CN101213077A - Polyethylenic resin laminated film - Google Patents

Polyethylenic resin laminated film Download PDF

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Publication number
CN101213077A
CN101213077A CNA200680023975XA CN200680023975A CN101213077A CN 101213077 A CN101213077 A CN 101213077A CN A200680023975X A CNA200680023975X A CN A200680023975XA CN 200680023975 A CN200680023975 A CN 200680023975A CN 101213077 A CN101213077 A CN 101213077A
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CN
China
Prior art keywords
film
density
layer
resin
laminated film
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CNA200680023975XA
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CN101213077B (en
Inventor
大野真一
渡边哲也
小田尚伸
久世胜朗
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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

Abstract

The present invention provides a polyethylene resin laminate film, more specifically a polyethylene resin film having a good balance of heat-sealing property and stiffness of the film, having less fish-eyes, having little fisheyes and also having less unevenness in thickness. [MEANS FOR SOLVING PROBLEMS] A polyethylene resin laminate film having at least a laminate layer (A) and a seal layer (B), the laminate layer (A) comprising at least two polyethylene resins each having a density of 900 to 970 kg/m<3> and a molecular weight distribution (Mw/Mn) of 2.0 to 3.5, the densities of the at least two polyethylene resins being different from each other, the average density of the laminate layer being 920 to 945 kg/m<3>, the seal layer (B) comprising a polyethylene resin having a density of 900 to 930 kg/m<3>, and the average density of the laminate layer (A) being larger than that of the seal layer (B).

Description

Polyethylenic resin laminated film
Technical field
The present invention relates to a kind of polyethylenic resin laminated film.More specifically, relate to and a kind ofly can obtain the balance of heat sealability, resistance to blocking and film rigidity and white point is few, the thickness spot of film is few polyethylene-based resin film.
In addition, the invention still further relates to a kind of independence (corresponding Japanese: independence) container polyethylenic resin laminated film.More specifically, relate to and a kind ofly can obtain the balance of heat sealability, resistance to blocking and film rigidity and white point is few, the thickness spot of film is few independence container polyethylene-based resin film.
Background technology
Heat sealability, the resistance to impact of polyethylene-based resin film are outstanding, are widely used in the packing or the container of food or sundry goods etc.
In recent years, owing to convenience, resource-saving, attenuating use the packing of film or container to be used in extensive fields to carrying capacity of environment etc.Compare with forming containers such as blow molding bottle in the past, have light-duty, easy waste treatment, advantage that circulation cost is cheap.
In heat sealability polyethylene-based resin film, the stacked polyethylene-based no oriented film of the balance that can obtain heat sealability and resistance to blocking is disclosed.(for example with reference to patent documentation 1 etc.).
Patent documentation 1: No. 3291969 communique of patent
In recent years, along with consumer's safe pointing becomes strongly,, the market demands of the foreign matter that contains in the film are also being become strict even in this heat sealability polyethylene-based resin film.
For example, as be used as under the situation of inner layer material of wrapper, can not see in the normal state even begin to occur the consumer, but wrapper is opened by tearing for recovery, thereby the consumer see the phenomenons such as worry of arousing security.In addition, as under the situation of transparent wrapper bag, because the color or the form of content, the white point as the piece of the little spherical shape that produces in the goods of film etc. becomes very significantly foreign matter sometimes.Since these market demands, and must carry out strict control.Particularly since this white point mainly constitute by the insoluble matter of polymer or gelling material etc., in the method that the use filter filters in film making process that can be used as the scheme that lowers foreign matter content, the composition that forms this white point deforms when filtering sometimes and by filter, is not effective means sometimes.
In addition, in recent years, for the heat sealability film, also more and more stricter about the market demands of the thickness spot of this film.If the change of the thickness spot of film is big, then owing to film is being the phenomenon of crispaturaing that takes place when the roller shape is preserved, the thickness spot of film can cause problems such as relaxing of film.So, under the situation of the big film of thickness spot, for example be used as under the stacked raw-material situation, add man-hour stacked, the lax distortion that waits causes the generation of gauffer or being involved in of air, so the process operation reduction, and may cause the bad order of gauffer, speculum etc. of the goods that obtain or stacked intensity change etc.
