CN105793037A - Polyolefin-based unstretched multilayer film - Google Patents
Polyolefin-based unstretched multilayer film Download PDFInfo
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- CN105793037A CN105793037A CN201480061423.2A CN201480061423A CN105793037A CN 105793037 A CN105793037 A CN 105793037A CN 201480061423 A CN201480061423 A CN 201480061423A CN 105793037 A CN105793037 A CN 105793037A
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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
- B32B27/32—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
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- 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
-
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
- B32B2307/70—Other properties
- B32B2307/702—Amorphous
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- 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
The present invention provides a polyolefin-based unstretched multilayer film, which has excellent optical characteristics, blocking resistance, heat sealing properties, hermetic sealing properties, package openability by tearing and easy peeling properties. This polyolefin-based unstretched multilayer film comprises a laminate layer, at least one intermediate layer, and a heat sealing layer. At least one intermediate layer is formed of a polyolefin-based resin containing a long-chain branched LLDPE. The long-chain branched LLDPE in the polyolefin-based resin of the intermediate layer has a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene as determined by gel permeation chromatography, namely Mw/Mn of 7.5-15.0 and an amorphous content of 1-4% by weight as determined by a temperature raising elution fractionation method. The long-chain branched LLDPE in the polyolefin-based resin of the intermediate layer has 1.5-5.0 branches, each of which has 8 or more carbon atoms, per 1,000 carbon atoms as determined by 13C-NMR.
Description
Technical field
The present invention relates to the non-stretched multilayer film of polyolefin.In particular it relates to high transparent, high-luster, high mapping
Etc. each physical properties excellent such as optical characteristics, resistance to blocking, low temperature heat seal；Simultaneously with base material film laminating and heat when making composite membrane
Also the excellent non-stretched multilayer films of polyolefin such as sealing strength, sealing, the tear Kaifeng property of package body or even release performance.
Background technology
Polyolefin-based resins film is widely used as the material packing various goods.For example, packaging for foodstuff purposes；
The packaging applications of the sundry goods product such as fiber, dress material；The packaging applications etc. of industrial part.Particularly, polypropylene-based resin film by
In rigidity and excellent heat resistance, the stiffness of film is the highest, and therefore the adaptability for Bag Making Machine is high, is widely used.But,
Polypropylene-based resin film at least its heat sealability (particularly low temperature heat seal) and impact resistance are insufficient.Therefore, attempted wanting
By making the Polypropylene copolymer materialization of membrane material, thus improve heat sealability and impact resistance.But, especially under low temperature
Impact resistance, does not obtain such effect.If additionally, heat sealability to be improved, the then problem producing adhesion.Therefore, on
State the trial of copolymerization materialization unsuccessful.
In this respect, in Unexamined Patent 5-147179 publication, it is proposed that a kind of polyolefin multilayer film, it is by using
Straight-chain ethene-alpha-olefin copolymer (LLDPE) is as intermediate layer, using this intermediate layer and the polypropylene-based resin as two outer layers
Layer stackup and improve impact resistance.According to the method, really observe the raising of impact resistance, but the optical characteristics of stacked film
(transparency, glossiness, mapping etc.) are impaired.Additionally, tearing when above-mentioned stacked film being fitted with base material film and makes composite membrane
Resistance to spalling becomes the highest, and tear Kaifeng property when therefore using it as packaging material is the most impaired.
In JP 2004-276373 publication, it is proposed that a kind of polyolefin multilayer film, it is by with the most poly-third
Alkene based polymer is as two outer layers, using itself and the LLDPE layer stackup as intermediate layer, thus improves low temperature heat seal and anti-stick
Lian Xing.According to this technology, the tearing strength of the composite membrane obtained is the highest, but tear Kaifeng when using it as packaging material
Property is not being met.
But, in such as packaging for foodstuff purposes, particularly in the little packaging grab a bite etc., when Kaifeng, except above-mentioned
Tear Kaifeng property beyond, also require by peel off heat-sealing portion break a seal.In a word, the thin of bag for facing each other is constituted
Film, seizes the vicinity in its respective heat-sealing portion often, this part is vertically pulled open to separate direction relative to pellicular front
Peel off heat-sealing portion, thus broken a seal.The easiness of the stripping in this heat-sealing portion is referred to as " release performance ".
Even if in the case of there are the packaging material of release performance, in addition to being used for food applications etc., in addition it is also necessary to
Maintain sealing.But, in conventional technology, for the sealing of maintenance package package material grinding of release performance can be improved again
Studying carefully and the most also do not have, this is present situation.
Summary of the invention
The present invention completes in view of the present situation of above-mentioned this area.
It is an object of the invention to provide optical characteristics, resistance to blocking, low temperature heat seal, heat seal strength, sealing etc. each
Physical properties excellent, simultaneously the tear Kaifeng property of package body and the also excellent non-stretched multilayer film of polyolefin of release performance.
According to the present invention, the above object and advantages of the present invention are realized by following multilayer film:
This multilayer film is to have as outermost laminate layers, at least 1 layer of intermediate layer and as another outermost heat-sealing
The non-stretched multilayer film of polyolefin of layer, it is characterised in that
Above-mentioned laminate layers contains polyolefin-based resins,
At least one of which in above-mentioned intermediate layer comprises the polyolefin-based resins containing long chain branching LLDPE,
Above-mentioned hot sealing layer comprises the polyolefin-based resins containing polypropylene-based resin,
The fusing point of the polyolefin-based resins of above-mentioned laminate layers is higher than the fusing point of the polypropylene-based resin in above-mentioned hot sealing layer,
Long chain branching LLDPE in polyolefin-based resins in above-mentioned intermediate layer uses pressing of gel permeation chromatography mensuration
Weight average molecular weight Mw of polystyrene conversion is 7.5～15.0 with the ratio Mw/Mn of number-average molecular weight Mn,
The amorphism component amount using temperature rising elution fraction to measure is 1～4 weight %, and uses13C-NMR measures
The side chain number of carbon number more than 8 is to have 1.5～5.0 in every 1,000 carbon atoms.
Detailed description of the invention
The non-stretched multilayer film of polyolefin of the present invention has: as outermost laminate layers, at least 1 layer of intermediate layer and work
For another outermost hot sealing layer.
＜ laminate layers ＞
Laminate layers in the multilayer film of the present invention contains polyolefin-based resins.
The fusing point of above-mentioned polyolefin-based resins is higher than the fusing point of the polypropylene-based resin in hot sealing layer described later.This polyene
The fusing point of hydrocarbon system resin is preferably high than the fusing point of the polypropylene-based resin in hot sealing layer more than 3 DEG C, the highest more than 5 DEG C, enters
One step is the highest 15 DEG C.Thus, sufficient heat resistance can be obtained when manufacture or lamination, the heat-sealing etc. of multilayer film of the present invention.
On the other hand, the fusing point of said polyolefins system resin preferably remains in 20 with the difference of the fusing point of the polypropylene-based resin in hot sealing layer
Below DEG C.If this is because, fusing point difference is excessive, then multilayer film tends to occur curling.
