CN117120262A - Multilayer film, packaging material, and package - Google Patents

Multilayer film, packaging material, and package Download PDF

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Publication number
CN117120262A
CN117120262A CN202280027824.0A CN202280027824A CN117120262A CN 117120262 A CN117120262 A CN 117120262A CN 202280027824 A CN202280027824 A CN 202280027824A CN 117120262 A CN117120262 A CN 117120262A
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CN
China
Prior art keywords
propylene
ethylene
multilayer film
mass
outer layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280027824.0A
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Chinese (zh)
Inventor
滨田大辅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toppan Inc
Original Assignee
Toppan Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toppan Printing Co Ltd filed Critical Toppan Printing Co Ltd
Priority claimed from PCT/JP2022/019845 external-priority patent/WO2022255041A1/en
Publication of CN117120262A publication Critical patent/CN117120262A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
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    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
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    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

The present disclosure relates to a multilayer film, which sequentially includes: a first outer layer as a heat-sealing layer containing a propylene homopolymer (A) and a propylene-ethylene random copolymer (B); an inner layer containing a propylene-ethylene block copolymer (C) and an ethylene-propylene copolymer elastomer (D); and a second outer layer containing a propylene homopolymer (A) and a propylene-ethylene random copolymer (B), wherein at least any one of the first outer layer, the inner layer and the second outer layer further contains a polyphenol compound.

Description

Multilayer film, packaging material, and package
Technical Field
The present disclosure relates to multilayer films, packaging materials, and packages. More specifically, the present disclosure relates to a polypropylene-based multilayer film which can be preferably used as a sealant film for packaging, and which can be used for severe treatments such as boiling water treatment and retort treatment, and a packaging material and a packaging body obtained using the polypropylene-based multilayer film.
Background
Polypropylene films are excellent in rigidity and heat resistance and are inexpensive, and therefore, they are sometimes used as sealant films for various packaging materials such as food packaging. The polypropylene film is used mainly for packaging foods for retort foods, which are sterilized or disinfected by a pressure treatment at high temperature.
In packaged foods subjected to sterilization at high temperature, such as retort foods, there are cases where the contents are degraded or modified to generate a modified odor due to heat sterilization or long-term storage during production. The source of the modified odor is carbohydrates, oils and fats, proteins, and the like, and among them, the modified odor of proteins contained in meat, fish, soybean, egg, and the like, particularly sulfur odor derived from sulfur compounds, is a problem in many cases.
Patent document 1 proposes a package characterized in that a coating agent comprising a zinc compound and a solvent or a dispersion medium is coated on the surface of an oxygen barrier material which is a film formed from a resin layer containing a polycarboxylic acid polymer and is formed on a base film.
Patent document 2 proposes a laminate for heat sterilization treatment comprising a heat-sealable resin and SiO 2 /Al 2 O 3 A hydrophobic zeolite sealant layer having a molar ratio of 30/1 to 8000/1.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-018551
Patent document 2: japanese patent laid-open publication No. 2019-177521
Disclosure of Invention
Technical problem to be solved by the invention
The packages described in patent documents 1 and 2 exhibit deodorizing effects against sulfur odor, but there is room for improvement in visibility of the contents.
The present disclosure has been made in view of the above-described facts, and an object thereof is to provide a multilayer film excellent in deodorizing property against sulfur odor generated from contents and visibility of the contents. The present disclosure also aims to provide a packaging material and a package obtained using the multilayer film.
Means for solving the technical problems
As a result of intensive studies to solve the above-mentioned problems, the inventors have found that it is important to blend a polyphenol compound into at least one of a plurality of polypropylene-based layers constituting a polypropylene-based multilayer film, and thus the following multilayer film has been completed.
The multilayer film according to one aspect of the present disclosure comprises, in order: a first outer layer as a heat-sealing layer containing a propylene homopolymer (A) and a propylene-ethylene random copolymer (B); an inner layer containing a propylene-ethylene block copolymer (C) and an ethylene-propylene copolymer elastomer (D); and a second outer layer containing a propylene homopolymer (A) and a propylene-ethylene random copolymer (B), wherein at least any one of the first outer layer, the inner layer and the second outer layer further contains a polyphenol compound.
