KR101749854B1 - Easily openable laminated film and use therefor - Google Patents
Easily openable laminated film and use therefor Download PDFInfo
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- KR101749854B1 KR101749854B1 KR1020157030244A KR20157030244A KR101749854B1 KR 101749854 B1 KR101749854 B1 KR 101749854B1 KR 1020157030244 A KR1020157030244 A KR 1020157030244A KR 20157030244 A KR20157030244 A KR 20157030244A KR 101749854 B1 KR101749854 B1 KR 101749854B1
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- based polymer
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- propylene
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Abstract
Based polymer composition (E) comprising the propylene-based polymer (A-1), the ethylene-based polymer (B-1), the ethylene /? - olefin random copolymer (C-1) and the tackifier resin (D- (B) and an ethylene-based polymer (B-4) composed of an ethylene-based polymer composition (F) composed of a heat-sealable layer, an ethylene-based polymer (B-2) and a high- Layer laminated film comprising the above-mentioned laminate film. The easy-to-open laminating laminated film is excellent in sealing property, that is, even when the package is placed at a temperature higher than the room temperature, the pressure-sensitive adhesive layer is also excellent in pressure (external pressure) It has a sealing strength that can withstand.
Description
The present invention relates to an easy - to - open resin laminated film exhibiting excellent sealing properties and easy - to - open properties for various materials, improved sealing properties, and use thereof.
Packaged snack foods such as mackerel and potato chips, or food packaging such as jelly, milk, yogurt, pudding, tofu and miso drinks, blister packaging, other medicines, medical instruments, daily necessities, , A bottle, and a plastic container in the form of a cup or a tray are sealed with a cap member made of a plastic laminate film or an aluminum foil laminate film. What is required for such packaging is mechanical strength to withstand a distribution route, seal strength that can maintain sanitary property, and good openability at the time of use.
As one of the materials used for such packaging, a film of a category called easy peelability (easy peeling property, easy peeling property) film is used as a package which is used in a bag made of a heat fusing layer as the innermost layer, Sieve is widely used. However, the various heat-sealable layers proposed so far have high heat seal strength for sealing, but they are not always sufficient for easy peeling at the time of opening, and it is required to take an appropriate balance between them.
Examples of such a film having easy releasability (easy peeling property) include a readily peelable package comprising an easy peeling layer composed of a mixture layer of a polypropylene resin and a polyethylene resin and a high-density polyethylene resin layer (see Patent Document 1), poly A capant sealant film of a polypropylene container composed of an adhesive layer (easy peeling layer) made of a mixed resin of propylene and polyethylene and a support layer (laminate layer) (see Patent Document 2), an ethylene-alpha-olefin copolymer, (Refer to Patent Document 3), a polypropylene resin, an ethylene /? - olefin random copolymer resin having a density of 930 kg / m 3 or less, and a sealant made of a polyethylene resin composition (See Patent Document 4), and the like. However, a film in which a layer of a mixture of a polypropylene resin and a polyethylene resin is simply formed as a heat-sealable layer is not necessarily satisfactory in terms of the balance of sealing property, easy openability, heat resistance, and oil resistance.
As a method for improving such a problem, there has been proposed an easy-to-open laminate film using a heat-sealable layer composed of a polyolefin composition in which an ethylene /? - olefin random copolymer and a tackifier are added to a propylene polymer and an ethylene polymer (See Patent Document 5).
The easy-to-open laminated film described in Patent Document 5 exhibits excellent sealing properties and easy opening properties, but it is found that the performance is insufficient in an area where sealing property is more demanded.
It is an object of the present invention to provide a packaging material which can withstand sealing pressure (external pressure) or pressure (internal pressure) from the inside even when the package is placed at a temperature higher than room temperature while maintaining excellent sealing property and easy opening property To obtain an easy-to-open laminate film having a sealing strength.
The present invention relates to an easy-to-open laminate film and its use. Among them, the easily releasable laminated film is composed of a heat-sealable layer, an intermediate layer and a laminate layer.
The heat-
79.8 to 94% by mass of the propylene-based polymer (A-1)
Having a density of 900 kg / m 3 or more
4 to 10% by mass of the ethylene-based polymer (B-1)
Density greater than 860 kg / m 3
Less than 900 kg / m 3
1.5 to 7.5% by mass of the ethylene /? - olefin random copolymer (C-1)
And
0.5 to 2.7% by mass of the tackifier resin (D-1)
Based polymer composition (E) consisting of an olefinic polymer composition (A-1) + (B-1) + (C-1) + (D-1) = 100 mass%.
In addition,
Having a density in the range of 940 to 970 kg / m 3
50 to 95% by mass of the ethylene-based polymer (B-2)
And
Having a density in the range of 905 to 935 kg / m 3
5 to 50 mass% of high-pressure processed low-density polyethylene (B-3)
Based polymer composition (F) composed of the ethylene-based polymer composition (B-2) + (B-3) = 100 mass%.
The laminate layer is composed of an ethylene polymer (B-4) having a density of 900 to 950 kg / m 3 , preferably 910 to 940 kg / m 3 , and more preferably 920 to 940 kg / m 3 .
The easy-to-open laminate film of the present invention is excellent in heat-seal strength (peel strength) in a wide temperature range when the laminate film is thermally fused with the propylene-based polymer layer, (External pressure) or pressure (internal pressure) from the inside, and can be easily peeled off at the time of peeling (opening), and further, there is no thread-like slack in the peeling surface and a soft feeling.