As the present invention constitutes the polyolefin-based resins of laminate layers, such as, can enumerate polypropylene-based resin, ethylene homo
Thing, ethene-alpha-olefin copolymer, thermoplastic elastomer (TPE) etc..They can be used alone, or two or more is used in mixed way.This
The fusing point of a little polyolefin-based resins is preferably in the scope of 120～165 DEG C, and melt flow rate (MFR) MFR is preferably in 1～30g/10
Minute scope.Above-mentioned fusing point is the summit temperature (Tm) of the maximum endothermic peak in differential scanning calorimeter (DSC) curve map；
Above-mentioned MFR is that (in this manual, fusing point, MFR are the most all same to the value according to JIS K 7210 mensuration
).
As above-mentioned polypropylene-based resin, the copolymer of Noblen, propylene and copolymer composition can be enumerated.As this altogether
Be polymerized to point, the most such as ethene and alpha-olefin, the most such as can enumerate ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc., it is possible to use more than a kind selected from which.This polypropylene-based tree
The ratio of the copolymer composition in fat, preferably 10 moles below %, more preferably 5 moles below %, more preferably 3 rub
You are below %.
Above-mentioned ethene-alpha-olefin copolymer does not comprise the composition being equivalent to above-mentioned polypropylene-based resin.As above-mentioned ethene-
Copolymer composition alpha-olefin in alpha olefin copolymer, such as, can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-
Octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc., it is possible to use more than a kind selected from which.Ethene-alpha-olefin is altogether
The ratio of the α-olefin content in polymers, preferably 1～20 mole %, more preferably 5～15 moles %.
Polyolefin-based resins in the laminate layers of multilayer film of the present invention, preferably comprises polypropylene-based resin as described above.
Laminate layers can comprise only polypropylene-based resin, it is also possible to containing other polymer while containing polypropylene-based resin.
Other polymer used herein are preferably from above-mentioned Alathon, ethene-alpha-olefin copolymer and thermoplastic elastomer (TPE)
Select.
All relative to polyolefin-based resins, the content ratio of other polymer is preferably below 10 weight %, more preferably
It is below 5 weight %, most preferably without other polymer.
[any composition]
The laminate layers of multilayer film of the present invention is in addition to polyolefin-based resins as described above, as arbitrary additive,
Such as can enumerate heat stabilizer, processing stabilizers, lubricant, increasing core agent, antistatic additive, antifoggant, antiblocking agent, anti-oxidant
Agent, ultra-violet absorber, pigment etc..These additives can use in the polymer being fitted directly to constitute polyolefin-based resins
Method is added, or the method carrying out coordinating as the masterbatch containing these additives with high concentration can be used to add.Make
Base resin for masterbatch, it is possible to use any one in above-mentioned polyolefin-based resins.
Relative to the entirety of polyolefin-based resins, the use ratio of any composition as described above be preferably 10 weight % with
Under, below more preferably 5 weight %.Most preferably do not contain such any composition.
[thickness of laminate layers]
The thickness of the laminate layers in multilayer film of the present invention is preferably 1.0～30 μm, more preferably 2.5～25 μm.By inciting somebody to action
Laminate layers is set as the thickness of this scope, for obtained multilayer film and composite membrane, is not damaging heat resistance and Kaifeng property ground
The impact resistance aspect obtaining height is preferred.
＜ intermediate layer ＞
At least 1 layer of intermediate layer in multilayer film of the present invention comprises the polyolefin tree containing long chain branching LLDPE (B1)
Fat.
[long chain branching LLDPE]
The straight-chain low density polyethylene (LDPE) that long chain branching LLDPE (B1) is the side chain with carbon number more than 8 in the present invention.
In terms of as having the low density polyethylene (LDPE) of side chain, the LLDPE used in the film of conventional art and the present invention
Long chain branching LLDPE (B1) and LDPE (low density polyethylene (LDPE)) be general.But, the long chain branching LLDPE in the present invention
(B1) at least in content, Mw/Mn and these several respects of amorphism component amount of its long chain branch, with the LLDPE of conventional art and
LDPE is different.
The long chain branching LLDPE (B1) of the present invention by13The side chain number of the carbon number more than 8 that C-NMR measures is every 1,000 carbon
Atom has 1.5～5.0.This value is preferably 2.0～5.0, more preferably 2.5～4.5.Had such by use
The LLDPE of long chain branch, when making package body by the multilayer film of the present invention, it is possible to obtain has tear Kaifeng property concurrently and is easily peeled
The advantage of property.
In this respect, the LLDPE of conventional art is to preponderate, even if there is carbon with the situation that carbon number is less than 6 of side chain
The side chain of several more than 8, its amount is also little, is usually less than 1, is the most only less than 2 in every 1,000 carbon atom.
On the other hand, LDPE exists13In the mensuration of C-NMR, the composition detected as the side chain of carbon number more than 8, every 1,000
Individual carbon number is more than 5.
Therefore, the long chain branching LLDPE (B1) of the present invention, according to by13The amount of the side chain of the carbon number more than 8 that C-NMR measures,
Can distinguish with LLDPE and LDPE of conventional art.
The branched structure of long chain branching LLDPE (B1) for the present invention exists with the branched structure of the LLDPE of conventional art13How C-NMR aspect measures carries out following description.Herein, as side chain, it is conceived to the C of long chain branching LLDPE8Side chain (1-last of the ten Heavenly stems
Alkene structure) and the C of LLDPE of conventional art6Side chain (1-octene structure).
Mesomethylene carbon present on the main chain of polyethylene can be13C-NMR is upper to be observed at chemical shift δ=30ppm.C8
Side chain and C6The methyl carbon of the branch terminals of both side chains all occurs at chemical shift δ=14.06ppm.But, from a last-in-chain(LIC)
The 2nd and the 3rd the respective chemical shift of mesomethylene carbon are held, for C8Side chain and C6For side chain, difference is as in table 1 below
Shown in.
[table 1]
Table 1. side chain-(CH 2 ) n -C γ H 2 -C β H 2 -C α H 3 The chemical shift (ppm) of (n=3 or 5)
| n | Main chain-CH2- | -CγH2- | -CβH2- | -CαH3 | |
| C6Side chain (octene structure) | 3 | 30 | 32.20 | 22.90 | 14.06 |
| C8Side chain (decene structure) | 5 | 30 | 32.17 | 22.87 | 14.06 |
In the present invention, it is conceived to the 2nd mesomethylene carbon from branch terminals therein, judges side chain according to its chemical shift
Whether carbon number is more than 8.
When carrying out Practical Calculation, evaluate the area at the peak occurred at chemical shift δ=22.87ppm relative to returning
Belong to the relative value of the area at the peak occurred at the chemical shift δ=30ppm of main chain mesomethylene carbon.
As described above13The mensuration of C-NMR can use the model " JNM-ECS400 " etc. that such as NEC's (strain) makes
Suitable NMR analysis devices, is carried out by following condition.