In the above multilayer film, by blending the polyphenol compound in the polypropylene film, an excellent deodorizing effect against sulfur odor derived from a sulfur compound can be obtained by utilizing a strong reducing force by hydroxyl groups possessed by the polyphenol compound. In addition, when a polyphenol compound is used as a material for imparting a deodorizing effect, it is possible to suppress the random reflection of light in the film and to obtain excellent transparency, as compared with the case of blending an inorganic compound. Such a film can obtain a deodorizing effect while further improving the visibility of the content, compared with the case where a coating agent containing zinc oxide particles is used (for example, patent document 1) or the case where a sealant layer containing hydrophobic zeolite is used (for example, patent document 2). The effect is preferable in particular for food high-temperature retort treatment applications which are prone to sulfur odor. In addition, the polyphenol compound has an advantage of having little influence on the environment or human health as compared with other organic or inorganic deodorant which is not a natural source.
In one embodiment, the polyphenol compound may be contained in an amount of 1.5 to 8.0 mass% based on the total amount of the multilayer film. This makes it possible to achieve more excellent deodorizing properties and visibility.
One way may be: the inner layer contains 90 to 50 parts by mass of a propylene-ethylene block copolymer (C) and 10 to 50 parts by mass of an ethylene-propylene copolymer elastomer (D), and further contains a polyphenol compound. The inner layer contains 90 to 50 parts by mass of the propylene-ethylene block copolymer (C) and 10 to 50 parts by mass of the ethylene-propylene copolymer elastomer (D), so that the flexibility of the film can be easily maintained and excellent cold resistance impact can be easily obtained. Further, the polyphenol compound is contained in the inner layer, whereby a deodorizing function can be imparted to the multilayer film. In particular, by including a polyphenol compound in an inner layer having a tendency to be thicker than an outer layer, the apparent amount of polyphenol compound is reduced, and transparency is easily ensured.
One way may be: the first and second outer layers contain 70 to 30 parts by mass of a propylene homopolymer (A) and 30 to 70 parts by mass of a propylene-ethylene random copolymer (B), and further contain a polyphenol compound. By using the propylene homopolymer (a) and the propylene-ethylene random copolymer (B) having high smoothness, surface irregularities, which are factors for reducing the transparency of the film, can be easily suppressed. This makes it possible to achieve both heat resistance and transparency. Further, the polyphenol compound is contained in the outer layer, whereby a deodorizing function can be imparted to the multilayer film.
In one embodiment, the polyphenol compound may be a condensed tannin. This makes it possible to achieve more excellent deodorizing properties and visibility.
In one embodiment, the total thickness of the first outer layer and the second outer layer may be 25 to 42% based on the thickness of the multilayer film. This makes it easy to achieve both transparency and heat sealability.
In one embodiment, the thickness of the inner layer may be 30 μm or more. Thus, the flexibility of the film can be easily maintained, and excellent cold shock resistance can be easily obtained.
The packaging material according to one aspect of the present disclosure is provided with the above-described multilayer film and a substrate.
The package body according to one aspect of the present disclosure is formed by bagging the above-described packaging material.
Effects of the invention
According to the present disclosure, a multilayer film excellent in deodorizing property against sulfur odor generated from the content and visibility of the content can be provided. The present disclosure may also provide a packaging material and a package obtained using the multilayer film. According to the present disclosure, a multilayer film can be provided that can significantly improve transparency while maintaining a high hydrogen sulfide reduction rate, as compared with, for example, using the same amount of inorganic particles instead of the polyphenol compound.
Drawings
Fig. 1 is a cross-sectional view of a multilayer film of one embodiment of the present disclosure.
Fig. 2 is a cross-sectional view of a packaging material of one embodiment of the present disclosure.
FIG. 3 is a graph showing the total heat of fusion of the propylene-ethylene random copolymer (B) used in the examples and the result of dividing the heat of fusion at 135 ℃.
Detailed Description
< multilayer film >
Fig. 1 is a cross-sectional view of a multilayer film of one embodiment of the present disclosure. The multilayer film 10 includes, in order, a first outer layer 1a, an inner layer 2, and a second outer layer 1b. The multilayer film is a polypropylene multilayer film and can be used as a polypropylene unstretched sealant film.
