CN103895307B - The non-stretched multilayer film of polyolefin - Google Patents
The non-stretched multilayer film of polyolefin Download PDFInfo
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- CN103895307B CN103895307B CN201310747232.9A CN201310747232A CN103895307B CN 103895307 B CN103895307 B CN 103895307B CN 201310747232 A CN201310747232 A CN 201310747232A CN 103895307 B CN103895307 B CN 103895307B
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- based resin
- polypropylene
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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
-
- 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
- B32B15/085—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 polyolefins
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- 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
- 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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- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
The non-stretched multilayer film of polyolefin, it has：Laminate layer, it contains polypropylene-based resin, and the polypropylene-based resin contains that Mw/Mn is polypropylene-based resin that more than 4, MFR is 1~30g/10 minutes and Mw/Mn is propylene ethylene copolymers that 1.5~3.5, MFR is 1~30g/10 minutes；Intermediate layer, it contains polyethylene-based resin, and the polyethylene-based resin contains density for 0.90~0.94g/cm3, the ethylene-alpha-olefin copolymer that MFR is 0.5~20g/10 minutes；Hot sealing layer, it contains polypropylene-based resin, and it is the propylene ethylene copolymers that 1.5~3.5, MFR is 1~30g/10 minutes, fusing point is 125~140 DEG C that the polypropylene-based resin contains Mw/Mn.
Description
Technical field
The present invention relates to the non-stretched multilayer film of polyolefin.In particular it relates to high transparency, high-luster, mapping high
Etc. optical characteristics；Resistance to blocking；Each physical properties excellent such as low temperature heat seal, while heat when being pasted with base material film and being made composite membrane
Sealing strength；The tear Kaifeng property of packaging；Also the excellent non-stretched multilayer film of polyolefin such as the resistance to pinprick in heat-sealing portion.
Background technology
Polyolefin-based resins film is widely utilized as the material for packing various products.For example, packaging for foodstuff purposes；
The packaging applicationss of the sundry goods product such as fiber, dress material；Packaging applicationss of industrial part etc..Especially, polypropylene-based resin film by
In rigidity and excellent heat resistance, the very sense of film is also high therefore high for the adaptability of Bag Making Machine, has been widely used.But, gather
The resistance to pinprick in propylene resin film at least heat sealability (particularly low temperature heat seal), impact resistance and heat-sealing portion is insufficient.Cause
This, having attempted will be by making the Polypropylene copolymer materialization of membrane material, so as to improve heat sealability and impact resistance.But, particularly
For the impact resistance under low temperature, such effect is not obtained.If additionally, to improve heat sealability, producing adhesion
Problem.Therefore, the trial of above-mentioned copolymerization materialization is simultaneously failed.
In this respect, in Unexamined Patent 5-147179, it is proposed that polyolefin multilayer film, wherein by using straight-chain
Ethene-alpha-olefin copolymer (LLDPE) is closed layer by layer as intermediate layer using the intermediate layer and as the polypropylene-based resin of two outer layers
And improve impact resistance.According to the method, optical characteristics (transparency, the light of the raising of confirmation impact resistance, but laminate film really
Pool property, mapping etc.) it is impaired.Additionally, tearing strength when above-mentioned laminate film is pasted with base material film and is made composite membrane becomes
It is very high, therefore tear Kaifeng property when using it as packaging material is significantly damaged.
In JP 2004-276373, it is proposed that polyolefin multilayer film, wherein by with specific polypropylene-based polymerization
Thing closes it with the LLDPE as intermediate layer as two outer layers layer by layer, so as to improve low temperature heat seal and resistance to blocking.Root
According to the technology, the tearing strength of the composite membrane for obtaining is very high, and tear Kaifeng property when using it as packaging material can not expire
Foot.
The resistance to pinprick in so-called above-mentioned heat-sealing portion, is to represent complete in the absence of fine path, sealing in the region of heat-sealing
Full index.If having fine path in heat-sealing portion, the sealing of packaging, therefore particularly being packed in food are damaged
In way, from the viewpoint of freshness holding, long-term preservation from content etc., not preferably.The resistance to pinprick in the heat-sealing portion is and heat
The entirely different concept of sealing strength.In the prior art, for polypropylene-based resin film, heat-sealing portion to be improved almost is not carried out
The trial of resistance to pinprick.
Therefore, the optical characteristics such as high transparency, high-luster, mapping high；Resistance to blocking；Each physical property such as low temperature heat seal
It is excellent, while heat seal strength when being pasted with base material film and being made composite membrane；The tear Kaifeng property of packaging；The resistance to pinprick in heat-sealing portion
Also the excellent non-stretched multilayer films of polyolefin such as property, are so far unknown.
The content of the invention
The present invention in view of above-mentioned actual conditions and complete.
Therefore, it is an object of the invention to provide optical characteristics such as high transparency, high-luster, mappings high；Resist blocking and that
Property；Each physical properties excellent such as low temperature heat seal, while heat seal strength when being pasted with base material film and being made composite membrane；The tear of packaging
Kaifeng property；Also the excellent non-stretched multilayer film of polyolefin such as the resistance to pinprick in heat-sealing portion.
According to the present invention, above object and advantages of the invention are realized by following multilayer films：
The multilayer film is that have as outermost laminate layer, at least 1 layer of intermediate layer and as another outermost
The non-stretched multilayer film of polyolefin of hot sealing layer, it is characterised in that
Above-mentioned laminate layer contains polypropylene-based resin, and the polypropylene-based resin contains the polypropylene-based of 10-50 weight portions
Propylene-ethylene copolymers (A2) (also, above-mentioned polypropylene-based resin (A1) and above-mentioned third of resin (A1) and 50-90 weight portions
Alkene-ethylene copolymer (A2) adds up to 100 weight portions.),
The molecular weight distribution represented by the ratio between weight average molecular weight Mw and number-average molecular weight Mn of the polypropylene-based resin (A1)
Mw/Mn is more than 4, and the melt flow rate (MFR) MFR determined with load 2.16kg at 230 DEG C according to JIS K7210 is 1~30g/
10 minutes, the molecular weight distribution mw/mn of the propylene-ethylene copolymers (A2) was 1.5~3.5, according to JIS K7210 at 230 DEG C
The melt flow rate (MFR) MFR that lower use load 2.16kg is determined is 1~30g/10 minutes, be polymerized using metallocene series catalysts and
Into,
Polyethylene-based resin is contained in above-mentioned intermediate layer, and the polyethylene-based resin contains ethene-α-alkene more than 70 weight %
Hydrocarbon copolymer (B), the density of the ethene-alpha-olefin copolymer (B) is 0.90~0.94g/cm3, according to JIS K7210 190
The melt flow rate (MFR) MFR determined with load 2.16kg at DEG C is 0.5~20g/10 minutes,
Above-mentioned hot sealing layer contains polypropylene-based resin, and the polypropylene-based resin contains propylene-ethylenes more than 70 weight %
Copolymer (C), the molecular weight distribution mw/mn of the propylene-ethylene copolymers (C) is 1.5~3.5, according to JIS K7210 230
The melt flow rate (MFR) MFR determined with load 2.16kg at DEG C is 1~30g/10 minutes, and fusing point is 125~140 DEG C, uses cyclopentadienyl
Metal system polymerization catalyst is formed.