Disclosed stacked polyethylene-based no oriented film in described patent documentation 1 grade, in the balance of heat sealability and resistance to blocking, can satisfy the market demands of height, but about described white point or thickness spot, height market demands in recent years relatively, sometimes can not satisfy market demands fully, expect its improvement strongly.
In addition, the independence container is developed into one of purposes of heat sealability polyethylene-based resin film with raw material.Even as these independence container raw material, the also described market demands of strong request.Particularly in recent years, not only in toilet articles for use (ト イ レ リ one) field, and increasing carrying out also of beverage or field of food, about this quality, higher requirement is becoming strong.
The heat sealability polyethylene-based resin film that uses in the independence container is used must have characteristics such as heat sealability or resistance to blocking, but also need the essential characteristics of independence container such as rigidity or impact strength, disclose the improvement technology (for example with reference to patent documentation 2,3 etc.) of this characteristic.
Patent documentation 2: the spy opens flat 9-235425 communique
Patent documentation 3: the spy opens the 2000-238212 communique
But, in these patent documentations, in the disclosed polyethylene-based resin film, utilize the manufacturing of inflation film system embrane method, can not satisfy requirement fully to the thickness spot of film.In addition, also do not consider the attenuating of white point fully.
In addition, the independence container is with compound uses of other raw material such as polyethylene-based resin film and polyester films, to the requirement of the productivity ratio of the processing ease degree of the film in the manufacturing procedures such as for example stacked processing in this compoundization or processing also at High Level.
Summary of the invention
The present invention proposes as a setting with the problem of conventional art just, relates to polyethylenic resin laminated film.More specifically, provide a kind of balance of the rigidity that can obtain heat sealability, resistance to blocking and film and the polyethylene-based resin film that white point is few, the thickness spot is few.
In addition, the present invention also provides a kind of balance of the rigidity that can obtain heat sealability, resistance to blocking and film and the independence container polyethylene-based resin film that white point is few, the thickness spot is few.
The inventor etc. concentrate on studies in order to solve described problem, and the result is so that finish the present invention.Promptly, the present invention is a kind of polyethylenic resin laminated film, it is characterized in that, it is the polyethylenic resin laminated film that is made of layer laminate (A) and sealant (B) at least, satisfy condition as described below simultaneously, that is: layer laminate (A) is that the two or more density of cooperation are 900～970kg/m 3And molecular weight distribution (Mw/Mn) is that 2.0～3.5 the different polyvinyl resin of density forms, and its averag density is 920～945kg/m 3, sealant (B) is 900～930kg/m by density 3Polyvinyl resin constitute, and the averag density of layer laminate (A) is greater than the averag density of sealant (B).
In this case, the maximum gauge of preferred described film is that the above white point of 0.2mm is 5/1000cm 2Below.
In addition, in this case, the thickness spot of the width of preferred described film is in 7%.
And then in addition, in this case, preferably being provided with by averag density between the layer laminate (A) of described film and sealant (B) is 900～935kg/m 3The intermediate layer (C) that constitutes of polyvinyl resin form.
And then in addition, in this case, the averag density of the polyvinyl resin of described each layer of preferred described film is layer laminate (A)＞intermediate layer (C) 〉=sealant (B).
And then, in addition, in this case, preferably in the intermediate layer of described film (C), cooperate 10～30 quality % to reclaim resin and form.
And then in addition, in this case, the preferred spherical inorganic particulate of 0.5～1.5 quality % average grain diameter, 5～13 μ m and the non-spherical inorganic particulate of 0.1～1.0 quality % average grain diameter, 1～6 μ m of cooperating in the sealant (B) of described film at least forms.
And then in addition, in this case, the present invention is characterised in that for a kind of the gross thickness of described film is the independence container polyethylenic resin laminated film of 90～150 μ m.
Polyethylenic resin laminated film of the present invention can obtain the balance of heat sealability and film rigidity and white point is few and the thickness spot is few, so for example can be preferred in the independence container purposes such as food or sundry goods.
The specific embodiment
Below the present invention is described in detail.