[ first outer layer and second outer layer ]
The first outer layer and the second outer layer contain a propylene homopolymer (A) and a propylene-ethylene random copolymer (B). The first outer layer and the second outer layer may be formed of a propylene homopolymer (a) and a propylene-ethylene random copolymer (B). The first outer layer and the second outer layer are sometimes collectively referred to as the outer layers only. The first outer layer and the second outer layer may have the same composition, and may also have different compositions. When used as a packaging material, the first outer layer functions as a heat seal layer and is disposed so as to be in contact with the content.
(propylene homopolymer (A))
The method for producing the propylene homopolymer (a) is not particularly limited, and it can be obtained, for example, by a method of homopolymerizing propylene using a ziegler-natta catalyst, a metallocene catalyst, or a half-metallocene catalyst. The outer layer contains the propylene homopolymer (a), and thus can impart excellent heat resistance to the outer layer.
As the propylene homopolymer (A), those having a melting start temperature of 150℃or higher and a melting peak temperature of 155℃or higher in the differential scanning calorimetry (JIS K7121) can be used. The melting start temperature and the melting peak temperature are both in this range, and have excellent heat resistance, for example, it is difficult for melt adhesion to occur on the inner surface of the package after the high-temperature retort treatment at high temperature.
As the propylene homopolymer (A), a melt flow rate (MFR: ISO 1133) (temperature 230 ℃ C., load of 2.16 kg) of 2.0 to 7.0g/10 minutes can be used. The melt flow rate is a parameter indicating fluidity of the polymer material when it is melted, and may be a parameter indicating molecular weight. Therefore, when the melt flow rate is too high, the impact resistance of the polymer material tends to be low, while when too low, the extruder load during molding increases, the processing speed decreases, and the productivity tends to decrease. From these viewpoints, the melt flow rate may be 2.0 to 6.0g/10 minutes, and may be 2.0 to 5.0g/10 minutes.
(propylene-ethylene random copolymer (B))
The method for producing the propylene-ethylene random copolymer (B) is not particularly limited, and it can be obtained by copolymerizing ethylene as a comonomer in a main monomer formed from propylene using, for example, a ziegler-natta catalyst, a metallocene catalyst, or a half-metallocene catalyst. The outer layer contains the propylene-ethylene random copolymer (B), whereby a multilayer film having excellent transparency and flexibility can be obtained.
As the propylene-ethylene random copolymer (B), those having a melting start temperature of 140℃or higher and a melting peak temperature of 145℃or higher in the case of differential scanning calorimetry (JIS K7121) can be used. The melting start temperature and the melting peak temperature are both in this range, and have excellent heat resistance, for example, it is difficult for melt adhesion to occur on the inner surface of the package after a severe high-temperature retort treatment at 135 ℃ for 40 minutes.
As the propylene-ethylene random copolymer (B), a heat of fusion ΔH at a temperature higher than 135℃at the measurement temperature in the differential scanning calorimetry (JIS K7121) can be used h And a heat of fusion delta H at a lower temperature side l Ratio DeltaH of (2) h /ΔH l 1.5 to 2.5. When the ratio is not more than the upper limit, the film can be cooked at a high temperature while maintaining the flexibilityAfter the treatment, the cracking of the heat-sealed portion can be suppressed, and the heat-sealing strength is hardly lowered. The lower limit of the above ratio may be 1.5 from the viewpoint of the difficulty in melt adhesion on the inner surface of the package after the high temperature retort treatment.
The ethylene content of the propylene-ethylene random copolymer (B) may be 5.0 mass% or less. When the ethylene content is not more than the upper limit, the heat resistance is not excessively lowered while maintaining the transparency, and the fusion bonding on the inner surface of the package after the retort treatment is easily suppressed. From this viewpoint, the ethylene content may be 4.5 mass% or less, or may be 4.0 mass% or less. The lower limit of the ethylene content is not particularly limited, and may be 2.0 mass% in view of maintaining the flexibility of the film, suppressing cracking of the heat-sealed portion after the retort treatment, and hardly reducing the heat-sealing strength.
The ethylene content of the propylene-ethylene random copolymer (B) can be measured by a method for quantifying the ethylene content (IR method) described on pages 412 to 413 of the society for high molecular analysis, japan society for analysis, which is incorporated into the high molecular analysis Manual (5/10/3 rd printing, 2013).