Specific embodiment
The non-stretched multilayer film of polyolefin of the invention has：As outermost laminate layer, at least 1 layer of intermediate layer
With as another outermost hot sealing layer.
<Laminate layer>
Laminate layer in the non-stretched multilayer film of polyolefin of the invention contains polypropylene-based resin, the polypropylene-based tree
Fat contains 10~50 parts by weight of polypropylene systems resin (A1) and 50~90 parts by weight propylene-ethylene copolymer (A2).(also, on
That states polypropylene-based resin (A1) and aforesaid propylene-ethylene copolymer (A2) adds up to 100 weight portions.)
[polypropylene-based resin (A1)]
Above-mentioned polypropylene-based resin (A1), the molecular weight distribution represented with the ratio between weight average molecular weight Mw and number-average molecular weight Mn
Mw/Mn is more than 4.The value of Mw/Mn is preferably 4.5~10, more preferably 5~8.The Mw/Mn of polypropylene-based resin (A1) is smaller than 4
When, the multilayer film that obtains and the tearing strength using its composite membrane for manufacturing excessively are uprised, the tear Kaifeng property in packaging material
Improvement do not manifest.This is considered as resulting from：Mw/Mn was difficult to generation melting and takes than 4 hours during the manufacture of multilayer film
To.On the other hand, melting tension force when multilayer film is manufactured rests on appropriate scope, it is ensured that resistance to viscous when being made multilayer film
Even from the viewpoint of property, Mw/Mn is preferably less than 10.Above-mentioned polypropylene-based resin (A1), its Mw is preferably 450,000~100,000, more
Preferably 400,000~200,000.
Above-mentioned weight average molecular weight Mw and number-average molecular weight Mn are the polystyrene determined using gel permeation chromatography (GPC)
The value (in this specification similarly hereinafter) of conversion.
Above-mentioned polypropylene-based resin (A1), according to the melt flows that JIS K7210 are determined at 230 DEG C with load 2.16kg
Speed MFR is 1~30g/10 minutes.The value is preferably 5~15g/10 minutes.If MFR is smaller than 1g/10 minutes, melt viscosity
It is too low, thus multilayer film manufacture when film-making machine (such as extruder) in excessive pressure raise, sometimes productivity ratio reduction.Enter
And, the bad orders such as membrane thickness unevenness, melt fracture are caused sometimes.On the other hand, if MFR was more than 30g/10 minutes, cause
Become too much in the melt viscosity difference with the resin in intermediate layer, the thickness of outer layer becomes uneven sometimes.In addition, damage sometimes
Evil is made resistance to adhesive during multilayer film.
Above-mentioned polypropylene-based resin (A1), preferably fusing point is 120~150 DEG C, more preferably 130~145 DEG C.In the scope
Temperature in show the polypropylene-based resin (A1) of fusing point, from manufacture multilayer film when heat resistance be made multilayer film and composite membrane
When transparent balancing good in terms of from the point of view of and it is preferred that.Wherein, the fusing point of so-called resin, refers to differential scanning calorimeter
(DSC) summit temperature (Tm) (in this specification similarly hereinafter) of the maximum endothermic peak in figure.
Above-mentioned polypropylene-based resin (A1), can be homopolymers, or propylene and the copolymerization of copolymer composition of propylene
Thing.Used as copolymer composition used herein, optimal ethylene and alpha-olefin specifically, can enumerate such as ethene, 1- butylene, 1- penta
Alkene, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene, 4-methyl-1-pentene etc., can use 1 selected from these
More than kind.The ratio of the copolymer composition in polypropylene-based resin (A1) preferably 10 moles below %, more preferably 5 moles % with
Under, more preferably 3 moles below %.
As the polypropylene-based resin (A1) in the present invention, from the multilayer film and the optical characteristics of composite membrane for ensuring to obtain
Viewpoint is set out, and preferably uses homopolymers, the copolymerization of the copolymer and propylene and ethene and butylene of propylene and ethene from propylene
More than a kind selected in thing.
Above-mentioned polypropylene-based resin (A1), can be the product using the manufacture of any method as long as meeting above-mentioned condition.Energy
Enough use examples Ziegler-Natta catalyst as is well known, is preferably manufactured using appropriate donor compound simultaneously.Can make neat
Ge Le-Natta catalyst is carried on appropriate inorganic substances.
[propylene-ethylene copolymers (A2)]
The molecular weight represented by the ratio between weight average molecular weight Mw and number-average molecular weight Mn of aforesaid propylene-ethylene copolymer (A2)
Distribution Mw/Mn is 1.5~3.5.The value of Mw/Mn is preferably 1.8~3.2, more preferably 2.0~3.0.If propylene-ethylene is total to
The Mw/Mn of polymers (A2) is smaller than 1.5, and melting tension force becomes too small, therefore Film making properties are poor.On the other hand, from ensuring to be made multilayer
Resistance to adhesive during film, it is ensured that from the viewpoint of the optical characteristics in multilayer film and composite membrane, Mw/Mn is preferably less than 3.5.On
Propylene-ethylene copolymers (A2) are stated, its Mw is preferably 450,000~100,000, more preferably 400,000~200,000.
Aforesaid propylene-ethylene copolymer (A2), according to the melt that JIS K7210 are determined at 230 DEG C with load 2.16kg
Flow rate MFR is 1~30g/10 minutes.The value is preferably 5~15g/10 minutes.If MFR is smaller than 1g/10 minutes, melting
Viscosity is too low, therefore the excessive pressure rising during manufacture of multilayer film in film-making machine (such as extruder), sometimes productivity ratio reduction.
And then, the bad orders such as membrane thickness unevenness, melt fracture are caused sometimes.On the other hand, if MFR was more than 30g/10 minutes, rise
Because becoming too much in the melt viscosity difference with the resin in intermediate layer, the thickness of outer layer becomes uneven sometimes.In addition, sometimes
Infringement is made resistance to adhesive during multilayer film.
Aforesaid propylene-ethylene copolymer (A2), preferably fusing point is 120~145 DEG C, more preferably 120~140 DEG C, enters one
Step is preferably 120~135 DEG C.The propylene-ethylene copolymers (A2) of fusing point are shown in the temperature of the scope, from manufacture multilayer film
When heat resistance and transparent balancing good when being made multilayer film or composite membrane in terms of from the point of view of and it is preferred that.
The content ratio of the ethylene unit in aforesaid propylene-ethylene copolymer (A2), preferably 1~10 mole % is more excellent
Elect 2~5 moles of % as.Set within the range by by the content ratio of ethylene unit, in the multilayer film for obtaining, can be not
Manifest excellent resistance to adhesive in the case of the infringement transparency, preferably.
Aforesaid propylene-ethylene copolymer (A2) is polymerized using metallocene series catalysts.Use metallocene catalysis
The propylene-ethylene copolymers (A2) of agent polymerization, the resistance to adhesive of height is shown from the multilayer film that obtains, and be made multilayer film and
From the point of view of being shown during composite membrane in terms of excellent optical characteristics preferably.