The inventor etc. are in the disclosed stacked polyethylene-based no oriented film in described patent documentation 1 grade, on the balance basis of the rigidity of keeping heat sealability, resistance to blocking and film that this method has, the method that solves described problem is concentrated on studies, so that finish the present invention.Promptly, the present invention finds by using HMW body and the narrow polyvinyl resin of molecular weight distribution in the polyvinyl resin that is beneficial to very much the raw material that generates as white point, can suppress the generation of white point effectively, also find by using the narrow polyvinyl resin of this molecular weight distribution, can improve the deterioration of the thickness spot etc. of the film that the reduction of the melt fluidity of this resin causes, by cooperating the different two or more polyvinyl resin of density can improve white point, finished the method that can obtain the few and polyethylene-based laminate film that the thickness spot is few of white point on the basis of well-known features in the past keeping.
Polyethylenic resin laminated film of the present invention is the polyethylenic resin laminated film that is made of layer laminate (A) and sealant (B) at least, it satisfies condition as described below simultaneously is very important, that is: layer laminate (A) is that the two or more density of cooperation are 900～965kg/m 3And molecular weight distribution (Mw/Mn) is that 2.0～3.5 polyvinyl resin forms, and its averag density is 920～945kg/m 3, sealant (B) is 900～930kg/m by density 3Polyvinyl resin constitute, and the averag density of layer laminate (A) is greater than the averag density of sealant (B).
By becoming the duplexer of layer laminate (A) and sealant (B), can obtain the balance of strong ductility etc. etc., this strong ductility has influence on for be the resistance to blocking of the film of important characteristic or the damage resistibility of rigidity and sack etc. for the low-temperature heat-sealing of the necessary characteristic of heat sealability film, the operability of film etc.
In the present invention, preferably to cooperate two or more density be 900～970kg/m to layer laminate (A) 3And molecular weight distribution (Mw/Mn) is that 2.0～3.5 the different polyvinyl resin of density forms, and its averag density is 920～945kg/m 3By this reply, can give characteristics such as strong ductility, this strong ductility has influence on for the operability of film etc. and to be the rigidity of the film of important characteristic and the damage resistibility of sack etc., and the generation inhibition of described white point and thickness spot lower and become possibility.
Density is less than 900kg/m 3Polyvinyl resin because himself processing variation, so be not suitable for.In addition, density is greater than 970kg/m 3Polyvinyl resin owing to be difficult to polymerization, so be difficult to obtain, be not suitable for.The density range of the material polyethylene resin that uses in cooperation is 905～965kg/m more preferably 3, and then be preferably 910～960kg/m 3
The polyvinyl resin preferred molecular weight distribution of using in this cooperation (Mw/Mn) is 2.0～3.5.More preferably 2.2～3.3, and then be preferably 2.4～3.1.If use molecular weight distribution (Mw/Mn) is less than 2.0 polyethylene-based resin, then because the resin flow characteristic during fusion causes the generation of the width of cloth that contracts (neckin) etc., the difficulty so the steady production in the thin film fabrication becomes causes the deterioration of the thickness spot etc. of film.In addition, if use molecular weight distribution greater than 3.5 polyvinyl resin, then the generation of the white point that causes of HMW body increases, so be not suitable for.
In the present invention, the different polyvinyl resin of density that preferably cooperates two or more described density ranges.By this reply, as mentioned above, can reduce the white point that the high molecular weight components of described polyvinyl resin causes.Its reason is that under the situation of the polyvinyl resin that density is identical, if the density of resin uprises, then there is the trend that increases in the HMW body.Thereby the density of resin is high more, and then white point increases more.So, can infer, be that the situation of the single polyvinyl resin of equal densities is compared with mixture, it is low and polyvinyl resin that white point is few and density are high and have the situation of the polyvinyl resin of white point to mix two or more density, and its white point is still less.The density contrast of the resin during this is cooperated is unqualified, preferably gets poor more than 0.015.More preferably get poor more than 0.020.By this reply, the white point of the hybrid resin of cooperation tails off, so can realize effect of the present invention.
In addition, by this reply, can suppress the deterioration that reduction as the melt fluidity of this resin of the problem of using the narrow polyvinyl resin of described molecular weight distribution to cause makes the thickness spot etc. of film.Its reason it be unclear that, and can infer, the density contrast of resin has improved the melt flow characteristics such as dynamic viscosity of molten mass effectively.
In the present invention, the preferred averag density of described cooperation becomes 920～945kg/m 3925～940kg/m more preferably 3, and then be preferably 930～935kg/m 3Averag density is less than 920kg/m 3The time, the rigidity of laminate film reduces, and operability reduces, so not preferred.On the contrary, surpass 945kg/m 3Situation under, white point increases, so not preferred.