The outer layer may contain 70 to 30 parts by mass of the propylene homopolymer (A) and 30 to 70 parts by mass of the propylene-ethylene random copolymer (B). The content of the propylene homopolymer (a) of 30 parts by mass or more makes it easy to maintain excellent heat resistance. Further, the propylene homopolymer (a) is contained in an amount of 70 parts by mass or less, that is, the propylene-ethylene random copolymer (B) is contained in an amount of at least 30 parts by mass or more, whereby excellent transparency and heat sealability are easily exhibited. From these viewpoints, the outer layer may contain 60 to 40 parts by mass of the propylene homopolymer (a) and 40 to 60 parts by mass of the propylene-ethylene random copolymer (B).
[ inner layer ]
The inner layer contains a propylene-ethylene block copolymer (C) and an ethylene-propylene copolymer elastomer (D). The inner layer may be formed of a propylene-ethylene block copolymer (C) and an ethylene-propylene copolymer elastomer (D).
(propylene-ethylene Block copolymer (C))
The propylene-ethylene block copolymer (C) may be a copolymer obtained by producing the propylene polymer (C1) in the first step, followed by producing the ethylene-propylene copolymer (C2) by gas phase polymerization in the second step. The propylene-ethylene block copolymer (C) is not a block copolymer having a bond between the end of a propylene polymer and the end of an ethylene-propylene copolymer, but is a blended copolymer. By containing the propylene-ethylene block copolymer (C) in the inner layer, the film can be maintained in flexibility, cracking of the heat-sealed portion can be suppressed after the retort treatment, excellent heat sealability can be easily obtained, and excellent cold resistance impact resistance can be easily obtained.
As the propylene-ethylene block copolymer (C), one having a melt flow rate (MFR: ISO 1133) (temperature 230 ℃ C., load of 2.16 kg) of 0.5 to 2.5g/10 min can be used. When the melt flow rate is too high, the impact resistance of the film tends to be low, while when too low, the extruder load during molding increases, the processing speed decreases, and the productivity tends to decrease. From these viewpoints, the melt flow rate may be 1.0 to 2.5g/10 minutes, and may be 1.0 to 2.0g/10 minutes.
The propylene-ethylene block copolymer (C) may contain 90 to 60% by mass of the propylene polymer (C1) and 10 to 40% by mass of the ethylene-propylene copolymer (C2). By each component being in this range, excellent heat sealability can be easily obtained and excellent cold resistance impact resistance can be easily obtained.
The ethylene content of the ethylene-propylene copolymer (C2) contained in the propylene-ethylene block copolymer (C) is not particularly limited and may be 20 to 40 mass%. When the ethylene content is not more than the upper limit, tackiness of the product can be suppressed, contamination due to tackiness of the product is less likely to occur during production, and excellent productivity can be easily maintained. When the ethylene content is not less than the lower limit, the film can be kept flexible, cracking of the heat-sealed portion can be suppressed after the retort treatment, excellent heat sealability can be easily obtained, and excellent cold impact resistance can be easily obtained.
(ethylene-propylene copolymer elastomer (D))
The ethylene-propylene copolymer elastomer (D) can be obtained, for example, by a slurry polymerization method in the presence of an inert hydrocarbon such as hexane, heptane, kerosene, or a liquefied α -olefin solvent such as propylene, a gas phase polymerization method in the absence of a solvent, or the like. Specifically, the ethylene-propylene copolymer elastomer (D) can be obtained by a known multistage polymerization method. Namely, the polypropylene-based resin can be contained in a high-polymer rubber obtained by polymerizing propylene and/or a propylene- α -olefin polymer in the first reaction stage and then copolymerizing propylene and α -olefin in the second reaction stage. The ethylene-propylene copolymer elastomer (D) is contained in the inner layer, whereby flexibility is easily imparted to the film, cracking of the heat-sealed portion can be suppressed, excellent heat-sealing properties can be easily obtained, and excellent cold-resistant impact properties can be easily obtained.
As the ethylene-propylene copolymer elastomer (D), one having a melt flow rate (MFR: ISO 1133) (temperature 230 ℃ C., load of 2.16 kg) of 0.5 to 3.5g/10 min can be used. When the melt flow rate is equal to or higher than the lower limit, the extruder load during molding is reduced, the processing speed is hardly lowered, and excellent productivity is easily maintained. When the melt flow rate is not more than the upper limit, the compatibility between the propylene-ethylene block copolymer (C) and the ethylene-propylene copolymer elastomer (D) is good, and the transparency is hardly lowered.