Metallocene catalyst is comprising with least one, preferably 2 cyclopentadienyls of substituted or unsubstituted cyclopentadienyl ligands
The catalyst of metal mold transistion metal compound and co-catalyst.As above-mentioned co-catalyst, such as organo-aluminium chemical combination can be enumerated
Thing；The complex compound of organoboron compound and cation；Ion exchangeable silicate etc., can use a kind selected from these
More than.Metallocene catalyst can be carried on appropriate inorganic substances.Metallocene catalyst is in the art it is well known that this area skill
Art personnel can suitably select appropriate metallocene catalyst and use according to its purpose.
[any condition]
Polypropylene-based resin in the laminate layer of the non-stretched multilayer film of polyolefin of the invention contains above-mentioned poly- third
Alkene system resin (A1) and propylene-ethylene copolymers (A2) are not hindering the scope of effect of the invention as necessary composition
It is interior, the other polymers beyond these can be contained.The other polymer for wherein using are above-mentioned polypropylene-based resins (A1)
With the polymer beyond propylene-ethylene copolymers (A2).The content ratio of other polymer, relative to polypropylene-based resin
(A1), propylene-ethylene copolymers (A2) and other polymer is total, preferably below 10 weight %, more preferably 5 weights
Amount below %, most preferably without other polymer.
The laminate layer of the non-stretched multilayer film of polyolefin of the invention, in addition to above-mentioned polypropylene-based resin, makees
It is arbitrary additive, such as heat stabilizer, processing stabilizers can be enumerated, lubricant, increase core agent, antistatic additive, antifoggant, anti-
Adhesion agent, antioxidant, ultra-violet absorber, pigment etc..These additives, can be using directly in composition polypropylene-based resin
The method addition coordinated in polymer, or the method that the masterbatch that can be employed as containing these additives with high concentration coordinates adds
Plus.As the base resin of masterbatch, can using above-mentioned polypropylene-based resin (A1) and propylene-ethylene copolymers (A2), with
And more than a kind in other polymers when using.
[form of laminate layer]
Polypropylene-based resin in the laminate layer of the non-stretched multilayer film of polyolefin of the invention contains polypropylene-based tree
The weight portion of fat (A1) 10~50 and the weight portion of propylene-ethylene copolymers (A2) 50~90.Preferably, polypropylene-based resin is contained
(A1) 20~40 weight portions and the weight portion of propylene-ethylene copolymers (A2) 60~80.In above-mentioned, above-mentioned polypropylene-based resin (A1)
100 weight portions are added up to aforesaid propylene-ethylene copolymer (A2).
By coordinating polypropylene-based resin (A1) in the polypropylene-based resin of laminate layer, so as to the multilayer film that will be obtained
Appropriate scope is set in the tearing strength in composite membrane, the tear Kaifeng property of packaging material is improved.This be considered as because,
Due to the cooperation of polypropylene-based resin (A1), the molecular weight distribution for constituting the polypropylene-based resin of laminate layer (outer layer) broadens,
Therefore, melting orientation is susceptible to when multilayer film is manufactured.Due to it is such the reasons why, the present invention in laminate layer need to contain 10
Polypropylene-based resin (A1) more than weight portion, preferably comprises polypropylene-based resins (A1) more than 20 weight portions.
On the other hand, by coordinating propylene-ethylene copolymers (A2) in the polypropylene-based resin of laminate layer, obtain
The optical characteristics such as the transparency, glossiness, mapping is improved in multilayer film and composite membrane, while the resistance to adhesive of multilayer film is also carried
It is high.Therefore, the laminate layer in the present invention needs, containing propylene-ethylene copolymers (A2) more than 50 weight portions, to preferably comprise
Propylene-ethylene copolymers (A2) more than 60 weight portions.
As the polymer coordinated in the polypropylene-based resin of laminate layer, above-mentioned polypropylene-based resin is preferably only included
And propylene-ethylene copolymers (A2) (A1).
The thickness of the laminate layer in the non-stretched multilayer film of polyolefin of the invention, preferably 1.0~30 μm, more preferably
It is 2.5~25 μm.By the way that laminate layer to be set as the thickness of the scope, do not damage resistance to from the multilayer film and composite membrane that obtain
It is hot and tear Kaifeng property in the case of obtain height impact resistance in terms of from the point of view of and it is preferred that.
<Intermediate layer>
Polyethylene-based resin is contained in intermediate layer in the non-stretched multilayer film of polyolefin of the invention, the polyethylene-based resin
Ethene-alpha-olefin copolymer (B) containing more than 70 weight %.Polymer in the polyethylene-based resin in the intermediate layer can be wrapped only
Containing ethene-alpha-olefin copolymer (B), also other polymer can be contained while containing ethene-alpha-olefin copolymer (B).
[ethene-alpha-olefin copolymer (B)]
Above-mentioned ethene-alpha-olefin copolymer (B), its density is 0.90~0.94g/cm3.Ethene-alpha-olefin copolymer (B)
Density be preferably 0.91~0.93g/cm3.If density ratio 0.90g/cm3Small, the rigidity of the multilayer film for obtaining is not enough, makes
During with the multilayer film or composite membrane as packaging material, the treatment adaptability for Bag Making Machine is deteriorated.On the other hand, in order that obtaining
To multilayer film and the raising effect of impact resistance of composite membrane fully manifest, the density of ethene-alpha-olefin copolymer (B) is excellent
Elect 0.94g/cm as3Below.
Above-mentioned ethene-alpha-olefin copolymer (B), according to the melt that JIS K7210 are determined at 190 DEG C with load 2.16kg
Flow rate MFR is 0.5~20g/10 minutes.The MFR is preferably 1~10g/10 minutes.If MFR is smaller than 0.5g/10 minutes,
Melt viscosity is too high, therefore the excessive pressure rising during manufacture of multilayer film in film-making machine (such as extruder), sometimes productivity ratio
Reduce.And then, the uneven of thickness is caused sometimes.On the other hand, if MFR was more than 20g/10 minutes, result from and outer layer
The melt viscosity difference of resin becomes too much, and the thickness of outer layer becomes uneven sometimes.In addition, it is made thickness during multilayer film
Sometimes become uneven.
Above-mentioned ethene-alpha-olefin copolymer (B), its Mw is preferably 250,000~30,000, more preferably 200,000~50,000.
Above-mentioned ethene-alpha-olefin copolymer (B), preferably fusing point is 90~135 DEG C, more preferably 100~125 DEG C.At this
The ethene-alpha-olefin copolymer (B) of fusing point is shown in the temperature of scope, from the multilayer film and composite membrane that obtain impact resistance and
Rigid balance becomes from the point of view of excellent aspect preferably.
Above-mentioned ethene-alpha-olefin copolymer (B) is the copolymer of ethene and alpha-olefin.As alpha-olefin used herein,
Such as propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene, 4-methyl-1-pentene can be enumerated
Deng, can use from these select more than a kind.The ratio of the α-olefin content in ethene-alpha-olefin copolymer (B) is preferred
It is 1~25 mole of %, more preferably 5~20 moles %.