≪ Propylene-based polymer (A-1) >
The propylene-based polymer (A-1), which is one of the constituent components of the olefinic polymer composition (E) to be the heat-sealable layer of the easily openable laminated film of the present invention, And is usually a homopolymer of propylene having a density of about 890 to 930 kg / m 3 or a copolymer composed of propylene copolymer, that is, propylene and at least one comonomer selected from other small amounts of -olefins. In the copolymer, either a random copolymer or a block copolymer may be used. Examples of other? -Olefins in the definition of the copolymer of propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, And? -Olefins having about 4 to 20 carbon atoms. These other? -Olefins may be copolymerized singly or in combination of two or more? -Olefins.
Among these propylene-based polymers (A-1), a melting point based on a differential scanning calorimeter (DSC) is in the range of 110 to 145 占 폚, particularly 115 to 140 占 폚, in view of a balance between the heat- Propylene /? - olefin random copolymer is preferable.
The propylene-based polymer (A-1) according to the present invention is obtained by mixing the ethylene polymer (B-1), the ethylene /? - olefin random copolymer (C-1) and the tackifier resin (D- The melt flow rate (MFR) (ASTM D1238, 230 캜, 2160 g load) is not particularly limited as long as the olefinic polymer composition (E) having the film forming ability has a melt flow rate of 0.01 to 100 g / 10 min , Preferably 0.1 to 70 g / 10 min.
As the propylene polymer (A-1) according to the present invention, two or more propylene polymers may be used in combination.
The propylene-based polymer (A-1) according to the present invention can be produced by various well-known production methods, specifically, for example, a catalyst for olefin polymerization such as a Ziegler-Natta catalyst or a single site catalyst. In particular, it can be produced by using a single site catalyst. The single site catalyst is a catalyst in which the active sites are homogeneous (single site), for example, a metallocene catalyst (so-called Kminsky catalyst) or a Brookhart catalyst. The metallocene catalyst is a catalyst comprising at least one compound selected from the group consisting of a metallocene transition metal compound, an organoaluminum compound and a compound which reacts with the metallocene transition metal compound to form an ion pair, It may be carried on inorganic material.
≪ Ethylene polymer (B-1) >
The ethylene polymer (B-1) which is one of the constituent components of the olefinic polymer composition (E) to be the heat-sealable layer of the easily openable laminated film of the present invention has a density of 900 kg / m 3 or more, 970kg / m 3, more preferably an α- olefin, homopolymers or ethylene and a small amount of 3 to 10 carbon atoms of the ethylene in the range of 930~970kg / m 3, such as propylene, 1-butene, 1-heptene, (HP-LDPE), linear or linear low density polyethylene (L-LDPE), medium density polyethylene (1-hexene), 1-hexene, 1-octene and 4-methyl- MDPE), a homopolymer of ethylene or an ethylene /? - olefin copolymer which is called high density polyethylene (HDPE).
The ethylene polymer (B-1) according to the present invention may be a single polymer or a composition (mixture) of two or more ethylene polymers.
The melt flow rate (MFR) (ASTM D1238, 190 占 폚, 2160 g load) of the ethylene polymer (B-1) Is not particularly limited as long as it is capable of forming a film when it is mixed with the olefinic polymer composition (C-1) and the tackifier resin (D-1) to form the olefinic polymer composition (E), but is usually 0.01 to 100 g / 0.1 to 70 g / 10 min.
≪ Ethylene /? - olefin random copolymer (C-1)
Facilitate an ethylene · α- olefin random copolymer (C-1) one of the components of the olefin polymer composition (E) is a heat-sealable layer of the tear laminated film of the present invention, a density of 860kg / m 3 or more to 900kg / m 3, preferably less than 860kg / m 3 or more ~895kg / m 3 under ethylene and α- olefin of 3 to 10 carbon atoms, such as propylene, 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like.
The ethylene /? - olefin random copolymer (C-1) preferably has a density of 860 to 895 kg / m 3 and the? -Olefin is at least one ethylene /? - olefin having 4 to 10 carbon atoms the random copolymer (C1-1), and the density is composed of an ethylene-propylene random copolymer (C1-2) in the range of 865~875kg / m 3.
Preferably, 10 to 90 parts by mass of the ethylene /? - olefin random copolymer (C1-1), in particular 30 to 90 parts by mass, and 90 to 10 parts by mass of the ethylene / propylene random copolymer (C1-2) , And in particular 70 to 10 parts by mass (provided that (C1-1) + (C1-2) = 100 parts by mass).
On the other hand, the ethylene /? - olefin random copolymer (C1-1) is preferably a polymer having at least one of the following physical properties (c-1a) to (c-1c).
(c1-1a) the ethylene content is 85 to 93 mol%
(c1-1b) X-ray crystallinity is 7 to 30%
(c1-1c) A melting point determined from an endothermic curve at a heating rate of 10 占 폚 / min by a differential scanning calorimeter (DSC) is in a range of 60 to 90 占 폚
As the ethylene /? - olefin random copolymer (C1-1), an ethylene /? - olefin random copolymer (C1-1) having physical properties of (c1-1a), (c1-1b) ) And having physical properties of (c1-1a) and (c1-1b), properties of (c1-1a) and (c1-1c) or properties of (c1-1b) ? -olefin random copolymer (C1-1), and the ethylene /? - olefin random copolymer (C1-1) having the properties of (c1-1a), (c1-1b) have.
