layer,
The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified homopolypropylene resin,
In the said outer side resin film layer, the sum total of the content rate of the said 1st elastomer modified olefin resin and the content rate of the said 2nd elastomer modified olefin resin is 50 mass% or more, The laminated body for molded containers characterized by the above-mentioned. As a laminated body for shaping | molding container provided with the metal foil layer and the outer side resin film layer laminated | stacked on the surface which becomes the outer side of a container among the both surfaces of the said metal foil layer, and comprises the mat-like outer surface layer,
The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified product of a random copolymer containing propylene as one of the copolymerization components,
The said outer resin film layer WHEREIN: The sum total of the content rate of the said 1st elastomer modified olefin resin, and the content rate of the said 2nd elastomer modified olefin resin is 50 mass% or more, The laminated body for molded containers characterized by the above-mentioned. As a laminated body for shaping | molding container provided with the metal foil layer and the outer side resin film layer laminated | stacked on the surface which becomes the outer side of a container among the both surfaces of the said metal foil layer, and comprises the mat-like outer surface layer,
The outer resin film layer has 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, and a second elastomer having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. It consists of a resin composition containing a mercury modified olefin resin and an olefin elastomer,
The first elastomer-modified olefin resin and the second elastomer-modified olefin resin are each composed of an elastomer-modified homopolypropylene resin and an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified product of a random copolymer containing propylene as one of the copolymerization components,
The said outer resin film layer WHEREIN: The sum total of the content rate of the said 1st elastomer modified olefin resin, and the content rate of the said 2nd elastomer modified olefin resin is 50 mass% or more, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 3,
In the said outer side resin film layer, the content rate of the said 2nd elastomer-modified olefin resin is 1-50 mass%, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 4,
In the said outer side resin film layer, the content rate of the said 1st elastomer modified olefin resin is 49-98 mass%, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The said outer resin film layer WHEREIN: The content rate of the said olefin elastomer is 1-30 mass%, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 6,
The glossiness of the surface of the said outer side resin film layer is 0.5 to 12%, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 7,
The elastomer components of the first elastomer-modified olefin resin and the second elastomer-modified olefin resin are ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-, respectively. It is at least one of 1-butene elastomer, The laminated body for molded containers characterized by the above-mentioned. The method according to any one of claims 1 to 8,
The olefin elastomer is at least one of ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene elastomer. The method according to any one of claims 1 to 9,
The outer side resin film layer further includes at least one of inorganic fine particles, organic fine particles, and a slip agent. The method according to any one of claims 1 to 10,
Said second elastomer-modified olefin resin has two or more crystallization peaks in a differential scanning calorimetry graph. The method according to any one of claims 1 to 11,
A plurality of outer side resin film layers are laminated | stacked on the surface which becomes the outer side of a container among the both surfaces of the said metal foil layer, The said outer surface layer is comprised by the outermost of the outer side resin film layers of the said multiple layer, It is characterized by the above-mentioned. The laminated body for shaping | molding container to be made. The method according to any one of claims 1 to 12,
When a printing layer is formed between the metal foil layer and the outer side resin film layer, or a coloring component is added to the outer side resin film layer, a predetermined mark or decoration appears on the surface of the outer side resin film layer. The laminated body for shaping | molding container made into it. The molding container formed by shape | molding the laminated body for shaping | molding container in any one of Claims 1-13 in cup shape, and has a flange in the opening periphery, The molding container characterized by the above-mentioned. A cover is bonded to the flange of the molding container according to claim 14, wherein the lid is covered with the contents to cover the opening of the molding container.

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