Above-mentioned ethene-alpha-olefin copolymer (B), can be the product using the manufacture of any method as long as meeting above-mentioned condition
Thing.Can be using for example using known Ziegler-Natta catalyst, preferably while using the side of appropriate donor compound
Method；Method using philip catalyst etc. and manufacture.These catalyst can be carried on appropriate inorganic substances.
[other polymers]
The polyethylene-based resin in the intermediate layer in the non-stretched multilayer film of polyolefin of the invention contain above-mentioned ethene-α-
Olefin copolymer (B), in addition to the ethene-alpha-olefin copolymer (B), can contain other polymers.As can make herein
Other polymers, can enumerate such as homopolymers of polypropylene-based resin, ethene, thermoplastic elastomer (TPE) etc..It is poly- as other
Compound, in above-mentioned, the scope of appropriateness, impact resistance and packing timber is turned into from the multilayer film and the tearing strength of composite membrane for obtaining
The balance of the tear Kaifeng property of material becomes from the point of view of excellent aspect, preferably uses and is shown compared with ethene-alpha-olefin copolymer (B)
The homopolymers of the ethene of low MFR.The phenomenon is considered as resulting from, by by ethene-alpha-olefin copolymer (B) and above-mentioned second
The homopolymers of alkene is used in combination, so that melting orientation becomes stronger when multilayer film is manufactured.For the homopolymers of above-mentioned ethene, according to JIS
The melt flow rate (MFR) MFR that K7210 is determined at 190 DEG C with load 2.16kg is preferably 0.1~5g/10 minutes, more preferably
0.5~2.5g/10 minutes.The MFR, preferably with respect to the value of the MFR of ethene-alpha-olefin copolymer (B), is less than 50% value.
[additive]
Intermediate layer in the non-stretched multilayer film of polyolefin of the invention, in addition to above-mentioned polyethylene-based resin, can
Also contain additive.
As can additive as used herein, can enumerate for example heat stabilizer, processing stabilizers, lubricant, increase core agent,
Antistatic additive, antifoggant, antiblocking agent, antioxidant, ultra-violet absorber, pigment etc..These additives, can be existed using direct
The method addition coordinated in each resin, or the method that the masterbatch that can be employed as containing these additives with high concentration coordinates
Addition.Used as the base resin of masterbatch, other that can be using above-mentioned ethene-alpha-olefin copolymer (B) and when using gather
More than a kind in compound.
[form in intermediate layer]
Coordinate ethene-alpha-olefin copolymer (B) in the polyethylene-based resin in intermediate layer, in the multilayer film that obtains and compound
In film, contribute to the raising of impact resistance and mapping.If the ethene-alpha-olefin copolymerization in the polyethylene-based resin in intermediate layer
The ratio of thing (B) is fewer than 70 weight %, and the degree for manifesting of the effect above is not enough sometimes, not preferably.Intermediate layer it is polyethylene-based
The ratio of the ethene-alpha-olefin copolymer (B) in resin, preferably more than 75 weight %, more preferably more than 85 weight %.
Further, the polyethylene-based resin in the intermediate layer in the non-stretched multilayer film of polyolefin of the invention, as described above, matching somebody with somebody
Close the ethene-alpha-olefin copolymer (B) of more than half more than 70 weight %.Therefore, even if except ethene-alpha-olefin copolymer
(B) beyond, also coordinate the resin (such as polypropylene-based resin) beyond polyethylene-based resin, also do not hinder people in the art
Member is collectively referred to as polyethylene-based resin.
As the polymer coordinated in the polyethylene-based resin in intermediate layer, above-mentioned ethene-alpha-olefin copolymerization is preferably only included
Thing (B), or only comprising ethene-alpha-olefin copolymer (B) and above-mentioned other polymer (especially, with above-mentioned ethene-α-alkene
The homopolymers of the ethene of hydrocarbon copolymer (B) MFR low compared to display).
The thickness in the intermediate layer in the non-stretched multilayer film of polyolefin of the invention, preferably 5~80 μm, more preferably 10
~50 μm.By the way that intermediate layer to be set as the thickness of the scope, rigidity when being made multilayer film is never damaged, in the multilayer for obtaining
From the point of view of being obtained in terms of high impact properties and excellent mapping in film and composite membrane, preferably.
Intermediate layer can only include one layer, also can be laminated by more than two layers.In the case of the latter, constitute intermediate layer each layer from
Selected in above-mentioned polyethylene-based resin.Constitute the polyethylene-based resin of each layer, the species of respective polyethylene-based resin and
The presence or absence of any condition (other polymers and additive) and its species and content ratio all can be identical, 1 in these
More than can be different.
In the case that intermediate layer is made up of the lamination zoarium of polyethylene-based resin, its laminated number is preferably 2~4 layers, more excellent
Elect 2~3 layers as.The thickness of the lamilate is preferably in the above range as the thickness in intermediate layer.Constitute each layer of lamilate
Thickness be preferably 2~40 μm, more preferably 5~25 μm.
<Hot sealing layer>
Hot sealing layer in the non-stretched multilayer film of polyolefin of the invention contains polypropylene-based resin, the polypropylene-based resin
Propylene-ethylene copolymers (C) containing more than 70 weight %.Polymer in the polypropylene-based resin of the hot sealing layer can be included only
Propylene-ethylene copolymers (C), can also contain other polymer together with propylene-ethylene copolymers (C).
[propylene-ethylene copolymers (C)]
Aforesaid propylene-ethylene copolymer (C) is polymerized using metallocene series catalysts.The propylene-ethylene copolymerization
Thing (C), except using its fusing point as 125~140 DEG C as in addition to necessary condition, with for aforesaid propylene-ethylene copolymer
(A2) the identical characteristic.For the details of above-mentioned metallocene series catalysts, and in propylene-ethylene copolymers (A2)
The content illustrated in manufacture method is identical.
The fusing point of propylene-ethylene copolymers (C) is preferably 120~140 DEG C, more preferably 120~135 DEG C.
Propylene-ethylene copolymers (C) in hot sealing layer can be with the propylene-ethylene copolymers coordinated in laminate layer
(A2) other propylene-ethylene copolymers identical, or with different parameters.
[other polymers]
As above-mentioned other polymer, as long as not hindering effect of the invention, then can select to make with no particular limitation
With.But, it is considered to it is poly- as other during the raising of the property that broken a seal as the tear of the packaging material of one of principal character of the invention
Compound, preferably uses the polypropylene-based resin beyond aforesaid propylene-ethylene copolymer (C), particularly preferably using with layered product
The same polypropylene-based resin of the polypropylene-based resin (A1) of cooperation in layer.That is, it is that molecular weight distribution mw/mn is more than 4, according to
The melt flow rate (MFR) MFR that JIS K7210 are determined at 230 DEG C with load 2.16kg is 1~30g/10 minutes polypropylene-based
Resin.The fusing point of the polypropylene-based resin is preferably 120~150 DEG C, more preferably 130~145 DEG C.
[additive]
The polypropylene-based resin of the hot sealing layer in the non-stretched multilayer film of polyolefin of the invention, except above-mentioned propylene-
Beyond ethylene copolymer (C) and arbitrarily used other polypropylene-based resins, can also contain additive.