In addition, on the contrary, surpass 945kg/m 3Situation under, although the rigidity of film improves, independence improves, so the damage resistibility variation of the sack of film is not preferred.
Match ratio to the polyvinyl resin in the described cooperation is not particularly limited, and the polyvinyl resin that density is high is compared with low density polyvinyl resin, and the visible degradating trend of the generation of white point is so preferably reduce the use level of the high polyvinyl resin of density.In order to reduce the use level of the high polyvinyl resin of density as much as possible, preferably use the high as far as possible resin of density.For example, respectively with 5～15: 95～85 ratio (mass ratio) cooperates density height to 955～970kg/m 3Polyvinyl resin and density be low to moderate 900～935kg/m 3Polyvinyl resin, most preferred embodiment becomes 930～935kg/m for making averag density 3By this cooperation, can realize effect of the present invention effectively.
In the present invention, be 900～930kg/m by density preferably as another sealant (B) that constitutes layer 3Polyvinyl resin constitute, and the averag density of layer laminate (A) is greater than the averag density of sealant (B).By this reply, can obtain the balance of the rigidity of the low temperature seal of laminate film and film.The density of the polyvinyl resin of formation sealing layer (B) is 910～925kg/m more preferably 3Density is less than 900kg/m 3The time, adhesive worsens.On the contrary, if surpass 930kg/m 3, low temperature seal variation then.The polyvinyl resin that constitutes sealing layer (B) can be single system, also can similarly be the two or more systems that cooperates with layer laminate (A).Under the situation of the polyvinyl resin of formation sealing layer (B), because density is low, so compare with described layer laminate, molecular weight distribution diminishes to the influence of white point.
In the present invention, gross thickness is preferably 90～150 μ m.In the film that uses in the internal layer of independence container, if thickness is thinner than 90 μ m, then the damage resistibility deficiency of independence or sack has problems.In addition, flexible not enough if thickness is thicker than 150 μ m although then the damage resistibility of independence or sack improves, be difficult to operate the problem that becomes the independence container so exist.
Utilize described formation, can give characteristics such as strong ductility, this ductility has influence on for the operability of independence container film etc. and to be the rigidity of the film of important characteristic and the damage resistibility of sack etc., and the generation inhibition of described white point and thickness spot lower and become possibility.
Preferably satisfy above-described constitutive requirements simultaneously.By this reply, can realize effect of the present invention effectively.
In the present invention, also can between above layer laminate (A) and sealant (B), intermediate layer (C) be set.By this reply, the balance that obtains the various characteristics of laminate film becomes easier, so preferred.
The averag density that constitutes the polyvinyl resin in described intermediate layer (C) is 900～935kg/m 3, and the averag density of the polyvinyl resin of described each layer is preferably layer laminate (A)＞intermediate layer (C) 〉=sealant (B).This density is 910～925kg/m more preferably 3The polyvinyl resin that constitutes this intermediate layer (C) can be single system, also can similarly be the two or more systems that cooperates with layer laminate (A).Constitute under the situation of polyvinyl resin in this intermediate layer (C), because density is low, so molecular weight distribution becomes less than described layer laminate to the influence of white point.
The polyvinyl resin that constitutes this intermediate layer (C) can be single system, also can similarly be the two or more systems that cooperates with layer laminate (A).Preferred interlayer (C) is for cooperating two or more 900～970kg/m 3And molecular weight distribution (Mw/Mn) is that 2.0～3.5 the different polyethylene of density forms, and its density is 920～945kg/m 3
Density is less than 900kg/m 3Polyvinyl resin owing to himself do not have rigidity, be not suitable for.The density range of the material polyethylene resin that uses in cooperation is 905～965kg/m more preferably 3, and then be preferably 910～960kg/m 3
The polyvinyl resin preferred molecular weight distribution of using in this cooperation (Mw/Mn) is 2.0～3.5.More preferably 2.2～3.3, and then be preferably 2.4～3.1.