The ethylene / propylene random copolymer (C1-2) is preferably a polymer having at least one of the following physical properties (c1-2a) and (c1-2b).
(c1-2a) the ethylene content is 75 to 85 mol%
(c1-2b) Crystallinity by X-ray is amorphous or slightly crystallized in the range of less than 5%
As such an ethylene / propylene random copolymer (C1-2), there is an ethylene / propylene random copolymer (C1-2) having physical properties of (c1-2a) or (c1-2b) And an ethylene-propylene random copolymer (C1-2) having physical properties of (c1-2b).
Of these, the ethylene /? - olefin random copolymer (C-1) has an ethylene content of 85 to 93 mol% and an X-ray crystallinity of 7 to 10 mol% (C1-1) having a melting point in a range of 60 to 90 占 폚, which is determined from an endothermic curve at a temperature rise rate of 10 占 폚 / min by a differential scanning calorimeter (DSC) at 10 占 폚 / And a composition (mixture) comprising an ethylene / propylene random copolymer (C1-2) having an amorphous or slightly crystalline structure with an ethylene content of 75 to 85 mol% and a crystallinity by X-ray of less than 5% Is suitable.
Examples of the ethylene /? - olefin random copolymer (C-1) according to the present invention include the propylene polymer (A-1), the ethylene polymer (B-1) and the tackifier resin The melt flow rate (MFR) (ASTM D1238, 190 캜, 2160 g load) is not particularly limited so far as the olefinic polymer composition (E) It is preferable that the melt flow rate (MFR) (ASTM D1238, 190 캜, 2160 g load) is in the range of preferably 0.01 to 20 g / 10 min, more preferably 0.1 to 10 g / 10 min.
The ethylene /? - olefin random copolymer (C-1) according to the present invention can be obtained by copolymerizing ethylene and? -Olefin random copolymer (C-1) using a catalyst comprising a transition metal compound catalyst component such as a vanadium compound or zirconium compound and an organoaluminum compound catalyst component. Olefin copolymer.
≪ Adhesion-imparting resin (D-1) >
The tackifier resin (D-1) which is one of constituent components of the olefinic polymer composition (E) to be the heat-sealable layer of the easily openable laminated film of the present invention is a known resin which is manufactured and sold as a tackifier Specific examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosins, styrene resins, and coumarone / indene resins.
Examples of the aliphatic hydrocarbon resin include an oil fraction containing at least one of mono or di-olefins having 4 to 5 carbon atoms such as 1-butene, isobutene, butadiene, 1,3-pentadiene, and isoprene ). ≪ / RTI >
Examples of the alicyclic hydrocarbon resin include resin obtained by cyclization dimerization of the diene component in Spent C4 to C5 oil, resin obtained by polymerizing cyclic monomers such as cyclopentadiene, aromatic hydrocarbon resin, And a resin.
Examples of the aromatic hydrocarbon resin include a resin obtained by polymerizing an oil containing at least one C8-C10 vinyl aromatic hydrocarbon such as vinyltoluene, indene and? -Methylstyrene, or a resin obtained by polymerizing these aliphatic alcohols and the aliphatic hydrocarbon oil And resins obtained by copolymerization.
Examples of polyterpene resins include? -Pinene polymers,? -Pinene polymers, dipentene polymers, terpene-phenol copolymers,? -Pinene-phenol copolymers, and hydrogenated products thereof.
Examples of the rosins include rosins such as gum rosin, wood rosin and tall oil, and modified products thereof. Examples of the modified products include those modified by hydrogenation, disproportionation, dimerization, and esterification.
Examples of the styrene-based hydrocarbon resin include dendritic polymers having a low molecular weight obtained by polymerizing one or more styrene monomers such as styrene, vinyltoluene, α-methylstyrene and isopropyltoluene having high purity.
When the olefinic polymer composition (E) according to the present invention is used as an easy-to-open sealing material for food and beverage packaging, considering the odorlessness, food hygiene and compatibility with other components, It is preferable to use a hydrogenated resin or a polyterp resin.
≪ Ethylene polymer (B-2) >
The ethylene polymer (B-2) which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easily openable laminated film of the present invention has a density of 940 to 970 kg / m 3 , preferably 945 to 967 kg / m < 3 & gt ;, or a homopolymer of ethylene and a small amount of alpha-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-heptene, 1-hexene, 1-pentene and the like, and is a polymer mainly composed of ethylene which is produced and sold as high-density polyethylene (HDPE).
The melt flow rate (MFR) (ASTM D1238, 190 占 폚, 2160 g load) of the ethylene polymer (B-2) according to the present invention is an ethylene polymer composition F) is not particularly limited as long as it has film-forming ability, it is usually in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
<High Pressure Low Density Polyethylene (B-3)>
The high-pressure-treated low-density polyethylene (B-3) which is one of the components of the ethylene polymer composition (F) constituting the intermediate layer of the easily openable laminated film of the present invention has a density of 905 to 935 kg / m 3 , 925 kg / m < 3 & gt ;.
Here, the high-pressure processed low density polyethylene (B-3) is a homopolymer of ethylene which is usually produced and sold as high-pressure processed low density polyethylene (HP-LDPE), or a copolymer of ethylene and a small amount of vinyl acetate.