Solvent: the mixed solvent (75/25 volume %) of trichloro-benzenes/heavy benzol
Sample solution concentration: 80mg/2.5mL solution
Mode determination: 1H-decouples completely
Mensuration temperature: 120 DEG C
Pulse width: 90 degree of pulses
Pulse-recurrence time: 9 seconds
Cumulative number: 9,000 times
For the content of the long chain branch of the present invention, it is by from C8The end of side chain plays the 2nd carbon (chemical shift δ
=22.87ppm) peak area be 1 relative to constituting the peak area of mesomethylene carbon (chemical shift δ=30ppm) of polymer chain,
Relative value when 000 represents.Unit is (individual/1,000C).
The long chain branching LLDPE (B1) of the present invention use that gel permeation chromatography (GPC) measures by polystyrene conversion
Ratio Mw/Mn (molecular weight distribution) of weight average molecular weight Mw and number-average molecular weight Mn be 7.5～15.0.This value be preferably 8.5～
14.5, more preferably 9.5～13.5.Be there is the long chain branching LLDPE of such molecular weight distribution by use, when by the present invention
Multilayer film when making package body, it is possible to obtain have tear Kaifeng property and the advantage of release performance concurrently.
The long chain branching LLDPE (B1) of the present invention uses the excellent by weight average molecular weight Mw of polystyrene conversion of GPC mensuration
Elect 80,000～150 as, 000, more preferably 90,000～140,000.
The amorphism component amount that the long chain branching LLDPE (B1) of the present invention uses temperature rising elution fraction to measure is 1～4
Weight %.
Temperature rising elution fraction is a process that: polymer sample is at high temperature dissolved in regulation solvent and forms
Solution be supplied to TREF (Temperature Rising Elution Fractionation (Rising Elution Fractionation)) post, connect
Cooling and make polymer sample separate out in this post and be adsorbed, then post is slowly heated up, analyze the fraction of wash-out.At this
In invention, the pillar after being supplied by sample is initially supplied solvent after being cooled to 0 DEG C, will be maintained at the fraction that 0 DEG C of period elutes
As noncrystalline composition, this fraction is evaluated as amorphism component amount relative to the ratio of whole fractions.Long chain branching LLDPE
Amorphism component amount be preferably 1.5～3.0 weight %.
Such temperature rising elution fraction can use such as the TREF device special type etc. of (strain) セ Application シ ュ section length of schooling
Suitable Rising Elution Fractionation (TREF) device is carried out.
By use, there is crystalline long chain branching LLDPE as described above, it is possible to obtain guarantee multilayer film of the present invention
Resistance to blocking and the advantage of stiff feel (elastic).
For ease of reference, table 2 below shows the above-mentioned various parameters of representative commercially available product polyethylene.
The parameter of [table 2] various polyethylene compares
Which kind of side the long chain branching LLDPE (B1) of the present invention as described above, as long as meeting above-mentioned necessary condition, use
Method synthesizes.Can use and such as known Ziegler-Natta catalyst is used together with the most suitable compound donator
Method；The method using Phillips catalyst；The method etc. using metalloscene catalyst manufactures.Wherein, easily obtaining
Must have the polymer aspect of above-mentioned characteristic, it is preferred to use the method using metalloscene catalyst.
Metalloscene catalyst is to comprise to have at least 1, the gold of preferably 2 substituted or unsubstituted cyclopentadienyl ligands
Belong to cyclopentadienyl type transistion metal compound and the catalyst of co-catalyst.As above-mentioned co-catalyst, such as, can enumerate organo-aluminium chemical combination
Thing；Organoboron compound and the complex of cation；Ion exchangeable silicate etc., it is possible to use a kind selected from which with
On.Metalloscene catalyst can also be supported on suitable inorganic substances.Metalloscene catalyst is that many institutes are all in this area
Knowing, those skilled in the art suitably can select to use suitable metalloscene catalyst according to its purpose.
[other polymer]
Above-mentioned at least 1 layer of intermediate layer in multilayer film of the present invention, except containing long chain branching LLDPE as described above
(B1) beyond, it is also possible to containing other polymer.
As other polymer that can use herein, such as, can enumerate polypropylene-based resin (B2), except long chain branching
Polyethylene (B3) beyond LLDPE (B1), thermoplastic elastomer (TPE) etc..
As polypropylene-based resin (B2), for the polypropylene-based tree as the polyolefin-based resins such as constituting laminate layers
Fat, it is possible to use the resin as the resin of described above.
As the polyethylene (B3) in addition to long chain branching LLDPE (B1), such as, can enumerate HDPE, LLDPE, LDPE
Deng.
By making the intermediate layer in multilayer film of the present invention contain the polypropylene-based resin in other polymer above-mentioned
(B2) at least a kind of resin in polyethylene (B3) and in addition to long chain branching LLDPE (B1), can adjust by above-mentioned many
It is easily peeled intensity when tunic makes package body, is therefore preferred.
Consider from viewpoint as described above, the polyolefin tree in above-mentioned at least 1 layer of the intermediate layer of multilayer film of the present invention
Fat, preferably
Only comprise long chain branching LLDPE (B1), or,
Comprise long chain branching LLDPE (B1) and
Selected from polypropylene-based resin as described above (B2) and the polyethylene (B3) in addition to long chain branching LLDPE (B1)
In at least a kind of resin.
Above-mentioned at least 1 layer of the intermediate layer of multilayer film of the present invention, the most only comprises polyolefin-based resins as described above, and
Resin without other.
Polyolefin-based resins in above-mentioned at least 1 layer of the intermediate layer of multilayer film of the present invention, preferably respectively in the following proportions
Containing resin as described above.
Long chain branching LLDPE (B1): be preferably more than 40 weight %, more than more preferably 50 weight %；
Polypropylene-based resin (B2): be preferably below 30 weight %, below more preferably 25 weight %；And
Polyethylene (B3) in addition to long chain branching LLDPE (B1): be preferably below 50 weight %, more preferably 30 weights
Amount below %.
In described above, long chain branching LLDPE (B1), polypropylene-based resin (B2) and except long chain branching LLDPE
(B1) polyethylene (B3) beyond add up to 100 weight %.
[any composition]
The intermediate layer of multilayer film of the present invention can also be contained as described in any composition of laminate layers using same form
Additive.
[form in intermediate layer]
Intermediate layer in multilayer film of the present invention, can only be constituted by one layer, it is possible to laminated together by more than two layers.The latter
In the case of, each layer constituting intermediate layer selects from above-mentioned polyolefin-based resins.To the polyolefin-based resins constituting each layer
For, each of which is in the kind of polyolefin-based resins and whether there is other polymer as any composition and interpolation
Agent and kind thereof and content ratio aspect, can be the most identical, it is also possible to wherein more than 1 is different.
The thickness in intermediate layer is preferably 5～80 μm, more preferably 10～50 μm.Firm when never multilayer film is made in infringement
Property, from the standpoint of the multilayer film obtained and composite membrane obtain high impact properties and excellent mapping, preferably by centre
The thickness of layer is set as above-mentioned scope.