As the ethylene-propylene copolymer elastomer (D), one having a mass ratio of propylene content to ethylene content (propylene content/ethylene content) of 1.5 to 4.0 can be used. When the ratio is not less than the lower limit, the film can maintain the flexibility, and after the retort treatment, the heat-sealed portion can be prevented from cracking, and excellent heat-sealing properties can be easily obtained. When the ratio is not more than the upper limit, the compatibility between the propylene-ethylene block copolymer (C) and the ethylene-propylene copolymer elastomer (D) is good, and the transparency is hardly lowered.
The inner layer may contain 90 to 50 parts by mass of the propylene-ethylene block copolymer (C) and 10 to 50 parts by mass of the ethylene-propylene copolymer elastomer (D). The content of the propylene-ethylene block copolymer (C) is 50 parts by mass or more, whereby excellent heat sealability can be easily maintained. Further, the propylene-ethylene block copolymer (C) is contained in an amount of 90 parts by mass or less, that is, the ethylene-propylene copolymer elastomer (D) is contained in an amount of at least 10 parts by mass or more, whereby more excellent heat sealability and excellent cold impact resistance can be exhibited. From these viewpoints, the inner layer may contain 80 to 60 parts by mass of the propylene-ethylene block copolymer (C) and 20 to 40 parts by mass of the ethylene-propylene copolymer elastomer (D).
[ polyphenol Compound ]
At least any one of the first outer layer, the inner layer, and the second outer layer further contains a polyphenol compound. When the inner layer further contains a polyphenol compound in addition to the propylene-ethylene block copolymer (C) and the ethylene-propylene copolymer elastomer (D), a deodorizing function can be imparted to the film while maintaining the transparency of the film. When the outer layer further contains a polyphenol compound in addition to the propylene homopolymer (a) and the propylene-ethylene random copolymer (B), a deodorizing function can be imparted to the film.
The polyphenol compound may be contained in an amount of 1.5 to 8.0% by mass, or 1.5 to 5.0% by mass, or 2.0 to 4.5% by mass, or 3.0 to 4.0% by mass, based on the total amount of the multilayer film. When the content of the polyphenol compound is not less than the lower limit, an excellent deodorizing effect against sulfur odor derived from a sulfur compound can be easily obtained, and when it is not more than the upper limit, excellent transparency can be easily exhibited.
Examples of the polyphenol compound include tannins, gallic acid, condensed tannins which are high molecular polyphenols, and the like. Condensed tannins are contained in persimmon fruits (astringent persimmon), immature banana, grape pericarp, seeds, etc., and can be obtained as a concentrate by squeezing or solvent extraction. These polyphenol compounds may be used alone or in combination of 2 or more.
From the viewpoint of ensuring excellent deodorizing properties, persimmon tannin may be particularly used as the condensed tannin. As a recipe containing a large amount of persimmon tannin, astringent persimmon is known. Persimmon tannins, which are one of condensed tannins, are contained in large amounts in astringent persimmon. Persimmon tannin is a high molecular procyanidin polymer containing epicatechin, catechin-3-gallate, epigallocatechin, and gallocatechin-3-gallate as constituent components. Persimmon tannins have a plurality of hydroxyl groups with strong reactivity. It is therefore considered that the deodorizing effect can be exerted by binding and wrapping the deodorizing component. In addition, persimmon tannins have less influence on the environment or human health than other organic or inorganic deodorants or antibacterial agents that are not natural sources, and are particularly suitable for packaging materials for retort foods.
When persimmon tannin is contained in the multilayer film, for example, persimmon tannin obtained by refining may be used, or astringent persimmon itself containing persimmon tannin may be used. When astringent persimmon is used, the amount of tannin can be adjusted by using a thermoplastic resin. By using astringent persimmon, the step of refining persimmon tannin can be omitted, which is more excellent from an economical point of view.
The thickness of the multilayer film is not particularly limited as long as it can be used as a film for a packaging material, but there is a cost disadvantage when the film is too thick. Therefore, the thickness of the multilayer film may be 100 μm or less, or may be 50 to 70 μm.