The melt flow rate (MFR) (ASTM D1238, 190 캜, 2160 g load) of the high-pressure processed low density polyethylene (B-3) according to the present invention was measured by using an ethylene polymer composition (F ) Is not particularly limited as long as it has film-forming ability, it is usually in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min.
≪ Ethylene polymer (B-4) >
Facilitate the ethylene polymer (B-4) constituting the laminate layer of the laminated release film of the present invention, a density of the ethylene with a carbon number in the range of 900~950kg / m 3, preferably 920~940kg / m 3 1-hexene, 1-octene, 4-methyl-1-pentene and the like, and is usually a linear copolymer of linear or linear low density polyethylene (L- LDPE). ≪ / RTI >
As the ethylene polymer (B-4) according to the present invention, a random copolymer of ethylene and? -Olefin having 4 or more carbon atoms is preferable.
The melt flow rate (MFR) (ASTM D1238, 190 캜, 2160 g load) of the ethylene polymer (B-4) according to the present invention is not particularly limited as long as it has film forming ability, but is usually 0.01 to 100 g / Is in the range of 0.1 to 70 g / 10 min.
In the laminate layer, a polymer including an ethylene polymer other than the ethylene polymer (B-4) may be used in combination with the ethylene polymer (B-4). In this case, the other polymer is generally a polymer constituting the laminate layer By mass, more preferably not more than 30% by mass, and most preferably not more than 10% by mass.
The ethylene polymer (B-4) according to the present invention can be blended with various additives within the range not impairing the object of the present invention.
Examples of such additives include inorganic fillers such as silica and talc, antioxidants, weathering stabilizers, antistatic agents, anti-fogging agents, anti-blocking agents, slip agents and pigments. In addition, blending of an organic compound-type anti-blocking agent and slip agent is also effective for improvement of workability and workability at the time of film forming, laminating, packaging and the like.
As such organic compound-type anti-blocking agents and slip agents, there may be mentioned, for example, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmitamide, stearyl palmitamide, Various amides such as amide, methylenebisoleylamide, ethylenebisoleylamide and ethylenebisperic acid amide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, hydrogenated castor oil and the like.
≪ Olefinic polymer composition (E) >
The olefinic polymer composition (E) for forming the heat-sealable layer of the easy-to-open laminate film of the present invention,
79.8 to 94% by mass of the propylene-based polymer (A-1)
Preferably from 81.1 to 91.3% by mass,
4 to 10% by mass of the ethylene-based polymer (B-1)
Preferably from 5.5 to 9% by mass,
The ethylene /? - olefin
1.5 to 7.5% by mass of the random copolymer (C-1)
Preferably 2.5 to 7.5% by mass,
And
0.5 to 2.7% by mass of the tackifier resin (D-1)
Preferably 0.7 to 2.4 mass%
(A-1) + (B-1) + (C-1) + (D-1) = 100% by mass.
The propylene polymer (A-1), the ethylene polymer (B-1), the ethylene /? - olefin random copolymer (C-1) and the tackifier resin D-1) satisfies the above-mentioned range, the resulting easy-to-open laminate film has excellent balance between ease of opening and sealing strength.
The olefinic polymer composition (E) according to the present invention may contain various additives in such a range as not to impair the object of the present invention.
Examples of such additives include inorganic fillers such as silica and talc, antioxidants, weather stabilizers, antistatic agents, anti-fogging agents, anti-blocking agents, slip agents and pigments. In addition, blending of an organic compound-type anti-blocking agent and slip agent is also effective for improvement of workability and workability at the time of film forming, laminating, packaging and the like.
As such organic compound-type anti-blocking agents and slip agents, there may be mentioned, for example, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmitamide, stearyl palmitamide, Various amides such as amide, methylenebisoleylamide, ethylenebisoleylamide and ethylenebisperic acid amide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, hydrogenated castor oil and the like.
The olefinic polymer composition (E) according to the present invention is obtained by copolymerizing the propylene polymer (A-1), the ethylene polymer (B-1), the ethylene /? - olefin random copolymer (C- -1), and optional additives to be blended, either simultaneously or sequentially.
The heat-sealable layer contains the components (A-1) and (B-1) of the propylene polymer (A-1), the ethylene polymer (B-1), the ethylene /? - olefin random copolymer And other polymers other than these may be used in combination. In this case, the other polymer is generally less than 50% by mass of the polymer component constituting the heat-sealable layer, more preferably 30% Or less, more preferably 10 mass% or less.
In preparing the resin composition, it is preferable to melt-mix using a single-screw extruder, a twin-screw extruder, a Banbury mixer, various kneaders, etc., and there is no particular limitation on the mixing order.
≪ Ethylene-based polymer composition (F) >
The ethylene-based polymer composition (F) forming the intermediate layer of the easily openable laminated film of the present invention,
The ethylene-based polymer (B-2) is contained in an amount of 50 to 95%
Preferably 70 to 92 mass%
And
5 to 50% by mass of the high-pressure processed low-density polyethylene (B-3)
Preferably 8 to 30 mass%
(B-2) + (B-3) = 100% by mass.
When a composition having an ethylene polymer (B-2) content of less than 50% by mass is used as an intermediate layer, the filmability of the easily-openable laminate film to be obtained may be deteriorated or the film strength, heat resistance, (B-2) in an amount of more than 95% by mass is used as an intermediate layer, the sealing strength of the obtained easily openable laminated film becomes strong and the open performance such as complete sealing becomes poor There is a concern.