As can additive as used herein, can enumerate for example heat stabilizer, processing stabilizers, lubricant, increase core agent,
Antistatic additive, antifoggant, antiblocking agent, antioxidant, ultra-violet absorber, pigment etc..These additives, can be existed using direct
The method addition coordinated in each resin, or the method that the masterbatch that can be employed as containing these additives with high concentration coordinates adds
Plus.As the base resin of masterbatch, other polymers that can be using above-mentioned propylene-ethylene copolymers (C) and when using
In more than a kind.
[form of hot sealing layer]
Coordinate propylene-ethylene copolymers (C) in the polypropylene-based resin of hot sealing layer, in the multilayer film and composite membrane that obtain
In, contribute to the raising of the resistance to pinprick in resistance to adhesive, low temperature heat seal, the intensity in heat-sealing portion and heat-sealing portion.Hot sealing layer it is poly-
In the case that the ratio of the propylene-ethylene copolymers (C) in propylene resin is fewer than 70 weight %, the journey for manifesting of the effect above
Degree is not enough, not preferably.The ratio of the propylene-ethylene copolymers (C) in the polypropylene-based resin of hot sealing layer is preferably 80 weight %
More than, more preferably more than 90 weight %.
As the polymer coordinated in the polypropylene-based resin of hot sealing layer, aforesaid propylene-ethylene copolymer is preferably only included
(C) propylene-ethylene copolymers (C) and above-mentioned polypropylene-based resin, or are only included.
The thickness of the hot sealing layer in the non-stretched multilayer film of polyolefin of the invention, preferably 2~30 μm, more preferably
2.5~25 μm.By the way that hot sealing layer to be set as the thickness of the scope, Low Temperature Thermal is not damaged from the multilayer film and composite membrane that obtain
From the point of view of being obtained in the case of envelope property and resistance to pinprick in terms of the impact resistance of height, preferably.
<The thickness of the non-stretched multilayer film of polyolefin>
The thickness of the non-stretched multilayer film of polyolefin of the invention, can suitably be set according to it using form and purposes
It is fixed.Here so-called use form, be multilayer film of the invention use as packaging material as former state or with film base material stickup and
The selection used as composite membrane；So-called purposes, refers to species, weight of the content of packaging material etc..
The thickness of the non-stretched multilayer film of polyolefin of the invention, for example can be 10~100 μm, preferably 15~80 μm,
More preferably 20~75 μm.
<The manufacture method of the non-stretched multilayer film of polyolefin>
The non-stretched multilayer film of polyolefin of the invention, as long as substantially without the method for stretching, can use and appoint
The method manufacture of meaning.Wherein, so-called " substantially without stretching ", it is meant that produced in the manufacturing process for not being company's film minimum
Orientation is all forbidden, but film is not via the stretching process expressed.Thus, for example employing the stretching work under conditions of generally using
Some orientations are produced to allow in the case of sequence in the stretching direction.
Method as the non-stretched multilayer film of polyolefin of the invention is manufactured, can use such as extrusion molding, the tape casting
Etc. appropriate method.The resin of each layer of multilayer film of the invention is constituted, due to being respectively provided with appropriate MFR, for fusion
The adaptability of film-making machine is high, therefore from the point of view of in terms of manifesting to greatest extent effect of the invention, it is preferred to use on
Extrusion molding in stating.As the die head of extrusion molding, can be first-class using T-shaped mould head, annular die.But, from critically key-course
Thickness, obtain from the viewpoint of excellent optical characteristics, do not preferably use annular die, preferably use T-shaped mould head.
The non-stretched multilayer film of polyolefin of the invention, due to laminate layer, at least 1 layer of intermediate layer and heat-sealing
Layer, therefore with by least 3 layers sandwich construction for constituting.Method as film multiple stratification is made, can using such as coetrusion,
The known methods such as online laminating.As above-mentioned coetrusion, such as branch manifold method (Le of マ Le チ マ ニ ホ mono- can be enumerated
De, multimanifold), feed block method (feed block) etc..In these, from can equably be controlled respectively in width
From the point of view of in terms of the thickness of layer, it is preferred to use coetrusion.
The non-stretched multilayer film of polyolefin of the invention, plan is as former state or compound with paste itself and film base material by it
The form of film, as packaging material application.Therefore, in the case of the former, in order to express in outermost surface product source or
Person embodies the effect of design, and printing is implemented sometimes；In the case of the latter, on outermost surface (surface of usual laminate layer)
Paste film base material.Under such circumstances, in order to improve the compatibility or even adaptation with ink or adhesive, can be in outermost surface
Online or implementation surface treatment offline on (surface of usual laminate layer).As the surface treatment, such as corona can be enumerated
Discharge process, flame (flame) treatment etc..
<Composite membrane>
Composite membrane of the invention, by film base material by above-mentioned multilayer film using the lamination side of the multilayer film as viscous
Veneer is pasted and is obtained.Composite membrane of the invention, the resistance to pinprick in low temperature heat seal, heat seal strength and heat-sealing portion is good, and
Tear Kaifeng property when being made packaging material is also excellent.
[film base material]
As the material for constituting the film base material in composite membrane of the invention, can be suitably true according to the purposes of packaging material
It is fixed.Can enumerate for example from polypropylene-based resin, polyethylene-based resin, PET series resin and polyamide-based
The resin or metal selected in resin.Film base material can be the layer of the material containing more than a kind selected from these, or
Person, can the lamilate that constitutes of the layer as multiple.
The thickness of film base material, the purposes according to packaging material is arbitrary, for example, can be 5~75 μm, preferably 10~50 μ
m。
[thickness of composite membrane]
The gross thickness of composite membrane of the invention, can arbitrarily set according to the purposes of packaging material, for example, can be 15~180
μm, preferably 20~130 μm, more preferably 30~120 μm.
<The manufacture method of composite membrane>
The manufacture method of composite membrane, as long as multilayer film of the invention can be made with its laminate layer side on film base material
For the method that sticking veneer is pasted, then it is not particularly limited.
Bonding between film base material and the laminate layer of multilayer film can be appropriate adhesive, or thermo-compression bonding.
As adhesive as used herein, can be used commercially available adhesive, or usable molten resin (such as melting it is polyethylene-based
Resin).As the coating method of adhesive, such as gravure print roll coating, gravure roll-type reversion coating, offset printing roll-type can be enumerated and applied
The transfer means such as cloth；Rod, U Application マ バ first-class scraping means etc..
As by film base material and the laminated method of multilayer film (as needed via adhesive phase), can enumerate for example dry type layer
Platen press, lamination methods etc..
Embodiment
The present invention will be described to be exemplified below embodiment and comparative example, but the present invention is not limited to these embodiments.
Each evaluation in following embodiment and comparative example is respectively according to following order.
<The evaluation of multilayer film>
(1) mist degree
As the index of the transparency, Japanese electricity color industry (strain) system, haze meter (model are used：NDH5000), according to JIS
K7136 carries out the measure of mist degree.
(2) gloss
As the index of glossiness, ス ガ testing machines (strain) systems, gloss meter (model are used：UGV-5D), according to JIS
K7105 carries out the measure of gloss.