The thickness of the outer layer (i.e., the total thickness of the first outer layer and the second outer layer) may be 25 to 42% based on the thickness of the multilayer film. When the thickness ratio of the outer layer is equal to or greater than the lower limit, excellent transparency can be easily obtained, whereas when it is equal to or less than the upper limit, the heat sealability of the film can be suppressed from being lowered, and the practical use can be easily obtained.
The thickness of the outer layer (i.e., the total thickness of the first outer layer and the second outer layer) may be 10 μm or more, and may be 15 μm or more. This makes it easy to ensure transparency of the film and makes it difficult to reduce heat seal strength. The upper limit of the thickness of the outer layer is not particularly limited, and may be 40 μm or less, 30 μm or less, or 20 μm or less in order to easily secure cold resistance.
The thickness of the inner layer may be 30 μm or more, or 35 μm or more. Thus, the flexibility of the film can be maintained, the film is hardly broken after the high-temperature retort treatment, and the heat seal strength is hardly lowered. The upper limit of the thickness of the inner layer is not particularly limited, and may be 80 μm or less, or may be 70 μm or less, or may be 50 μm or less, for example, from the viewpoint of cost.
< method for producing multilayer film >
The method for producing the multilayer film is not particularly limited, and a known method can be used. For example, as a method of the thermoforming processing, a melt kneading method using a general mixer such as a single screw extruder, a twin screw extruder, a multi-screw extruder, or the like is given; and a method in which the components are dissolved or dispersed and mixed and then the solvent is removed by heating. In view of operability, a single screw extruder or a twin screw extruder may be used. When a single screw extruder is used, examples of the screw include a full flighted screw, a screw with a mixing element, a split screw, a grooved screw, and the like, and these can be used without particular limitation. The twin-screw extruder may be a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, or the like, and the screw shape may be a full-flighted screw, a kneading disc screw, or the like without any particular limitation.
Among the above methods, a method of melting a multilayer film by a single-screw extruder, a double-screw extruder, or the like, and then forming the film by a T die through an oil feed pipe or a multi-manifold can be used.
The resulting multilayer film may be subjected to a surface modification treatment to improve the suitability for the subsequent steps, if necessary. For example, in order to improve the printing suitability of the single film for use or the lamination suitability for lamination use, the surface to be in contact with the printing surface or the substrate may be subjected to a surface modification treatment. The surface modification treatment includes a treatment for generating a functional group by oxidizing the film surface, such as corona discharge treatment, plasma treatment, and flame treatment; or a modification treatment using a wet process for forming an easy-to-adhere layer by coating.
< packaging Material >
The multilayer film may be used as a single film or may be used after being laminated with a base material, and the method of using the multilayer film as a packaging material is not particularly limited.
When the multilayer film is used after being laminated with a base material, the packaging material may be provided with the multilayer film and the base material. Such a packaging material can be obtained by laminating at least 1 layer of a biaxially oriented polyamide film (ONy), a biaxially oriented polyester film (PET), a printing paper, a metal foil (Al foil), a transparent vapor deposited film, or the like on the above multilayer film to form a laminate. Fig. 2 is a cross-sectional view of a packaging material of one embodiment of the present disclosure. The packaging material 100 shown in the figure includes a multilayer film 10, an adhesive layer 3, a base film 4, an adhesive layer 5, and a transparent vapor deposition film 6 in this order. As a method for producing the laminate, a method of extrusion-laminating a multilayer film directly on a base film or the like as needed may be mentioned, in addition to a usual dry lamination method of adhering a base film or the like on a multilayer film using an adhesive in this way.
The laminate structure of the laminate may be appropriately adjusted according to the required characteristics of the package, for example, the barrier property during the quality maintenance of the packaged food, the size/impact resistance corresponding to the weight of the content, the visibility of the content, and the like.
< packaging body >
The package (bag) may be formed by bagging the above-mentioned packaging material, and the form of the bag is not particularly limited. For example, the packaging material (laminate) may be used in a flat bottom bag, a three-side sealed bag, a palm bag, an organ bag, a self-supporting bag, a spout bag, a spouted bag, or the like using a multilayer film as a sealing material.
Examples
The present disclosure will be described in detail using examples below, but the present disclosure is not limited to the examples below.
< preparation of various materials >
The propylene homopolymer (a), the propylene-ethylene random copolymer (B), the propylene-ethylene block copolymer (C), the ethylene-propylene copolymer elastomer (D) and the deodorant master batch (E) shown below were prepared.