In the present invention, preferably in described intermediate layer (C), be used the recovery resin that takes place in the manufacturing process at polyethylene-based laminate film of the present invention.By this reply, can lower the manufacturing cost of laminate film.In addition, can also suppress the variation of quality of the laminate film that the change of the usage ratio of this recovery resin causes.Under the situation with this method enforcement, the management of reclaiming resin also is the key factor that white point suppresses.Under many situations, utilize goods again, cut bits etc., in raw material, mix and use.Known have: these goods of fusion, cut bits etc., become the method for resin ball; Utilize pressure, under pressure, make these goods, cut bits etc. and become ball shape, tabular method; Under the semi-molten state, become the method for ball shape.Utilize fusion become the ball shape method since under the effect of heat fusion become ball, so in the inner cross-linking reaction that takes place of resin, the result becomes white point takes place easily.The method of utilizing pressure to become ball is unsuitable for soft film, even become ball, the strength of shape that reverts to original film is very strong, and along with the process of time, shape changes sometimes, is difficult to management.The method that becomes ball under the semi-molten state can not change along with the process of time like that, for homogeneous, be difficult to take place white point, so preferred.
Management attached to the dust on the goods that reclaim, the incision bits, foreign matter, thin rubbish etc. is also very important.If become the recovery raw material adhering under the states such as these dust, foreign matter, thin rubbish, then they can become nuclear, and white point takes place.Certainly it is very important reclaiming indoor air conditioning managing, and the effort that does not allow the raw material that is attached with dust, foreign matter, thin rubbish enter on the line of recovery is very important.As this method, preferably in clean room (clean room), carry out reclaimer operation.In addition, preferably electrostatic removal device is installed in order to remove the dust that is attached to film, foreign matter, thin rubbish at the retracting device inlet.
The polyethylene-based resin of Shi Yonging is preferably linear low density of polyethylene in the present invention.Linear low density of polyethylene is that 3～12 alpha olefin copolymer constitutes by ethene and carbon number, preferably carbon number is chosen in 4～8 the scope.As the concrete example of these combined polymerization compositions, can enumerate propylene, butene-1, amylene-1, hexene-1, heptene-1, octene-1, nonylene-1, decylene-1, laurylene-1,4-methyl-amylene-1,4-methyl-hexene-1 etc.
Manufacture method to described linear low density of polyethylene is not particularly limited, and can use and utilize so-called aromatic ring alkene metal derivative series catalysts such as Ziegler-sodium tower series catalysts or cyclopentadienyl-containing metal compound or non-aromatic cyclenes metal derivative is the linear low density of polyethylene that the method manufacturing such as solution polymerization process, slurry polymerization process, mass polymerization, solution polymerization process of the complex series catalysts of complex etc. forms.To the control method of the molecular weight distribution of the polyvinyl resin that constitutes layer laminate (A), unqualified.For example can use the polyvinyl resin of controlling molecular weight distribution of the complex series catalysts manufacturing that utilizes aromatic ring alkene metal derivative series catalysts or non-aromatic cyclenes metal derivative complex etc., also can wash-out tell the polyvinyl resin of general usefulness.
In addition, preferably in polyethylene-based resin, cooperate antioxidant, can and with phenol system or phosphate system or use the antioxidant that in a part, has phenol system and phosphate pastern bone frame separately.
In the present invention, preferably in sealant (B), cooperate the spherical inorganic particulate of 0.5～1.5 quality % average grain diameter, 5～13 μ m and the non-spherical inorganic particulate of 0.1～1.0 quality % average grain diameter, 1～6 μ m to form at least.By this reply, can keep low temperature seal, can give the anti-stick effect that connects of height.
Its reason may be, by cooperating inorganic particulate, forms projection at film surface, so the contact area of film reduces, the result can obtain the anti-stick effect that connects.And then, cooperate particle diameter or variform inorganic particulate in the recess of film surface, also to form complicated projection, obtain the higher anti-stick effect that connects.In addition, as required, described inorganic particulate also can be engaged among layer laminate (A) or intermediate layer (C).
By cooperating the spherical inorganic particulate of average grain diameter 5～10 μ m, can form high projection at film surface, by cooperating the non-spherical inorganic particulate of average grain diameter 1～6 μ m, can form low projection at film surface.Compare with the film that has the projection of equal height at film surface, the resistance to blocking of film of projection that has differing heights at film surface is outstanding.