(3) as vividness
As the index of mapping, ス ガ testing machines (strain) systems, mapping analyzer (model are used：ICM-1DP), according to
JIS K7105, make a width of 0.125mm of slit of optical comb (comb), carry out the measure as vividness.
(4) adhesion intensity
As the index of resistance to adhesive, adhesion intensity is investigated by following tension test.
The foursquare multilayer film of 120mm × 120mm will be cut to, intermembranous be connected with hot sealing layer with laminate layer what is connected
Mode by 10 overlaps, to the load of its uppermost comprehensive applyings 10kg in the state of, in 40 DEG C of temperature and humidity 70%
3 days (72 hours) are taken care of in the constant temperature and humidity machine of RH.In multilayer film after keeping, by 2 of upper strata and 2 removings of lower floor,
6 of middle are taken, every 2 pairings that will abut against are peeled off, and have obtained 3 groups of pairing.Each pairing is for the multilayer of 2
Film makes laminate layer connect what is crimped under these conditions with hot sealing layer.Each pairing is cut out the length of 30mm × 120mm
It is square, obtain 3 test films.Peeled off from one end of the short side of each test film, crimping portion is remained with the length of 40mm.
Crimping portion 30mm × the 40mm of each test film residual turns into the mensuration region of resistance to adhesive.
Then, (strain) Shimadzu Seisakusho Ltd. system, the ト ガ ラ Off (models of オ mono- are used：AG-500D), by the stripping of above-mentioned test film
Layer from part is clamped in 2 fixtures respectively, in 23 DEG C of atmosphere of temperature of the measurement, enters under conditions of draw speed 50mm/ minutes
Row tension test, investigates until the maximum of the stress that test film is fully exfoliated.Make n numbers be 3, take the average value of the maximum
(kPa), as adhesion intensity.
(5) impact strength
As the index of impact resistance, (strain) Toyo Seiki system, film impact tester are used, rushed under the following conditions
The measure of hit intensity.
Experiment chip size：120mm×120mm
Temperature of the measurement：23 DEG C of atmosphere and 0 DEG C of atmosphere
(6) tearing strength (trousers shape method of Tearing)
As the index of resistance to tearing, according to JIS K7128-1, (strain) Shimadzu Seisakusho Ltd. system, the ト グ グ Off of オ mono- are used
(model：AG-500D), the measure of tearing strength is carried out under the following conditions.
Experiment chip size：Vertical 150mm, horizontal 50mm
Slit：In the otch of the central minister 75mm of the short side (transverse direction) of test film
Draw speed：200mm/ minutes
Temperature of the measurement：23 DEG C of atmosphere
<The evaluation of composite membrane>
(7) heat seal strength
As the index of heat sealability, make 2 composite membrane hot sealing layer between connect, investigated by following tension test
Intensity when sealing at each temperature.
Composite membrane is cut out the rectangle of 15mm × 200mm, using 2 as one group, in the way of connecting between hot sealing layer
Overlap, use (strain) to pacify field essence mechanism and make made, YSS heat sealing machines, seal under the following conditions, obtained test film.
Sealing strip width：5mm
Seal pressure：0.1MPa
Sealing period：1.0 seconds
Seal temperature：It is variable with 150 DEG C, 160 DEG C and 170 DEG C
Turn into the measure of each heat seal strength as the region of the 5mm × 15mm of the heat seal lands of test film obtained above
Region.Wherein, make the rectangular side long situation consistent with the extrusion direction of film as the test film in " vertical " direction, make rectangle
Side long and film the orthogonal situation in extrusion direction as " horizontal stroke " direction test film, the composite membrane for a kind is made average out to
The test film of 2 direction × 3 temperature=6 kind.
Use (strain) Shimadzu Seisakusho Ltd. system, the ト グ ラ Off (models of オ mono-：AG-500D), the examination after sealing at each temperature
The partially opening without heat-sealing of piece is tested, is clamped in respectively in 2 fixtures, carried out under conditions of draw speed 300mm/ minutes
Tension test, investigates the maximum of stress.
If the maximum of above-mentioned stress is more than 3N/15mm, can be evaluated as obtaining at such a temperature sufficiently
Heat seal strength.
(8) resistance to pinprick
As the index of the resistance to pinprick in heat-sealing portion, the crank detection test in heat-sealing portion has been carried out.
Composite membrane is cut out the rectangle of 150mm × 100mm, in the central right of short side in the way of hot sealing layer turns into inner side
Folding.1 side in short side part is remained as opening portion, for remaining 2 at when long (1 rim portion in short side and), use
(strain) peace field essence mechanism makees made, YSS heat sealing machines, seals under the following conditions, has obtained the simulation bag body of sealed tube shape.
The close temperature of heat：160℃
Seal pressure：0.1MPa
The heat-sealing time：1.0 seconds
Sealed width：5mm
From the opening portion of the simulation bag body, (strain) タ セ ト systems, dyeing are impregnated with flaw detection agent, " liquid FP-S standards is impregnated with
Type " is sprayed, and the liquid leakage state from sealing is visually observed, by following benchmark evaluation.
Have no way of the liquid leakage in heat-sealing portion：Zero (resistance to pinprick is good)
There is the liquid leakage from heat-sealing portion：× (resistance to pinprick is bad)
(9) Kaifeng property
As the index of the Kaifeng property of packaging material, tearing apart after being sealed between 2 hot sealing layers of composite membrane is investigated
Feng Xing.
Composite membrane is cut out the rectangle of 150mm × 100mm, using 2 as one group, in the way of connecting between hot sealing layer
Overlap, use (strain) to pacify field essence mechanism and make made, YSS heat sealing machines, under the following conditions seal 4 sides, obtained simulation system
Bag.4 sides of the simulation bag body are heat sealed to end.
The close temperature of heat：160℃
Seal pressure：0.1MPa
The heat-sealing time：1.0 seconds
Sealed width：5mm
In a piece of heat-sealing portion of the simulation bag body for obtaining, vertically cut out 10mm's from end using cutter
Cut channel, the cut channel portion transversely (direction that face is parallel and direction of with cut channel is vertical with simulation bag body) tear is investigated
The state of power and tearing part needed for the tear, by following benchmark evaluation.
Cut off along straight line from cut channel with light power, stretching, grain raising without film etc.：A (extremely good)
Weight is slightly felt during tear, but is cut off as the crow flies：B (good)
Feel to weigh very much during tear, the film stretching of cut-out, grain raising：C (bad)
Film is stretched from cut channel, without cut-out：D (extremely bad)
Embodiment 1
(manufacture of the non-stretched multilayer film of polyolefin)
Using PP-1, (Japanese Port リ プ ロ (strain) are made, model：FW3GT, fusing point=148 DEG C, MFR=7.0g/10 minutes
(230 DEG C), Mw/Mn=5.3), PP-2 (Japanese Port リ プ ロ (strain) system, model：WFX4TA, fusing point=126 DEG C, MFR=7.0g/
10 minutes (230 DEG C), Mw/Mn=3.0) and PE-1 (kind polyethylene (strain) system of space portion ball, model：2040FC, fusing point=118 DEG C,
MFR=4.6g/10 minutes (190 DEG C), density=0.919g/cm3), multilayer film is manufactured using following method.