(propylene homopolymer (A))
A propylene homopolymer having a melting start temperature of 153℃and a melting peak temperature of 159℃and a melt flow rate (MFR: ISO 1133) (temperature 230℃and load of 2.16 kg) of 3.0g/10 min was subjected to differential scanning calorimeter measurement (JIS K7121).
(propylene-ethylene random copolymer (B))
Melting start temperature at 142℃and melting peak temperature at 147℃and ΔH in differential scanning calorimeter measurement (JIS K7121) h /ΔH l A propylene-ethylene random copolymer having an ethylene content of 1.84 and 3.4 mass%.
The ethylene content was measured by a method (IR method) for measuring ethylene content described on pages 412 to 413 of a polymer analysis manual (2013, 5, 10, 3 rd printing) incorporated by the society for polymer analysis solicitation of Japanese society for analysis.
ΔH h /ΔH l Is the heat of fusion DeltaH at a temperature higher than 135 ℃ at the time of differential scanning calorimetry (JIS K7121) h And a heat of fusion delta H at a lower temperature side l Is a ratio of (2). FIG. 3 is a graph showing the total heat of fusion of the propylene-ethylene random copolymer (B) and the result of dividing the heat of fusion at 135 ℃.
(propylene-ethylene Block copolymer (C))
A propylene-ethylene block copolymer having a melt flow rate (MFR: ISO 1133) (temperature 230 ℃ C., load of 2.16 kg) of 2.0g/10 min, containing 77.1% by mass of propylene polymer, 22.9% by mass of ethylene-propylene copolymer and an ethylene content of 28.7% by mass of ethylene-propylene copolymer.
(ethylene-propylene copolymer elastomer (D))
An ethylene-propylene copolymer elastomer having a melt flow rate (MFR: ISO 1133) (temperature 230 ℃ C., load of 2.16 kg) of 0.6g/10 min and a propylene content/ethylene content (mass ratio) of 2.7.
(deodorant masterbatch (E))
As the deodorant masterbatch (E), MB-FPW-PE manufactured by Rilis scientific Co., ltd was used.
< production of multilayer film (Polypropylene-based multilayer film)
Example 1
In the outer layer forming, a resin mixture was prepared in which 50 parts by mass of the propylene homopolymer (a) and 50 parts by mass of the propylene-ethylene random copolymer (B) were mixed in the form of pellets.
In the inner layer forming process, a resin mixture was prepared in which 67.8 parts by mass of the propylene-ethylene block copolymer (C) and 32.2 parts by mass of the ethylene-propylene copolymer elastomer (D) were mixed in the form of pellets, and 3.09 parts by mass (adjusted so that the persimmon tannin content in the multilayer film became 2.0% by mass) of the deodorant master batch (E) was mixed with respect to the total 100 parts by mass of the propylene-ethylene block copolymer (C) and the ethylene-propylene copolymer elastomer (D).
The respective resin mixtures were fed to an extruder which was adjusted to 250℃and kneaded in a molten state, and the films of example 1 were produced by laminating the resin mixtures in such a manner that the thicknesses of the first outer layer and the second outer layer were 10 μm and the thickness of the inner layer was 40. Mu.m, respectively, using a T-die extruder with an oil-feeding jacket.
Example 2
A film of example 2 was produced in the same manner as in example 1, except that the compounding ratio of the deodorant master batch (E) was changed as shown in table 1.
Example 3
A film of example 3 was produced in the same manner as in example 1, except that the compounding ratio of the deodorant master batch (E) was changed as shown in table 1.
Example 4
A film of example 4 was produced in the same manner as in example 1, except that the compounding ratio of the deodorant master batch (E) was changed as shown in table 1.
Comparative example 1
A film of comparative example 1 was produced in the same manner as in example 1, except that the deodorant masterbatch (E) was not blended.
< evaluation of various kinds >
The films obtained in each example were evaluated as follows. The results are shown in table 1.
[ haze measurement after high temperature boiling ]
The first outer layers of the multilayer films obtained in each example were heat-sealed with each other under a sealing pressure of 0.2MPa, a sealing time of 1 second, a sealing width of 5mm, and a sealing temperature of 200 ℃ using a heat sealer manufactured by Tester industrial co. Thereafter, the package was filled with water, and subjected to a high-temperature steaming treatment at 135℃for 40 minutes. The film subjected to the retort treatment was evaluated by using a spectroscopic color/haze tester (model COH 7700) manufactured by japan electric color industry co.