When intermediate layer comprises the layered product of polyolefin-based resins, its lamination number is preferably 2～4 layers, more preferably 2～3
Layer.The polyolefin-based resins of each layer can be identical, it is also possible to different.The thickness of this layered product, as the thickness in intermediate layer, preferably
For in above-mentioned scope.The thickness of each layer constituting layered product is preferably 2～40 μm, more preferably 5～25 μm.
＜ hot sealing layer ＞
Hot sealing layer in multilayer film of the present invention comprises the polyolefin-based resins containing polypropylene-based resin.
This polypropylene-based resin preferably comprises polypropylene-based resin, and this polypropylene-based resin contains the third of more than 70 weight %
Alkene-ethylene copolymer (C).Polymer in the polypropylene-based resin of this hot sealing layer can be only by aforesaid propylene-ethylene copolymer (C)
Constitute, it is possible to containing other polymer together with this propylene-ethylene copolymers (C).
The cooperation of the propylene-ethylene copolymers (C) in the polypropylene-based resin of hot sealing layer, is favorably improved the multilayer of gained
Film and composite membrane, resistance to blocking, low temperature heat seal, the intensity in heat-sealing portion and the resistance to pinprick in heat-sealing portion.When hot sealing layer
The ratio of the propylene-ethylene copolymers (C) in polypropylene-based resin less than 70 weight % time, the effect above manifest degree not
Foot, the most preferably.The ratio of the propylene-ethylene copolymers (C) in the polypropylene-based resin of hot sealing layer is preferably more than 80 weight %,
More than more preferably 90 weight %.
The molecular weight that the ratio by weight average molecular weight Mw with number-average molecular weight Mn of aforesaid propylene-ethylene copolymer (C) represents
Distribution Mw/Mn is preferably 1.5～3.5, more preferably 1.8～3.2, and more preferably 2.0～3.0.Propylene-ethylene copolymers
(C), when Mw/Mn is less than 1.5, melted tension force is too small, and masking is deteriorated.On the other hand, anti-stick in time guaranteeing to make multilayer film
Lian Xing, guarantee the optical characteristics of multilayer film and composite membrane from the viewpoint of, Mw/Mn is preferably less than 3.5.Aforesaid propylene-ethene
The Mw of copolymer (C) is preferably 450,000～100,000, more preferably 400,000～200,000.
Melt according to aforesaid propylene-ethylene copolymer (C) that JIS K 7210 measures by load 2.16kg at 230 DEG C
Flow rate MFR is preferably 1～30g/10 minute, more preferably 5～15g/10 minute.If MFR was less than 1g/10 minute, then
Melt viscosity is too high, and the excessive pressure in film-making machine (such as extruder) when therefore multilayer film manufactures raises, and makes raw sometimes
Productivity reduces, and additionally can cause the bad order such as membrane thickness unevenness, melt slight crack.On the other hand, if MFR is more than 30g/10
Minute, then owing to becoming excessive with the melt viscosity difference of the resin in intermediate layer, make the thickness of outer layer become uneven sometimes, this
Outward, resistance to blocking when making multilayer film can also be damaged.
The fusing point of aforesaid propylene-ethylene copolymer (C) is preferably 120～140 DEG C, more preferably 120～135 DEG C.At this
The temperature of scope shows the propylene-ethylene copolymers (C) of fusing point, from manufacture multilayer film time heat resistance with make multilayer film or
It is preferred from the standpoint of the balancing good of transparency during composite membrane.
The content ratio of the ethylene unit in aforesaid propylene-ethylene copolymer (C) is preferably 1～10 mole of %, more preferably
It is 2～5 moles of %.By the content ratio of ethylene unit is set within the range, for obtained multilayer film, can
Under conditions of not damaging the transparency, realize the resistance to blocking of excellence, be therefore preferred.
Aforesaid propylene-ethylene copolymer (C) is preferably used metallocene series catalysts and is polymerized, for using metallocene to urge
For the propylene-ethylene copolymers (C) that agent is polymerized, obtained multilayer film demonstrates the resistance to blocking of height, and
Demonstrate the optical characteristics of excellence when making multilayer film and composite membrane, it is preferred in these areas.
Metalloscene catalyst is to comprise to have at least 1, the gold of preferably 2 substituted or unsubstituted cyclopentadienyl ligands
Belong to cyclopentadienyl type transistion metal compound and the catalyst of co-catalyst.As above-mentioned co-catalyst, such as, can enumerate organo-aluminium chemical combination
Thing；Organoboron compound and the complex of cation；Ion exchangeable silicate etc., it is possible to use selected from more than a kind therein.
Metalloscene catalyst can also be supported on suitable inorganic substances.Metalloscene catalyst is generally well known in this area,
Those skilled in the art suitably can select to use suitable metalloscene catalyst according to its purpose.
[other polymer]
As other polymer above-mentioned, as long as not hindering the effect of the present invention, it is possible to select with being not particularly limited
Use.But, in the case of considering that raising is as the tear Kaifeng property of the packaging material of one of principal character of the present invention, as
Other polymer, is preferably used the polypropylene-based resin (A1) in addition to aforesaid propylene-ethylene copolymer (C).For poly-
Propylene resin (A1), the molecular weight distribution mw/mn represented with the ratio of weight average molecular weight Mw with number-average molecular weight Mn be preferably 4 with
On, more preferably 4.5～10, more preferably 5～8.When the Mw/Mn of polypropylene-based resin (A1) is less than 4, the multilayer obtained
The tearing strength of film and its composite membrane manufactured of use becomes too high, it is difficult to manifest the improvement tearing Kaifeng property in packaging material
Effect.This be considered because: when Mw/Mn is less than 4, multilayer film is difficult to occur melted orientation during fabrication.On the other hand, from making
Melted tension force when multilayer film manufactures is maintained at suitable scope, it is ensured that from the viewpoint of resistance to blocking when making multilayer film,
Mw/Mn is preferably less than 10.The Mw of above-mentioned polypropylene-based resin (A1) is preferably 450,000～100,000, more preferably 400,000～20
Ten thousand.
Weight average molecular weight Mw and number-average molecular weight Mn are all to use gel permeation chromatography (GPC) changing by polystyrene of measuring
The value calculated.
For polypropylene-based resin (A1), the melt flow measured by load 2.16kg at 230 DEG C according to JIS K 7210
Dynamic speed MFR is preferably 1～30g/10 minute, more preferably 5～15g/10 minute.If MFR is less than 1g/10 minute, then melt
Melt-viscosity is too high, and the excessive pressure in film-making machine (such as extruder) when therefore multilayer film manufactures raises, sometimes productivity ratio fall
Low, additionally, sometimes cause the bad order such as membrane thickness unevenness, melt slight crack.On the other hand, if MFR was more than 30g/10 minute,
Then owing to becoming excessive with the melt viscosity difference of the resin in intermediate layer, the thickness of outer layer becomes uneven sometimes, additionally, sometimes
Resistance to blocking during multilayer film is made in infringement.
The fusing point of above-mentioned polypropylene-based resin (A1) is preferably 120～150 DEG C, more preferably 130～145 DEG C.At this model
The temperature enclosed shows the polypropylene-based resin (A1) of fusing point, from manufacture multilayer film time heat resistance with make multilayer film and be combined
During film the transparency balancing good from the standpoint of and preferred.Herein, the fusing point of so-called resin, refer to differential scanning calorimeter
(DSC) summit temperature (Tm) of maximum endothermic peak in curve map.