The use level of the spherical inorganic particulate of average grain diameter 5～10 μ m is preferably 0.5～1.5 quality %.If use level is less than 0.5 quality %, then resistance to blocking deficiency.In addition, if use level more than 1.5 quality %, the transparent variation of film then.The use level of the non-spherical inorganic particulate of average grain diameter 1～6 weight % is preferably 0.1～1.0 quality %.If use level is less than 0.1 quality %, then resistance to blocking deficiency.In addition, if use level greater than 1.0 quality %, the transparent variation of film then.
Composition to the spherical inorganic particulate of 5～13 μ m is unqualified, preferred silica or zeolite etc.And then preferred surface is the narrow spherical inorganic particulate of aporate, size distribution.Its reason is that the surface is under the cavernous situation, under the influence of the moisture that is attached to inorganic particulate, and film foaming sometimes, degraded appearance.In addition, if size distribution is wide, then in the manufacturing of film, inorganic particulate is piled up in the lip of T die head sometimes, hinders productivity ratio.Composition to this non-spherical inorganic particulate is also unqualified, preferred diatomite or talcum etc.They are compared with spherical inorganic particulate, and average grain diameter is little, and use level is also little, so even be that cellular, size distribution are wide, also can.
In the present invention, preferably in layer laminate (A), cooperate the spherical inorganic particulate of 0.1～0.8 quality % average grain diameter, 5～13 μ m to form.Average grain diameter is 7～11 μ m more preferably.In addition, use level is preferably 0.2～0.7 quality %.Low temperature seal property polyethylene resin laminated film of the present invention is soft, enters the volume gauffer easily in the operation that winding film is become the roller shape.That is, have the problem of the batching property reduction of film, it is very important satisfying described layer structure, but by described reply, can further improve the batching property of film.By satisfying described scope, taking into account the transparency of film and the batching property of film becomes possibility.For example, average grain diameter or use level surpass under the situation of the upper limit, and so the transparency deterioration of film is not preferred.On the contrary, under the situation less than lower limit, the batching property of film improve the effect deficiency, so not preferred.
The average grain diameter of inorganic particulate is measured with the laser diffraction formula particle size distribution method of JIS K 1150 records.Use Leeds﹠amp; Northrup corporate system form: Microtrac HRA model 9320-X100 measures.
In order to obtain the transparency, the preferred T die head of manufacture method method.
The poly transparency has influence on its crystalline texture.Particularly, by becoming spheroidal cementite, the transparency improves, in order to obtain spheroidal cementite, the essential cooling velocity that improves film.In inflation film process, the cooling medium are air, and are relative therewith, in T die head method, owing to use chill roll, so be the manufacture method that helps improving cooling velocity.
As the structure of polyethylenic resin laminated film, the layer of layer laminate is than being preferably 5～40%.More preferably 10～30%, and then be preferably 15～25%.If the layer ratio of layer laminate is less than 5%, then the elasticity deficiency of film according to the purposes difference, impairs important quality such as independence.If layer is than surpassing 40%, then film strength reduces, and causes the broken bag of finished product.Compare 5～40% by the layer that makes layer laminate, can obtain the elasticity of film and cooperating of film strength.
The gross thickness of polyethylene-based laminate film of the present invention is preferably 30～150 μ m.This be because, if be thinner than 30 μ m, the final packaging goods solution broken bag that becomes then, if be thicker than 150 μ m, then the final packaging goods become and are difficult to operation, convenience worsens.For example, under the situation of packaging for foodstuff, content is light-duty, so use 30～80 μ m usually.In addition, the pack that repeats of washing agent is used under the situation of standard bag sundry goods such as (stand pouch), and content is heavier, and commodity self must be supported oneself, so used thickness is 90～150 μ m.
In the present invention, preferably in hot sealing layer (B), cooperate organic lubricant 100～1500ppm at least.More preferably 200～1400ppm, and then preferred 300～1300ppm.By this reply, the lubricity of laminate film or the anti-stick effect that connects improve, and the operability of film improves.Its reason may be that organic lubricant oozes out, and is present in film surface, thereby shows lubricant effect or stripping result.Organic lubricant can be enumerated fatty acid amide, fatty acid ester.Particularly, comprise oleamide, erucyl amide, behenamide, ethylenebisoleaamide, the two oleamides of hexa-methylene, ethylenebisoleaamide etc.They can use separately, but by and with two or more, even under too harsh environment, also can keep lubricity or the anti-stick effect that connects, so preferably.For example, if erucyl amide less than 100ppm, lubricity deficiency then if surpass 1500ppm, although then can satisfy lubricity, can not satisfy the anti-stick effect that connects at high temperature.In this case, with the higher ethylenebisoleaamide of fusing point, the anti-stick effect that connects under the high temperature can be improved, lubricity and the anti-stick effect that connects can be taken into account by also.