Use the single screw extrusion machine 1 of the screw diameter 75mm by intermediate layer, two outer layers (laminate layer and heat-sealing
Layer) total 3 of single screw extrusion machine 2 of screw diameter 50mm extruder composition the 3 kinds 3 layers T-shaped mould for constituting
100 weight portion PE-1 are supplied intermediate layer extruder, by 30 weight portion PP-1 and 70 weight portions by head mode film film forming apparatus
100 weight portion PP-2 are supplied hot sealing layer extruder by the product supply laminate layer extruder of PP-2 mixing.Then, it is right
In 3 extruders each, all under conditions of 250 DEG C of resin temperature, 1 minute holdup time, 240 DEG C of T-shaped die head temperature from
Each T-shaped mould head extrusion, by 3 layers of chill roll of 25 DEG C of merga pass, has obtained multilayer film.The multilayer film is 3 layers of composition, gross thickness
It it is 50 μm, 3 layers of thickness constitutes substantially 1：2：1.
Next, implement Corona discharge Treatment, so that the wetting index on the surface of the laminate layer side of the multilayer film is
42mN/m, so carried out at 40 DEG C 24 hours it is aging, obtained the non-stretched multilayer film of polyolefin.
Using the non-stretched multilayer film of the polyolefin, the evaluation of above-mentioned (1)-(6) has been carried out.Evaluation result is shown in table 2.
(manufacture of composite membrane)
The layered product aspect that said polyolefins are non-stretched multilayer film is pasted on biaxial-stretched polypropylene films, manufacture is compound
Film.
For サ Application ト ッ Network ス (strain) systems, biaxial-stretched polypropylene films (model：サ Application ト Star Network ス-OP PA20, thickness
Degree：25 μm, one side sided corona treatment product) sided corona treatment face, with spreader (being set as 2 mils) be coated with dry lamination adhesive
(host (the model of the ト Application (strain) of Japan モ mono- system：TM-595) curing agent (the model of 15g, the society：CAT-56) 2.7g and vinegar
The solution of acetoacetic ester 36.8g mixing), dried 1 minute at 80 DEG C.Next, on the adhesive phase, will be obtained above poly-
The laminate layer side of the non-stretched multilayer film of olefin-based with hand roller squish lip it is laminated after, aging 3 days at 40 DEG C, be combined
Film.Further, above-mentioned unit " mil " means 0.001 inch, 1 mil is equivalent to about 25.3995 μm.
Using composite membrane obtained above, the evaluation of above-mentioned (7)~(9) is carried out.Evaluation result is shown in table 2.
Embodiment 2~10 and comparative example 1~6
In above-described embodiment 1, the species and use level of the resin of the extruder except making each layer of supply are respectively as in table 1
As shown in, the non-stretched multilayer film of polyolefin and composite membrane are manufactured similarly to Example 1, evaluate respectively.
Evaluation result is shown in table 2.
Further, in embodiment 4 and 5, as the resin of hot sealing layer, 2 kinds of mixed with resin is used；
In embodiment 9 and 10, as the resin in intermediate layer, 2 kinds of mixed with resin is used；
In comparative example 2, without cooperation polypropylene-based resin (A1) in the polypropylene-based resin of laminate layer,
In comparative example 5, without cooperation propylene-ethylene copolymers (A2) in the polypropylene-based resin of laminate layer；And
And
In comparative example 6, as the resin of laminate layer, without using in propylene-ethylene copolymers (A2), and conduct
The resin of interbed, polypropylene (PP-3) has been used instead of polyethylene-based resin.
The cooperation (1/3) of each layer in the 1st table non-stretched multilayer film of polyolefins
(the 1st table is continued)
The cooperation (1/3) of each layer in the 1st table non-stretched multilayer film of polyolefins
(the 1st table is continued)
The cooperation (2/3) of each layer in the 1st table non-stretched multilayer film of polyolefins
(the 1st table is continued)
The cooperation (3/3) of each layer in the 1st table non-stretched multilayer film of polyolefins
(the 1st end of list (EOL))
Should illustrate, the abbreviation of the resin raw material in above-mentioned table 1 is respectively following meanings.
PP-1：Japanese Port リ プ ロ (strain) system, model：FW3GT, fusing point=148 DEG C, MFR=7.0g/10 minutes (230
DEG C), Mw/Mn=5.3
PP-2：Japanese Port リ プ ロ (strain) system, model：WFX4TA, fusing point=126 DEG C, MFR=7.0g/10 minutes (230
DEG C), Mw/Mn=3.0
PP-3：Japanese Port リ プ ロ (strain) system, model：FW4B, fusing point=139 DEG C, MFR=7.0g/10 minutes (230 DEG C),
Mw/Mn=4.5
PP-4：Japanese Port リ プ ロ (strain) system, model：WFW4, fusing point=134 DEG C, MFR=7.5g/10 minutes (230 DEG C),
Mw/Mn=2.9
PE-1：Kind polyethylene (strain) system of space portion ball, model：2040FC, fusing point=118 DEG C, MFR=4.6g/10 minutes
(190 DEG C), density=0.919g/cm3
PE-2：Kind polyethylene (strain) system of space portion ball, model：1540F, fusing point=113 DEG C, MFR=3.6g/10 minutes (190
DEG C), density=0.913g/cm3
PE-3：Kind polyethylene (strain) system of space portion ball, model：R500, MFR=0.5g/10 minute (190 DEG C)
PE-4：Kind polyethylene (strain) system of space portion ball, model：Z372, fusing point=119 DEG C, MFR=5.3g/10 minutes (190
DEG C), density=0.934g/cm3
PE-5：Sumitomo Chemical (strain) system, model：FV402, fusing point=109 DEG C, MFR=3.6g/10 minutes (190 DEG C), close
Degree=0.913g/cm3
The effect of invention
The non-stretched multilayer film of polyolefin of the invention, due to optical characteristics such as high transparency, high-luster, mappings high
It is excellent, therefore when being used as packaging material, the visibility and design of content are excellent.Multilayer film of the invention, by
It is excellent in resistance to adhesive, therefore, it is possible to be taken care of for a long time as coiling body.Multilayer film of the invention is as film monomer or incites somebody to action
When it is pasted with film base material and is made composite membrane, because the resistance to pinprick in low temperature heat seal, heat seal strength and heat-sealing portion is also excellent,
Therefore, it is possible to be taken care of steadily in the long term after content is sealed.And then, multilayer film of the invention, because the tear with appropriateness is strong
Degree, therefore durability and the balancing good of tear Kaifeng property as packaging material.
Therefore, the non-stretched multilayer film of polyolefin of the invention can be extremely suitable for being used as in packaging material and packaging material
Sealant.