In the intermediate layer, a polymer including an ethylene polymer other than the ethylene polymer (B-2) and the high-pressure processed low density polyethylene (B-3) may be used in combination. In this case, Of the polymer component constituting the intermediate layer is less than 50 mass%, particularly 30 mass% or less, more preferably 10 mass% or less.
The ethylene polymer composition (F) constituting the intermediate layer according to the present invention may be compounded with various additives within the range not impairing the object of the present invention.
Such additives may include inorganic fillers such as silica and talc, antioxidants, weather stabilizers, antistatic agents, anti-fogging agents, anti-blocking agents, slip agents, pigments and the like. In addition, blending of an organic compound-type anti-blocking agent and slip agent is also effective for improvement of workability and workability at the time of film forming, laminating, packaging and the like.
As such organic compound-type anti-blocking agents and slip agents, there may be mentioned, for example, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, oleyl palmitamide, stearyl palmitamide, Various amides such as amide, methylenebisoleylamide, ethylenebisoleylamide and ethylenebisperic acid amide, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, hydrogenated castor oil and the like.
≪ Easy Openable Laminated Film &
The easy-to-open laminating film of the present invention is characterized in that the heat-sealable layer composed of the olefinic polymer composition (E), the intermediate layer composed of the ethylene polymer composition (F) and the ethylene polymer (B-4) Laminate layer.
The intermediate layer constituting the easily openable laminated film of the present invention may be one layer or two or more layers as long as it is composed of the ethylene-based polymer composition (F).
The thickness of the easily openable laminated film of the present invention may be varied depending on the application. In the case of a three-layer structure, the thickness of the heat-sealable layer is usually 1 to 80 m, preferably 2 to 50 m, And the thickness of the laminate layer is in the range of 1 to 80 m, preferably 2 to 50 m, the thickness of the entire easy-to-open laminate film is 10 to 500 m, preferably 20 to 100 m Range.
The easy-to-open laminate film of the present invention can be produced by subjecting the surface of the laminate layer to surface activation treatment such as corona treatment, flame treatment, plasma treatment, undercoating treatment or the like in order to improve the printability or adhesion with the base layer You can leave it.
The term "substrate layer"
The easily openable laminated film of the present invention can be laminated with a substrate layer and used for various purposes. The substrate layer to be laminated with the laminate layer of the easily openable laminated film of the present invention is composed of a sheet or film made of thermoplastic resin, paper, aluminum foil or the like.
Examples of the thermoplastic resin include various known thermoplastic resins such as polyolefins (polyethylene, polypropylene, poly 4-methyl-1-pentene, polybutene and the like), polyesters (polyethylene terephthalate, polytrimethylene terephthalate, (Nylon-6, nylon-66, polymethylaylene adipamide and the like), polyvinyl chloride, polyimide, ethylene-vinyl acetate copolymer or a saponification product thereof, poly (ethylene terephthalate, polyethylene naphthalate and the like) Vinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. Among these, thermoplastic resins having good stretchability and transparency such as polypropylene, polyethylene terephthalate and polyamide are preferable. The substrate made of such a thermoplastic resin film may be a non-oriented film, a stretched film, or a laminate of one or more kinds of pneumatic exhibits, extruded laminated products, dry laminated products and the like.
In order to improve the adhesiveness of the easily-openable laminated film of the present invention to the laminate layer, the surface or both surfaces of the substrate layer is subjected to surface activation treatment such as corona treatment, flame treatment, plasma treatment, undercoating treatment and the like You can leave it. The thickness of the base layer is usually in the range of 5 to 1000 m, preferably 9 to 100 m.
≪ Method for producing easily-openable laminated film >
Various known film forming methods may be employed in the production of the easily openable laminated film of the present invention. At this time, the olefinic polymer composition (E) having the above-mentioned composition constituting the heat-sealable layer may be prepared in advance before the laminated film molding, and the propylene polymer (A-1), the ethylene polymer a predetermined amount of the? -olefin random copolymer (C-1) and the tackifier resin (D-1) may be metered into the film-forming machine directly. The ethylene polymer (B) and the high-pressure low-density polyethylene (B-3) may be preliminarily prepared in the same manner for the intermediate layer, and the ethylene polymer You can. These laminated films may be separately bonded and then joined together, but a method by co-extrusion molding using a multilayer die of at least a three-layer structure is most preferable.
<Container cap>
The easy-to-open laminate film of the present invention or the easy-to-open laminate film laminated with the base layer can be used as various packaging materials. As an example of a suitable packaging material, there is a container cap material using the heat-sealable layer as the innermost layer of the container. When used as a container cap material, the easy-to-open laminate film may be used as a cap material, or may be printed and used. It may also be formed as a cap material by bonding with printed or non-printed paper, aluminum foil or the like. In addition, depending on the use, a cap material may be cut according to the shape of the container in advance. In the case of using a container cap material, it is preferable to use a heat-sealable laminated film provided with a base layer.