Above-mentioned polypropylene-based resin (A1) can be Noblen, it is also possible to be the copolymer of propylene and copolymer composition.
As copolymer composition used herein, optimal ethylene and alpha-olefin, the most such as, can enumerate ethene, 1-butylene, 1-amylene, 1-
Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc., it is possible to use more than a kind in these.
The ratio of the copolymer composition in polypropylene-based resin (A1) is preferably 10 moles of below %, more preferably 5 moles below %, enters one
Step is preferably 3 moles of below %.
Hot sealing layer is the most only made up of aforesaid propylene-ethylene copolymer (C), or the most only by propylene-ethylene copolymers
(C) constitute with polypropylene-based resin (A1).
[any composition]
The hot sealing layer of multilayer film of the present invention can also contain any composition record as laminate layers using same form
Additive.
[thickness of hot sealing layer]
The thickness of the hot sealing layer in multilayer film of the present invention is preferably 2～30 μm, more preferably 2.5～25 μm.By by heat
Sealing is set as the thickness of this scope, is not damaging low temperature heat seal and resistance to pin for the multilayer film for obtaining and composite membrane
Eye property in the case of obtain height impact resistance from the standpoint of and preferred.
Thickness G T.GT.GT of the non-stretched multilayer film of ＜ polyolefin
The thickness of the non-stretched multilayer film of polyolefin of the present invention, can use form and purposes suitably to set according to it
Fixed.Here so-called use form, be the multilayer film former state of the present invention is used as packaging material or fits with film base material and
The selection used as composite membrane；So-called purposes, refers to the kind of the content of packaging material, weight etc..
The thickness of the non-stretched multilayer film of polyolefin of the present invention can be such as 10～200 μm, preferably 15～150 μ
M, more preferably 18～100 μm.
Manufacture method ＞ of the non-stretched multilayer film of ＜ polyolefin
The multilayer film of the present invention, as long as substantially without the method for stretching, it is possible to use arbitrary method manufacture.
" substantially without stretching " is not meant to that in the manufacture process of film the raw minimum orientation of running fire is all forbidden, and refers to that film is not
Through obvious stretching process.It is, therefore, understood that such as in the feelings of the extrusion operation that have employed under conditions of generally using
Under condition, produce some orientations in extrusion direction and allow.
As the method for the multilayer film manufacturing the present invention, the method that such as extrusion molding, the tape casting etc. are suitable can be used.Structure
Becoming the resin of each layer of multilayer film of the present invention, owing to being respectively provided with the MFR of appropriateness, the adaptability for the film-making machine of fusion is high,
Therefore from the standpoint of the effect of the present invention can be made to greatest extent to manifest, it is preferred to use extrusion molding above.As
The die head of extrusion molding, can use T-shaped die head, annular die first-class.But, from the thickness of critically key-course, obtain excellence
From the viewpoint of optical characteristics, annular die is not preferably used and T-shaped die head etc. is preferably used.
Owing to the multilayer film of the present invention has laminate layers, at least 1 layer of intermediate layer and hot sealing layer, therefore have by least 3 layers
The sandwich construction constituted.As the method making film multiple stratification, known side such as such as coetrusion, online laminating etc. can be used
Method.As above-mentioned coetrusion, such as, can enumerate branch manifold method (multimanifold), feed block method (feed block) etc..
In these methods, owing to can control the thickness of each layer equably at width, it is preferred to use coetrusion.
The multilayer film of the present invention, plan by its former state or with its with film base material the form of the composite membrane of laminating, as bag
Package material is applied.Therefore, in the former case, in order to express the source of goods at outermost surface or embody the effect of design
Really, printing is sometimes implemented；In the latter case, outermost surface (surface of usual laminate layers) attaches film base material.?
In this case, in order to improve and ink or the compatibility of adhesive or even adaptation, can be at outermost surface (usual laminate layers
Surface) on implement online or off-line surface and process.Process as this surface, such as, can enumerate Corona discharge Treatment, flame
Process
＜ composite membrane ＞
The composite membrane of the present invention can by film base material by above-mentioned multilayer film using the laminate layers side of this multilayer film as
Attaching face attaches and obtains.The resistance to pinprick in the low temperature heat seal of composite membrane of the present invention, heat seal strength and heat-sealing portion is good, and makes
Become tear Kaifeng property during packaging material the most excellent.
[film base material]
As the material of the film base material constituted in composite membrane of the present invention, can be the most true according to the purposes of packaging material
Fixed.Such as can enumerate selected from polypropylene-based resin, polyethylene-based resin, PET series resin and polyamide
It is the resin in resin or metal.Film base material can be the layer containing more than the a kind material selected from these materials, or
Person, can be the layered product being made up of multiple such layers.
The thickness of film base material can be arbitrary according to the purposes of packaging material, such as, can be 5～75 μm, preferably 10
～50 μm.
[thickness of composite membrane]
The gross thickness of the composite membrane of the present invention at random can set according to the purposes of packaging material, can be such as 15～
250 μm, preferably 20～200 μm, more preferably 23～150 μm.
Manufacture method ＞ of ＜ composite membrane
The manufacture method of composite membrane, as long as can on film base material by the multilayer film of the present invention using its laminate layers side as
The method that attaching face attaches, is just not particularly limited.
Bonding between film base material and the laminate layers of multilayer film can use suitable adhesive, it would however also be possible to employ hot pressing
Connect.As adhesive as used herein, commercially available adhesive can be used, or molten resin can be used, such as melted poly-second
Alkene system resin.As the coating process of adhesive, such as, can enumerate gravure, the coating of reverse intaglio plate, hectographic printing coating
Deng transfer device；The scratch devices etc. such as rod, comma bar type coating.
As method film base material and multilayer film (as required via adhesive phase) being laminated, such as, can enumerate dry type layer
Platen press, lamination methods etc..
Embodiment
The present invention will be described below to enumerate embodiment and comparative example, but the present invention is not limited to these embodiments.
Each evaluation in below example and comparative example is carried out according to following order respectively.
The evaluation ＞ of ＜ multilayer film
(1) mist degree
As the index of the transparency, use Japan's electricity look industry (strain) system, haze meter (model: NDH5000), according to JIS
K 7136 carries out the mensuration of mist degree.
(2) gloss
As the index of glossiness, use Suga testing machine (strain) system, gloss meter (model: UGV-5D), according to JIS K
7105 mensuration carrying out gloss.The evaluation of this gloss, respectively to the face of the face of the laminate layers side of multilayer film and hot sealing layer side this two
Face is evaluated.
(3) image definition
As the index of mapping, use Suga testing machine (strain) system, mapping analyzer (model: ICM-1DP), according to
JIS K 7105, makes a width of 0.125mm of slit of optical comb, carries out the mensuration of image definition.
(4) adhesion intensity
As the index of resistance to blocking, investigate adhesion intensity by following tension test.