[ Hydrogen sulfide reduction Rate ]
Using a urethane adhesive, a biaxially stretched polyester film (PET) having a thickness of 12 μm, an Al foil having a thickness of 7 μm, a biaxially stretched polyamide film (ONy) having a thickness of 15 μm, and the multilayer films obtained in each example were bonded by a usual dry lamination method to form a laminate having the following constitution.
The laminate is formed by: PET/adhesive/Al foil/adhesive/ONy/adhesive/multilayer film.
The multilayer films (first outer layer) of the laminate were heat-sealed with each other under a sealing pressure of 0.2MPa, a sealing time of 1 second, a sealing width of 5mm, and a sealing temperature of 200 ℃ by using a heat sealer manufactured by Tester industrial co. Thereafter, the package was filled with an aqueous solution of cysteine containing 0.03 mass% of L-cysteine, and subjected to a high-temperature steaming treatment at 135℃for 40 minutes. After the high-temperature steaming treatment, the solution in the package was collected, and the hydrogen sulfide reduction rate was measured using PACKTEST (model WAK-S) manufactured by Co-ordination physical and chemical research, inc. The hydrogen sulfide reduction rate was calculated from the reduction rate of absorbance measured using the multilayer film obtained in each example relative to absorbance measured using the multilayer film without the deodorant (comparative example 1) by measuring absorbance at 668nm by a spectrophotometer after the collected solution was reacted with the PACKTEST reagent.
TABLE 1
* The amount of the deodorant masterbatch is 100 parts by mass based on the component (C) and the component (D).
Industrial applicability
The polypropylene-based multilayer film of the present disclosure can be preferably used in a sealant film for retort packaging having excellent deodorizing effect against sulfur odor generated from retort foods while having excellent high transparency required for viewing contents.
Symbol description
10 multilayer films, 100 packaging materials, 1a first outer layer, 1b second outer layer, 2 inner layers, 3 bonding layers, 4 base material films, 5 bonding layers and 6 transparent vapor deposition films.

Claims (9)

1. A multilayer film is provided with:
a first outer layer as a heat-sealing layer containing a propylene homopolymer (A) and a propylene-ethylene random copolymer (B);
an inner layer containing a propylene-ethylene block copolymer (C) and an ethylene-propylene copolymer elastomer (D); and
a second outer layer comprising a propylene homopolymer (A) and a propylene-ethylene random copolymer (B),
wherein at least any one of the first outer layer, the inner layer, and the second outer layer further contains a polyphenol compound.
2. The multilayer film according to claim 1, wherein the content of the polyphenol compound is 1.5 to 8.0 mass% based on the total amount of the multilayer film.
3. The multilayer film according to claim 1 or 2, wherein the inner layer contains 90 to 50 parts by mass of the propylene-ethylene block copolymer (C) and 10 to 50 parts by mass of the ethylene-propylene copolymer elastomer (D), and further contains the polyphenol compound.
4. The multilayer film according to claim 1 or 2, wherein the first and second outer layers contain 70 to 30 parts by mass of the propylene homopolymer (a) and 30 to 70 parts by mass of the propylene-ethylene random copolymer (B), and further contain the polyphenol compound.
5. The multilayer film of any one of claims 1-4, wherein the polyphenolic compound is a condensed tannin.
6. The multilayer film of any one of claims 1-5, wherein the total thickness of the first and second outer layers is 25-42% based on the thickness of the multilayer film.
7. The multilayer film according to any one of claims 1 to 6, wherein the thickness of the inner layer is 30 μm or more.
8. A packaging material comprising the multilayer film according to any one of claims 1 to 7 and a base material.
9. A package formed by bagging the packaging material of claim 8.
CN202280027824.0A 2021-05-31 2022-05-10 Multilayer film, packaging material, and package Pending CN117120262A (en)

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JPH0623925A (en) * 1992-07-06 1994-02-01 Mitsubishi Kasei Corp Packaging film
JP4904526B2 (en) * 2006-09-07 2012-03-28 東レペフ加工品株式会社 Polyolefin-based resin laminate foam having deodorizing function, and cylindrical body or molded body comprising the same
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