<Adherend>
The easy-to-open laminate film of the present invention can form a single layer at the time of heat-setting by thermally fusing it to various adherends. Examples of such an adherend include a propylene-based polymer, polystyrene, polyester, polycarbonate, polyvinyl chloride and the like. These adherends may be of various shapes such as films, sheets, trays, cups, bottles, and the like. Among these, it is preferable that the propylene-based polymer is an adherend, because it has excellent sealability in one layer at the time of heat, easy openability, heat resistance, oil resistance and the like. These propylene-based polymers are of the same category as propylene-based polymer (A-1), but may have the same or different physical properties. For example, in an adherend made of a propylene-based polymer, a propylene-based polymer molded into various shapes such as a film, a sheet, a tray, a cup and a bottle may be used in accordance with the material to be packed. In the case of a film or sheet, it can be produced by the same method as the easy-to-open laminate film. In the case of a tray or a cup, the sheet can be manufactured by once forming the sheet by the above-mentioned method, and then forming the container such as a tray or a cup by thermoforming such as vacuum forming or pressure forming. In the case of a cup or bottle, it can be molded as a container by injection molding, injection blow molding (injection blow), blow molding or the like.
<Package>
When the easy-to-open laminated film of the present invention is used as a packaging material, the easy-to-open laminated film itself may be folded into three folds or two packed easily-openable laminated films may be wrapped, The easy-to-open laminating film may be formed with one layer at the time of forming the package with various adherends. The shape of the package of the present invention may take various shapes depending on the shape, shape, or use of the material to be packaged. For example, as a flexible flexible packaging material, a three-side bag made of a film having a ten-layer structure including an easy-to-open laminate film and a propylene-based polymer layer is filled with a material to be packed, (Sealing material) comprising a thermally fusible layer of an easy-to-open laminate film as a innermost layer after filling a material to be packed in a sheet, tray, cup, bottle, And a package made by sealing the upper surface.
According to the present invention, the following method of producing a package can be provided.
That is, as one example of the production method, the content is contained in a plastic container having a ten-layer structure composed of a propylene-based polymer layer, and then the easily peelable laminated film of the present invention is used as a cap material, and the olefinic polymer composition (E) There can be exemplified a method of thermally fusing one layer of the plastic container as a face facing the thermally fusible layer to be formed at a temperature of 160 ° C to 210 ° C, preferably 170 ° C to 200 ° C.
Example
EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples unless they depart from the spirit thereof.
The polymers used in Examples and Comparative Examples are shown below.
(1) Propylene-based polymer (A-1)
(1-1) Propylene / ethylene random copolymer (R-PP-1):
density; 910 kg / m 3 ,
Melt flow rate (MFR) (230 占 폚); 9 g / 10 min,
Melting point; 115 ° C.
(1-2) Propylene / ethylene / 1-butene random copolymer (R-PP-2):
Ethylene content; 3.6 mol% (2.4 wt%),
1-butene content; 1.9 mol% (2.5 wt%),
density; 910 kg / m 3 ,
Melt flow rate (MFR) (230 占 폚); 7.2 g / 10 min,
Melting point; 143 ° C.
(2) Ethylene-based polymer (B-1)
High density polyethylene (HDPE-1):
density; 954 kg / m 3 ,
MFR (190 占 폚); 1.1 g / 10 min,
Melting point; 132 ° C.
(3) Ethylene /? - olefin random copolymer (C-1)
(3-1) Ethylene / 1-butene random copolymer (EBR):
Ethylene content; 89.1 mol%
Crystallinity; 10%,
density; 886 kg / m 3 ,
MFR (190 占 폚); 4.0 g / 10 min.
(3-2) Ethylene-Propylene Copolymer (EPR):
Ethylene content; 82.6 mol%
density; 870 kg / m 3 ,
MFR (190 占 폚); 2.9 g / 10 min.
(4) Adhesion-imparting resin (D-1)
Hydrogenated aromatic hydrocarbon resin (ARCON) (ARAKAWA CHEMICAL CO., LTD., Trade name: ARCON P115, ring method softening point 115 캜)
(5) Ethylene-based polymer (B-2)
High density polyethylene (HDPE-2):
density; 954 kg / m 3 ,
MFR (190 占 폚); 1.1 g / 10 min,
Melting point; 132 ° C.
(6) High-pressure method low-density polyethylene (B-3)
High Pressure Low Density Polyethylene (HP-LDPE):
density; 917 kg / m 3 ,
MFR; 7.2 g / 10 min.
(7) The ethylene polymer (B-4)
Linear or linear low density polyethylene (L-LDPE)
Ethylene 4-methyl-1-pentene random copolymer (which belongs to L-LDPE):
density; 935 kg / m 3 ,
MFR; 2.3 g / 10 min,
Melting point; 124 ° C.
The properties of the heat-sealable laminated films obtained in Examples and Comparative Examples of the present invention were measured by the following methods.
(1) Evaluation of ease of peeling
In order to evaluate the ease of peelability, a biaxially oriented polyethylene terephthalate film (PET) having a thickness of 12 탆 was laminated by dry lamination using a urethane-based adhesive on the surface of the film obtained in each of the examples and comparative examples subjected to corona treatment A laminated film was prepared, and a polypropylene sheet having a thickness of 300 mu m was prepared as one layer at the time of heat treatment.