To be cut to the foursquare multilayer film of 120mm × 120mm, intermembranous connect with hot sealing layer with laminate layers connect
Mode is by 10 overlaps, under the state to its uppermost whole load applying 10kg, in temperature 40 DEG C and humidity 70%
Keeping 3 days in the constant temperature and humidity machine of RH, i.e. 72 hours.In multilayer film after keeping, 2 of the 2 of upper strata and lower floor are removed
Going, take 6 of middle, every 2 pairings that will abut against are peeled off, and have obtained the pairing of 3 groups.Each pairing is for more than 2
Tunic make laminate layers connect with hot sealing layer and under these conditions crimping.This is respectively matched and is cut out 30mm × 120mm
Rectangle, obtained 3 test films.From one end strip off of the minor face of each test film, make crimping portion residual with the length of 40mm
Stay.On each test film, the crimping portion 30mm × 40mm of residual becomes the mensuration region of resistance to blocking.
Then, (strain) Shimadzu Seisakusho Ltd. system, autoplotter (model: AG-500D) are used, by the stripping of above-mentioned test film
The layer of part is clamped in 2 fixtures respectively, carries out under conditions of 50mm/ minute measuring 23 DEG C of atmosphere of temperature, draw speed
Tension test, investigates until the maximum of stress that is fully exfoliated of test film.Making n number is 3, takes the mean value of this maximum
(kPa), as adhesion intensity.
(5) impact strength
As the index of impact resistance, use the film impact tester (autograph) of (strain) Toyo Seiki, following
Under the conditions of carry out the mensuration of impact strength.
Test film size: 120mm × 120mm
Mensuration temperature: 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 K 7128-1, use the autoplotter of (strain) Shimadzu Seisakusho Ltd.
(model: AG-500D), carries out the mensuration of tearing strength under the following conditions.
Test film size: long limit (indulging) 100mm, minor face (horizontal) 50mm
Slit: at the central portion (position of distance limit 25mm) of a minor face of test film, arrange abreast with long limit
The otch of long 20mm
Draw speed: 500mm/ minute
Mensuration temperature: 23 DEG C of atmosphere
The evaluation ＞ of ＜ composite membrane
(7) heat seal strength
As the index of heat sealability, make to connect between the hot sealing layer of 2 composite membranes, examined by the tension test of the following stated
Examine 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) peace field essence mechanism to make made YSS heat sealing machine, seal under the following conditions, obtain test film.
Sealing strip width: 5mm
Seal pressure: 0.1MPa
Sealing period: 1.0 seconds
Seal temperature: with 150 DEG C, 160 DEG C and 170 DEG C as variable
Using the region of the heat seal lands 5mm × 15mm of test film obtained above as the measurement region of each heat seal strength
Territory.Wherein, using situation consistent for the extrusion direction of rectangular long limit and film as " indulging " to test film, by rectangular length
The orthogonal situation in the extrusion direction of limit and film as " horizontal " to test film, for a kind of composite membrane, make 2 direction × 3 temperature
Spend the test film of=6 kinds.
Use the autoplotter (model: AG-500D) of (strain) Shimadzu Seisakusho Ltd., by the examination after heat-sealing at each temperature
That tests sheet does not has partially opening of heat-sealing, it is clamped in respectively in 2 fixtures, under conditions of draw speed 300mm/ minute
Carry out tension test, investigate the maximum of stress.
If the maximum of above-mentioned stress is more than 3N/15mm, then can be evaluated as having obtained at such a temperature sufficiently
Heat seal strength；
If at below 13N/15mm, then can be evaluated as that there is release performance.
(8) release performance (sense test)
In order to investigate release performance, carry out the sense test broken a seal by package body with staff.
Use vertical pillow type packing machine ((strain) Tokyo Automatic Machinery Works Ltd system, model " TWX1N "), by the heat of composite membrane
By following condition heat-sealing between sealing, obtain long 120mm and the package body of wide 100mm.
Heat-sealing temperature 120 DEG C
0.6 second heat-sealing time
Heat-sealing pressure 0.5MPa
In the part of the sack top 30mm that package body distance obtained above is heat-sealed, divide with the finger tip of the right hand and left hand
Will not seal and opposed composite membrane two surface maintains, break a seal with staff.
According to following benchmark evaluation thoughts and feelings (peeling off sense) now, as the index of release performance.
A: the situation (the best) that can easily and successfully peel off
B: slightly resist the situation (well) felt but can be easily peeled off
Slightly larger but strippable situation is felt in C: opposing (can)
D: the situation (bad) being partially destroyed beyond situation about can not peel off or heat-sealing portion
(9) tear Kaifeng property
Tear Kaifeng property after investigating heat-sealing between the hot sealing layer of 2 composite membranes.
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) peace field essence mechanism to make made YSS heat sealing machine, under the following conditions by 4 limit heat-sealings, obtained simulation system
Bag.4 limits of this simulation bag body are heat sealed to end.
Heat-sealing temperature: 160 DEG C
Seal pressure: 0.1MPa
The heat-sealing time: 1.0 seconds
Sealed width: 5mm
In a piece of heat-sealing portion of obtained simulation bag body, cutter are used vertically to cut out 10mm from end
Cut channel, this cut channel portion is transversely torn with hand (with the vertical direction, parallel and with cut channel direction, face of simulation bag body)
Split, investigate the state of the power needed for this tear and tearing part, judge by following benchmark, commented by following calculating formula
Valency.
Linearly cut off from cut channel by light power, without the stretching of film and grain raising etc.: A (the best)
Slightly feel weight during tear, but cut off as the crow flies: B (well)
Feel during tear to weigh very much, the film stretching of cut-out, grain raising: C (bad)
Film stretches from cut channel, is not cut off: D (the worst)
Test and carried out by 3 each personal 10 test films of laboratory technician, the ratio being judged to " A " in 30 test films will be added up to
It is expressed as a percentage by following mathematical expression (1) and evaluates.
It is judged to ratio (%)=(being judged to number ÷ 30 of " A ") × 100...... (1) of " A "
(10) resistance to pinprick
As the index of the resistance to pinprick in heat-sealing portion, carry out the crank detection test in heat-sealing portion.
Composite membrane is cut out the rectangle of 150mm × 100mm, right in the central authorities of minor face in the way of hot sealing layer becomes inner side
Folding.Using in short side part while remaining as opening portion, to remaining both sides (rim portion in minor face and long limit), use
(strain) peace field essence mechanism is made made YSS heat sealing machine and is sealed by following condition, obtains the simulation bag body of sealed tube shape.
Heat-sealing temperature: 160 DEG C
Seal pressure: 0.1MPa
The heat-sealing time: 1.0 seconds
Sealed width: 5mm
From the opening portion of this simulation bag body, the dyeing of (strain) タ セ ト is impregnated with flaw detection agent and " is impregnated with liquid FP-S mark
Pseudotype " spraying, visual observations, from the liquid leak condition of sealing, is evaluated by following benchmark.