Claims (5)
1. multilayer film, is had as outermost laminate layer, at least 1 layer of intermediate layer and as another outermost heat-sealing
The non-stretched multilayer film of polyolefin of layer, 15~80 μm of thickness, the multilayer film is used to for the laminate layer to be pasted onto film base
Composite membrane is formed on material, it is characterised in that
Above-mentioned laminate layer contains polypropylene-based resin, and the polypropylene-based resin contains the polypropylene-based resin of 10~50 weight portions
The propylene-ethylene copolymers A2 of A1 and 50~90 weight portions, also, above-mentioned polypropylene-based resin A1 and aforesaid propylene-ethene are common
Polymers A2's adds up to 100 weight portions,
Polypropylene-based resin A1 by the ratio between weight average molecular weight Mw and number-average molecular weight Mn represent molecular weight distribution mw/mn be
More than 4, the melt flow rate (MFR) MFR determined with load 2.16kg at 230 DEG C according to JIS K 7210 is 1~30g/10 points
Clock；
The molecular weight distribution mw/mn of propylene-ethylene copolymers A2 is 1.5~3.5, is used at 230 DEG C according to JIS K 7210
The melt flow rate (MFR) MFR that load 2.16kg is determined is 1~30g/10 minutes, is polymerized using metallocene series catalysts；
Polyethylene-based resin is contained in above-mentioned intermediate layer, and the ethene-alpha-olefin that the polyethylene-based resin contains more than 70 weight % is total to
The density of polymers B, ethene-alpha-olefin copolymer B is 0.90~0.94g/cm3, used at 190 DEG C according to JIS K 7210 and carried
The melt flow rate (MFR) MFR that lotus 2.16kg is determined is 0.5~20g/10 minutes；
Above-mentioned hot sealing layer contains polypropylene-based resin, and the polypropylene-based resin contains propylene-ethylene copolymerization more than 70 weight %
Thing C；
The molecular weight distribution mw/mn of propylene-ethylene copolymers C is 1.5~3.5, is used at 230 DEG C according to JIS K 7210 and carried
The melt flow rate (MFR) MFR that lotus 2.16kg is determined is 1~30g/10 minutes, and fusing point is 125~140 DEG C, and using metallocene, system urges
Agent is polymerized.
2. the multilayer film described in claim 1, wherein, the polymer in the polypropylene-based resin of above-mentioned hot sealing layer is only comprising above-mentioned
Propylene-ethylene copolymers C.
3. the multilayer film described in claim 1 or 2, wherein, above-mentioned laminate layer, intermediate layer and hot sealing layer are using coetrusion layer
Conjunction is formed.
4. composite membrane, it is characterised in that by the multilayer film described in claim 1 or 2 with the lamination of the multilayer film on film base material
Pasted as sticking veneer and obtained in side.
5. the composite membrane described in claim 4, wherein, above-mentioned film base material at least has by selected from polypropylene-based resin, polyethylene
It is the layer of resin or the metal formation in resin, PET series resin and polyamide series resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-282157 | 2012-12-26 | ||
| JP2012282157A JP6030947B2 (en) | 2012-12-26 | 2012-12-26 | Polyolefin-based unstretched multilayer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103895307A CN103895307A (en) | 2014-07-02 |
| CN103895307B true CN103895307B (en) | 2017-07-07 |
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ID=50987029
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310747232.9A Expired - Fee Related CN103895307B (en) | 2012-12-26 | 2013-12-26 | The non-stretched multilayer film of polyolefin |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6030947B2 (en) |
| KR (1) | KR20140083910A (en) |
| CN (1) | CN103895307B (en) |
| TW (1) | TWI566933B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6083081B2 (en) * | 2014-08-22 | 2017-02-22 | 中川製袋化工株式会社 | Cleaning cover made of air-cooled inflation molded multilayer film |
| JP6798268B2 (en) * | 2015-11-30 | 2020-12-09 | 住友化学株式会社 | Multilayer film |
| JP6859651B2 (en) * | 2016-10-07 | 2021-04-14 | 凸版印刷株式会社 | Exterior material for power storage devices |
| TWI787379B (en) * | 2017-11-08 | 2022-12-21 | 日商東洋紡股份有限公司 | Production method of polyethylene-based resin film |
| JP7193307B2 (en) * | 2018-11-07 | 2022-12-20 | フタムラ化学株式会社 | Unstretched polypropylene resin film |
| CN113891798B (en) * | 2019-06-06 | 2023-12-05 | 日本他喜龙希爱株式会社 | Telescopic film |
| TW202100631A (en) * | 2019-06-20 | 2021-01-01 | 日商東洋紡股份有限公司 | Polyolefin-based resin film, and laminate using same |
| TWI828911B (en) * | 2019-06-20 | 2024-01-11 | 日商東洋紡股份有限公司 | Polyolefin resin films, laminates and packaging materials using polyolefin resin films |
| JP7306098B2 (en) * | 2019-06-21 | 2023-07-11 | Dic株式会社 | Laminated films and packaging materials |
| CN111002672A (en) * | 2019-12-13 | 2020-04-14 | 成都新柯力化工科技有限公司 | Plastic sheet for packaging frozen food and preparation method thereof |
| CN112078210A (en) * | 2020-08-27 | 2020-12-15 | 上海春宜药品包装材料有限公司 | Polyethylene composite medical packaging film and preparation method of production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009154332A (en) * | 2007-12-25 | 2009-07-16 | Japan Polyethylene Corp | Laminate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016525A1 (en) * | 2000-08-22 | 2002-02-28 | Mitsui Chemicals, Inc. | Sealing resin composition, sealing films and use thereof |
| US6703115B2 (en) * | 2001-05-01 | 2004-03-09 | Eastman Chemical Company | Multilayer films |
| EP1484345A1 (en) * | 2003-06-06 | 2004-12-08 | Borealis Technology Oy | Process for the production of polypropylene using a Ziegler-Natta catalyst |
| JP2007136866A (en) * | 2005-11-18 | 2007-06-07 | Dainippon Ink & Chem Inc | Coextruded multilayer film and laminated film using the film |
| JP2008114436A (en) * | 2006-11-02 | 2008-05-22 | Dainippon Printing Co Ltd | Multilayered laminated film for lid material of packaging container |
| JP5088575B2 (en) * | 2008-06-27 | 2012-12-05 | 東レフィルム加工株式会社 | Composite film |
| JP5224108B2 (en) * | 2008-08-01 | 2013-07-03 | サン・トックス株式会社 | Packaging material |
| JP2010173326A (en) * | 2010-03-16 | 2010-08-12 | Tohcello Co Ltd | Hot-melt propylene-based polymer laminated film and use thereof |
-
2012
- 2012-12-26 JP JP2012282157A patent/JP6030947B2/en active Active
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2013
- 2013-12-25 TW TW102148187A patent/TWI566933B/en active
- 2013-12-26 CN CN201310747232.9A patent/CN103895307B/en not_active Expired - Fee Related
- 2013-12-26 KR KR1020130163772A patent/KR20140083910A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009154332A (en) * | 2007-12-25 | 2009-07-16 | Japan Polyethylene Corp | Laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6030947B2 (en) | 2016-11-24 |
| JP2014124818A (en) | 2014-07-07 |
| KR20140083910A (en) | 2014-07-04 |
| TWI566933B (en) | 2017-01-21 |
| TW201444682A (en) | 2014-12-01 |
| CN103895307A (en) | 2014-07-02 |
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