Next, the thermally fusible layer of each laminated film and the polypropylene sheet were overlapped and sealed at a predetermined temperature shown in Table 1 for 1 second at a pressure of 0.2 MPa using a seal bar having a width of 5 mm and then allowed to cool. Thereafter, the heat-sealed test pieces were treated at 115 ° C for 30 minutes using a high-temperature high-pressure sterilizing apparatus (retort processing apparatus), and then the test pieces were cooled. A test piece with a width of 15 mm was cut therefrom, and the heat-sealed portion was peeled off at a crosshead speed of 500 mm / min. The strength was defined as a heat seal strength (N / 15 mm).
Evaluation of easiness peelability was evaluated as ○, in which the heat seal strength did not exceed 15.0 N / 15 mm, and the peeling between the layers with the tendency of cohesive peeling was observed, and the thread was not shed in a thread shape or dirty in a film form. The heat seal strength was evaluated as & cir & that the heat seal strength exceeded 15.0 N / 15 mm even if there was no problem in the peeling state. The heat seal strength was more than 15.0 N / 15 mm and the seal was likely to be completely sealed.
(2) Evaluation of simple sealability (packed product of pulpy jelly filled with convenience)
The sealability was evaluated using a PP-based barrier container (PP / adhesive layer / EVOH / adhesive layer / PP) which was used as a cap material for a laminate product prepared in order to evaluate easy releasability. The content of the commercial flesh jellies was melted by heating at 60 DEG C and transferred to a container to be measured. The laminate was capped using a cup sealer at a temperature of 185 DEG C, a time of 1.0 second and a pressure of 1,600 N / Heat sealed with cup. Immediately after the heat sealing, the rubber sheet piece with the adhesive tape was stuck on the upper surface of the cap material while the contents were held at about 60 DEG C, the needle was pierced from the sheet surface and the internal pressure was applied at the room temperature, Or the strength at the time of opening by edge cutting was determined as the sealing strength (MPa). This measurement was carried out using a sealing strength meter (according to JIS-Z0238) manufactured by Sun Science Co., Ltd.
In the sealing evaluation,? Indicates that the average value of the strength was 0.045 MPa or more,? Was the average value was less than 0.045 MPa.
(3) Overall evaluation
As a comprehensive evaluation, the peeled state was shown to be a thread-like sagging or film-like peeling, and the heat seal strength did not exceed 15.0 N / 15 mm and the average sealing strength was 0.045 MPa or higher. The peeled state was stretched in the form of a thread, and the heat seal strength, which tends to peel off dirtily in the form of a film or tends to be completely sealed, was stronger than 20 N / 15 mm, The heat seal strength was more than 15.0 N / 15 mm, or the seal strength was 0.045 MPa or less.
[Examples 1 to 5]
(E) prepared by adjusting the amounts of R-PP-1, R-PP-2, HDPE-1, EBR, EPR and arcon as shown in Table 1 as the heat sealable layer and using the HDPE -2 at 85% by mass and the HP-LDPE; LDPE as a laminate layer were separately supplied to the respective extruders, and heat-sealable layers / intermediate layers / laminates were laminated by a T-die method. Laminated film composed of a three-layer coextruded film having a constitution of being a laminated layer was formed, and the laminate layer was subjected to corona treatment to obtain a readily openable laminated film. The total thickness of the easy-to-open laminated film was 50 mu m, and the thickness of each layer was the heat-sealable layer / interlayer / laminate layer = 5.0 / 40.0 / 5.0 mu m.
The physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 1.
[Comparative Examples 1 to 3]
2, HDPE-1, EBR, EPR and ARCON as the heat-sealable layer were adjusted to the blend amounts shown in Table 2. The olefinic polymer composition was prepared by mixing 85% by mass of HDPE- And the HP-LDPE; 15 mass% of the ethylene-based polymer composition obtained by dry blending was fed to an extruder separately using the above-mentioned L-LDPE as a laminate layer, and the thermally fusing layer / intermediate layer / laminate layer Layered coextruded film was formed, and the laminate layer was subjected to corona treatment to obtain a readily openable laminated film. The total thickness of the easy-to-open laminated film was 50 mu m, and the thickness of each layer was the heat-sealable layer / interlayer / laminate layer = 5.0 / 40.0 / 5.0 mu m.
The physical properties of the obtained easily openable laminated film were measured by the method described above. The results are shown in Table 2.
[Comparative Example 4]
1, R-PP-2, HDPE-1, EBR, EPR and ARCON as the heat-sealable layer were adjusted to the blend amounts shown in Table 2, and 100 parts by mass of the HDPE-2 Were used in place of the ethylene-based polymer composition of Comparative Examples 1 to 3, respectively. The results are shown in Table 2.
As shown in Table 1, the easy-to-open laminated films obtained in Examples 1 to 5 had strengths that were easy to open with a heat seal strength of about 10 to 15 N / 15 mm, and they did not sag in a thread- And the sealing strength was high sealing strength even though the contents were at a high temperature of about 60 캜.
On the other hand, as shown in Table 2, in the easily openable laminated film obtained in Comparative Examples 1 to 4, the heat seal strength was as high as 18 to 38 N / 15 mm, which was not suitable as an easy open film, There is a possibility that leakage occurs during transportation.