Liquid is not had to leak from heat-sealing portion: zero (resistance to pinprick is good)
Liquid is had to leak from heat-sealing portion: × (resistance to pinprick is bad)
Embodiment 1
The manufacture ＞ of ＜ multilayer film
Use by the single screw extrusion machine 1 of screw diameter 75mm in intermediate layer, two outer layers (laminate layers and hot sealing layer)
T-shaped die head formulas thin of these 3 kinds 3 layers compositions of totally 3 extruders composition of single screw extrusion machine 2 of screw diameter 50mm
Film film forming apparatus, supplies resin in the following manner with each extruder.
Intermediate layer extruder: b-LLDPE-1 (make, model: CU7004, fusing point=108 DEG C, MFR=by Sumitomo Chemical (strain)
3.0g/10 minute (190 DEG C), Mw/Mn=11.9, density=0.924g/cm3, amorphism composition=2.5 weight %, long-chain
Branching content=4.12/1,000C) 100 weight portions
Laminate layers extruder: PP-1 (Japan's Port リ プ ロ (strain) system, model: WFX4TA, fusing point=126 DEG C, MFR=
7.0g/10 minute (230 DEG C), Mw/Mn=3.0) 70 weight portions and PP-2 (Japan's Port リ プ ロ (strain) system, model: FW3GT,
Fusing point=148 DEG C, MFR=7.0g/10 minute (230 DEG C), Mw/Mn=5.3) mixture of 30 weight portions
Hot sealing layer extruder: PP-1 (Japan's Port リ プ ロ (strain) system, model: WFX4TA, fusing point=126 DEG C, MFR=
7.0g/10 minute (230 DEG C), Mw/Mn=3.0) 100 weight portions
Each, all at resin temperature 220 DEG C, 1 minute holdup time, T-shaped die head temperature 230 DEG C for 3 extruders
Under conditions of from each T-shaped die head extrude, by the chill roll of 3 layers of merga pass 25 DEG C, obtain multilayer film.This multilayer film is 3 layers of structure
Becoming, gross thickness is 30 μm, and the thickness of 3 layers constitutes substantially 1:2:1.
Then, Corona discharge Treatment is implemented, so that the wetting tension on the surface of the laminate layers side of this multilayer film is 42mN/m,
And then at 40 DEG C, carry out 24 hours burin-in process, obtain the non-stretched multilayer film of polyolefin.
Use the non-stretched multilayer film of this polyolefin, carry out above-mentioned (1)～the evaluation of (6).Evaluation result is shown in table 5.
The manufacture ＞ of ＜ composite membrane
It is that the face of the laminate layers of non-stretched multilayer film is attached on biaxial-stretched polypropylene films by said polyolefins, manufactures multiple
Close film.
Biaxial-stretched polypropylene films that サ Application ト ッ Network ス (strain) is made (model: サ Application ト ッ Network ス-OP PA20, thickness:
20 μm, one side sided corona treatment product) sided corona treatment face, (will with spreader (being set as 2 mils) coating dry lamination adhesive
Host (model: the TM-595) 15g that Japan モ ト Application (strain) makes, same company curing agent (model: CAT-56) 2.7g and
The solution that ethyl acetate 36.8g mixes), it is dried 1 minute at 80 DEG C.Then, on this adhesive phase, obtain above-mentioned
The laminate layers hand pressure roller of the non-stretched multilayer film of polyolefin extrude while being laminated, then at 40 DEG C aging 3 days, by
This obtains composite membrane.Being explained, above-mentioned unit " mil " refers to 0.001 inch, and 1 mil corresponds approximately to 25.3995 μm.
Use composite membrane obtained above, carry out above-mentioned (7)～the evaluation of (10).Evaluation result is shown in table 5.
Embodiment 2～10 and comparative example 1～4
In above-described embodiment 1, except making the kind of the resin of supply each layer extruder and use level respectively such as table 3 He
Beyond as shown in table 4, manufacture the non-stretched multilayer film of polyolefin and composite membrane similarly to Example 1, carry out respectively
Evaluate.
Evaluation result is shown in table 5 and table 6.
Being explained, the abbreviation of the resin raw material in table 3 and table 4 is respectively following meanings.
B-LLDPE-1: Sumitomo Chemical (strain) is made, model " CU7004 "
B-LLDPE-2: Sumitomo Chemical (strain) is made, model " GT140 "
B-LLDPE-3: Sumitomo Chemical (strain) is made, model " GH051 "
LLDPE-1: space portion ball is apt to polyethylene (strain) system, model " 1540F "
LLDPE-2: space portion ball is apt to polyethylene (strain) system, model " 2040FC "
LLDPE-3: DOW Chemical Japan (strain) system, model " KC8852G "
LDPE-1: Sumitomo Chemical (strain) is made, model " L405 "
PP-1: Japan's Port リ プ ロ (strain) system, model " WFX4TA "
PP-2: Japan's Port リ プ ロ (strain) system, model " FW3GT "
The parameter of above-mentioned resin raw material is shown in following table 7.
The numerical value on the MFR hurdle of table 7 is the melt flow rate (MFR) measured according to JIS K 7210 load 2.16kg.Measure temperature
Degree, for polyethylene-based resin, is 190 DEG C；For polypropylene-based resin, it it is 230 DEG C.
The peak temperature of the fusing point fusing point for measuring with differential scanning calorimeter (DSC).
The content of the long chain branch shown in " long chain branching " hurdle is to be measured by by following condition13The result of C-NMR, according to
The side chain number of the carbon number more than 8 in every 1,000 carbon atoms that following mathematical expression (2) calculates.
[13C-NMR condition determination]
Determinator: NEC's (strain) makes, model " JNM-ECS400 "
Solvent: the mixed solvent (75/25 volume %) of trichloro-benzenes/heavy benzol
Sample solution concentration: 80mg/2.5mL solution
Mode determination: 1H-decouples completely
Mensuration temperature: 120 DEG C
Pulse width: 90 degree of pulses
Pulse-recurrence time: 9 seconds
Cumulative number: 9,000 times
Long chain branch content (individual/1000C)=A ÷ B × 1,000 (2)
(in mathematical expression (2), A is the peak area of chemical shift δ=22.87ppm；B is the face, peak of chemical shift δ=30ppm
Long-pending.)
Noncrystalline component content is in temperature rising elution fraction under the following conditions, and the post after being supplied by sample is cooled to
It is initially supplied solvent after 0 DEG C, maintains fraction that period of 0 DEG C elutes relative to the weight ratio shared by whole fractions at column temperature
Example.
Determinator: (strain) セ Application シ ュ section length of schooling, model " TREF device special type "
Post: internal diameter 10mm × 300mm
Filler: Network ロ モ ソ Le Block P NAW (ジ エ Le サ イ エ Application ス (strain) makes, 30/60 mesh)
Sample solution concentration: 5mg/mL
Sample solution injection rate: 2mL
Solvent: o-dichlorohenzene
Flow velocity: 1mL/min
Sample implantation temperature: 140 DEG C
Cooling rate: 5 DEG C/h
Cooling arrival temperature: 0 DEG C
Holding time of cooling arrival temperature: 30 minutes
Programming rate: 5 DEG C/h
Detector: infrared detector
Mensuration wave number: 3.42 μm
Invention effect
The present invention provides each characteristics such as a kind of optical characteristics, resistance to blocking, low temperature heat seal, heat seal strength, sealing equal
The non-stretched multilayer film of polyolefin that excellence, the tear Kaifeng property simultaneously packed and release performance are also excellent.
The package body formed by multilayer film of the present invention is particularly suitable in such as packaging for foodstuff purposes etc..
Claims (6)
1. multilayer film, it is for having as outermost laminate layers, at least 1 layer of intermediate layer and as another outermost hot sealing layer
The non-stretched multilayer film of polyolefin, it is characterised in that
Above-mentioned laminate layers contains polyolefin-based resins,
At least 1 layer of above-mentioned intermediate layer comprises the polyolefin-based resins containing long chain branching LLDPE,
Above-mentioned hot sealing layer comprises the polyolefin-based resins containing polypropylene-based resin,
The fusing point of the polyolefin-based resins of above-mentioned laminate layers is higher than the fusing point of the polypropylene-based resin in above-mentioned hot sealing layer,
Long chain branching LLDPE in polyolefin-based resins in above-mentioned intermediate layer use that gel permeation chromatography measures by polyphenyl
Weight average molecular weight Mw of ethene conversion is 7.5～15.0 with the ratio Mw/Mn of number-average molecular weight Mn,
The amorphism component amount using temperature rising elution fraction to measure is 1～4 weight %, and uses13The carbon that C-NMR measures
The side chain number of several more than 8 is to have 1.5～5.0 in every 1000 carbon atoms.
2. the multilayer film described in claim 1, wherein, the long chain branching LLDPE in the polyolefin-based resins in above-mentioned intermediate layer
Density be 0.90～0.94g/cm3,
Melt flow rate (MFR) MFR measured by load 2.16kg at 190 DEG C according to JIS K 7210 is 0.1～20g/10 to divide
Clock.
3. the multilayer film described in claim 1 or 2, wherein, the polyolefin-based resins in above-mentioned intermediate layer contain 40 weight % with
On above-mentioned long chain branching LLDPE, the polypropylene-based resin below 30 weight % and the LLDPE below 50 weight %, but do not wrap
Include above-mentioned long chain branching LLDPE.
4. the multilayer film described in claim 1 or 2, wherein, molecular weight distribution Mw/ of the polypropylene-based resin in above-mentioned hot sealing layer
Mn is 1.5～3.5, according to JIS K 7210 at 230 DEG C with load 2.16kg measure melt flow rate (MFR) MFR be 1～
30g/10 minute, fusing point was 120～140 DEG C, and was polymerized containing use metallocene series catalysts more than 70 weight %
Propylene-ethylene copolymers.
5. composite membrane, it is formed by the laminate layers of the multilayer film described in any one of Claims 1 to 4 of fitting on film base material.
6. package body, it comprises the composite membrane described in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-257346 | 2013-12-12 | ||
| JP2013257346 | 2013-12-12 | ||
| PCT/JP2014/082906 WO2015087990A1 (en) | 2013-12-12 | 2014-12-05 | Polyolefin-based unstretched multilayer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105793037A true CN105793037A (en) | 2016-07-20 |
Family
ID=53371288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480061423.2A Pending CN105793037A (en) | 2013-12-12 | 2014-12-05 | Polyolefin-based unstretched multilayer film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6457402B2 (en) |
| KR (1) | KR20160096589A (en) |
| CN (1) | CN105793037A (en) |
| TW (1) | TW201538324A (en) |
| WO (1) | WO2015087990A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142897A (en) * | 2019-09-25 | 2020-12-29 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6032450B1 (en) * | 2015-12-25 | 2016-11-30 | 一夫 菱沼 | Method for selecting a sealant layer in a substrate |
| JP6808957B2 (en) * | 2016-03-30 | 2021-01-06 | 凸版印刷株式会社 | Film for packaging material, packaging material and packaging material using this |
| JP6843529B2 (en) * | 2016-06-14 | 2021-03-17 | 株式会社プライムポリマー | Polypropylene resin composition for sealant |
| JP6764754B2 (en) * | 2016-10-18 | 2020-10-07 | サン・トックス株式会社 | Stretched polypropylene film |
| KR20210012996A (en) * | 2018-05-21 | 2021-02-03 | 도레이 필름 카코우 가부시키가이샤 | Polypropylene composite film and packaging material using the same |
| JP7306098B2 (en) * | 2019-06-21 | 2023-07-11 | Dic株式会社 | Laminated films and packaging materials |
| WO2023129078A1 (en) * | 2021-12-29 | 2023-07-06 | Korozo Ambalaj Sanayi Ve Ticaret A.S. | A packaging film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003011301A (en) * | 2001-06-29 | 2003-01-15 | Grand Polymer Co Ltd | Multi-layer film of polypropylene resin |
| JP2008238532A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Chemical Co Ltd | Multi-layer film and bag |
| JP2011194642A (en) * | 2010-03-18 | 2011-10-06 | Sumitomo Chemical Co Ltd | Method of manufacturing polyethylene film |
| CN102234391A (en) * | 2010-04-23 | 2011-11-09 | 住友化学株式会社 | Film made via polyethylene system resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482532B1 (en) * | 2000-06-07 | 2002-11-19 | Dow Global Technologies Inc. | Easy tear non-halogenic food wrap |
| JP5158605B2 (en) * | 2009-03-17 | 2013-03-06 | サン・トックス株式会社 | Packaging material |
-
2014
- 2014-12-05 CN CN201480061423.2A patent/CN105793037A/en active Pending
- 2014-12-05 KR KR1020167011591A patent/KR20160096589A/en not_active Application Discontinuation
- 2014-12-05 JP JP2015552524A patent/JP6457402B2/en active Active
- 2014-12-05 WO PCT/JP2014/082906 patent/WO2015087990A1/en active Application Filing
- 2014-12-10 TW TW103143052A patent/TW201538324A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003011301A (en) * | 2001-06-29 | 2003-01-15 | Grand Polymer Co Ltd | Multi-layer film of polypropylene resin |
| JP2008238532A (en) * | 2007-03-27 | 2008-10-09 | Sumitomo Chemical Co Ltd | Multi-layer film and bag |
| JP2011194642A (en) * | 2010-03-18 | 2011-10-06 | Sumitomo Chemical Co Ltd | Method of manufacturing polyethylene film |
| CN102234391A (en) * | 2010-04-23 | 2011-11-09 | 住友化学株式会社 | Film made via polyethylene system resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142897A (en) * | 2019-09-25 | 2020-12-29 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
| CN112142897B (en) * | 2019-09-25 | 2021-07-27 | 中国科学院化学研究所 | Application of organosilane in preparation of linear low density polyethylene, linear low density polyethylene and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015087990A1 (en) | 2015-06-18 |
| JP6457402B2 (en) | 2019-01-23 |
| JPWO2015087990A1 (en) | 2017-03-16 |
| TW201538324A (en) | 2015-10-16 |
| KR20160096589A (en) | 2016-08-16 |
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Application publication date: 20160720 |