The easy-to-open laminate film of the present invention can be used as an easy-to-open laminate film having a low-temperature heat sealability, blocking resistance, impact resistance suitable for a packaging material, slipperiness, rigidity, transparency, It is suitable for capsules such as sheets, trays, cups, bottles, etc., and can be used as a packaging for snack foods such as mackerel, potato chips, or food packaging such as jelly, milk, yogurt, pudding, tofu, , Blister packaging, and packaging materials for packaging such as other daily commodities and miscellaneous goods, especially for packaging of fat and preservative foods, and can be suitably used for such purposes. In addition, for example, a container made of polypropylene, such as flesh jelly, pudding, tofu, and other easy-to-open containers, using various openable laminating films, high sealing in the case of a package such as a vertical pillow or a horizontal pillow pouch And is suitable as a packaging material.
Claims (9)
The heat-
79.8 to 94% by mass of the propylene-based polymer (A-1)
Having a density of 900 kg / m 3 or more
4 to 10% by mass of the ethylene-based polymer (B-1)
Density greater than 860 kg / m 3
Less than 900 kg / m 3
1.5 to 7.5% by mass of the ethylene /? - olefin random copolymer (C-1)
And
0.5 to 2.7% by mass of the tackifier resin (D-1)
Based polymer composition (E) comprising at least one olefin polymer composition (A-1) + (B-1) + (C-1) + (D-1) = 100 mass%
In the intermediate layer,
Having a density in the range of 940 to 970 kg / m 3
50 to 95% by mass of the ethylene-based polymer (B-2)
And
Having a density in the range of 905 to 935 kg / m 3
5 to 50 mass% of high-pressure processed low-density polyethylene (B-3)
Based polymer composition (F) composed of an ethylene-based polymer composition (B-2) + (B-3) = 100 mass%
The laminate layer is composed of an ethylene polymer (B-4) having a density in the range of 900 to 950 kg / m < 3 >
Easy - to - open laminated film.
Wherein the propylene-based polymer (A-1) is a propylene /? - olefin random copolymer having a melting point in the range of 110 to 145 占 폚.
Wherein the ethylene-based polymer (B-1) is an ethylene-based polymer having a density of 940 to 970 kg / m 3 .
Wherein the ethylene /? - olefin random copolymer (C-1) is at least one ethylene /? - olefin random copolymer having a density of 880 to 895 kg / m 3 and an? C1-1) and an ethylene / propylene random copolymer (C1-2) having a density in the range of 865 to 875 kg / m < 3 >.
(B-4) constituting the laminate layer is an ethylene /? - olefin random copolymer.
Wherein the thermally fusible layer, the intermediate layer and the laminate layer are obtained by co-extrusion molding.
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| JPJP-P-2013-143813 | 2013-07-09 | ||
| PCT/JP2014/068043 WO2015005279A1 (en) | 2013-07-09 | 2014-07-07 | Easily openable laminated film and use therefor |
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| JP2020163635A (en) * | 2019-03-28 | 2020-10-08 | 大日本印刷株式会社 | Resin film, laminate, lid material and container with lid |
| JP7383900B2 (en) * | 2019-04-05 | 2023-11-21 | 大日本印刷株式会社 | Quiet, easy-to-peel laminate and quiet, easy-to-open lid and container using the same |
| US11692086B2 (en) * | 2019-07-23 | 2023-07-04 | Dic Corporation | Multilayer film, laminated film, and packaging |
| JP7449688B2 (en) | 2019-12-16 | 2024-03-14 | ジェイフィルム株式会社 | Easy-open films and packaging |
| WO2023095618A1 (en) * | 2021-11-24 | 2023-06-01 | 三井化学株式会社 | Laminated film, container, cell culture container, cell culture method and method for manufacturing cell culture container |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004104088A1 (en) | 2003-05-26 | 2004-12-02 | Du Pont-Mitsui Polychemicals Co., Ltd. | Olefin polymer compositions and easy-peelable sealants made by using the same |
| JP2005028679A (en) * | 2003-07-10 | 2005-02-03 | Tohcello Co Ltd | Easily openable laminated film and its use |
| JP2005178216A (en) | 2003-12-19 | 2005-07-07 | Toyobo Co Ltd | Polypropylene multilayered sealant film and laminated film using the same |
| WO2009123286A1 (en) | 2008-04-03 | 2009-10-08 | 東セロ株式会社 | Heat-fusible multilayered film |
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| JPS63179741A (en) * | 1987-01-22 | 1988-07-23 | 昭和電工株式会社 | Composite film simultaneously having easily peelable property and heat sealing property |
| JP5301479B2 (en) * | 2010-02-10 | 2013-09-25 | 三井・デュポンポリケミカル株式会社 | Heat sealable resin composition for liquid crystal polymer, heat seal material for liquid crystal polymer, cover material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004104088A1 (en) | 2003-05-26 | 2004-12-02 | Du Pont-Mitsui Polychemicals Co., Ltd. | Olefin polymer compositions and easy-peelable sealants made by using the same |
| JP2005028679A (en) * | 2003-07-10 | 2005-02-03 | Tohcello Co Ltd | Easily openable laminated film and its use |
| JP2005178216A (en) | 2003-12-19 | 2005-07-07 | Toyobo Co Ltd | Polypropylene multilayered sealant film and laminated film using the same |
| WO2009123286A1 (en) | 2008-04-03 | 2009-10-08 | 東セロ株式会社 | Heat-fusible multilayered film |
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| TW201505837A (en) | 2015-02-16 |
| JP5968543B2 (en) | 2016-08-10 |
| TWI625238B (en) | 2018-06-01 |
| WO2015005279A1 (en) | 2015-01-15 |
| KR20150133802A (en) | 2015-11-30 |
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