In the present invention, preferably in hot sealing layer (B), cooperate the different two or more organic lubricant of fusing point to form at least.Have organic lubricant less than 115 ℃ fusing point by at least a cooperation 100～500ppm, the another kind of organic lubricant that cooperates 500～1500ppm to have the fusing point more than 115 ℃ can be given lubricity and resistance to blocking.
Have organic lubricant less than 115 ℃ fusing point effective aspect the lubricity of film, the organic lubricant with the fusing point more than 115 ℃ is effective aspect the resistance to blocking of film.So, compare with the film that cooperates any one organic lubricant, cooperate the film of two or more organic lubricants can make the both sides of lubricity and resistance to blocking all outstanding.
As the organic lubricant that has less than 115 ℃ fusing point, can enumerate oleamide, erucyl amide, palmitamide, stearic amide, behenamide etc.Because they move to film surface quickly, can help lubricity on a small quantity, get final product so use level is 100～500ppm.Be less than under the situation of 100ppm, the lubricity deficiency under the situation more than 500ppm, exists in film surface sometimes and separates out, and the problem of whiting occurs.
As organic lubricant, can enumerate ethylenebisoleaamide, the two oleamides of hexa-methylene, ethylenebis erucyl amide, ethylidene Shuan behenamide, ethylenebis stearic amide etc. with the fusing point more than 115 ℃.Because they move to film surface quickly, lack if cooperate, then resistance to blocking there is not benefit.Use level is that 500～1500ppm gets final product.Be less than under the situation of 500ppm, the resistance to blocking deficiency under the situation more than 1500ppm, exists in film surface sometimes and separates out, and the problem of whiting occurs.
The independence container is in the operation of filling content, and the bottom that must fold is successfully expanded, and adds insoluble matter in container.In addition, in the operation of making the independence container, transfer member successfully.So, compare with common packaging material purposes, must become the outstanding polyethylenic resin laminated film of lubricity or resistance to blocking.These can solve by described effort.
In the present invention, resistance to blocking is preferably below the 150mN/mm, and then is preferably 120mN/mm.
Can estimate resistance to blocking as described below.
In hot press (heat press) (テ ス one industry corporate system form: SA-303), the sample that overlaps between the mensuration face is carried out size 7cm * 7cm, 50 ℃ of temperature, pressure 1400Pa, the pressurized treatments of 15 minutes time.To autoplotter (Shimadzu Seisakusho Ltd. system form: UA-3122) install and finalize the design with this pressurized treatments that (diameter 6mm, material: aluminium oxide), analyzing rod is with the power of speed (200m/ branch) when peeling off setting section for the sample of (blocking) and bar (bar).In this case, prerequisite is that bar and release surface are level.To same sample determination 4 times, represent with mean value.
The preferred maximum gauge of polyethylene-based laminate film of the present invention is that the above white point of 0.2mm is 5/1000cm 2Below.4/1000cm more preferably 2Below, and then be preferably 3/1000cm 2Below.This white point surpasses 5/1000cm 2The time, for example under situation with this blister-pack, these white point naked eyes as seen, so that the commodity impression of package body reduce, so not preferred.
The attenuating of described white point can realize by satisfying described formation of the present invention, and then preferably carry out reply as described below.For example, the filter that uses in the filtration of molten resin is very important.Preferred implementation is for filtration precision being the following filter filtration of the 100 μ m resin of fusion in the melt extruded operation.At this, filter precision and be meant the performance of estimating according to the method for JIS B8356:1976 definition.Filter precision 80 μ m more preferably, and then be preferably 60 μ m.Surpass 100 μ m if filter precision, then form white point the gel foreign matter remove and microminiaturization worsens, so not preferred.The lower limit that filters precision is more less than the removing and the point of microminiaturization of gel foreign matter, and is good more, but with diminish proportionally, filter pressure drop and become big, so the essential filter area that strengthens.Thereby lower limit is preferably 30 μ m.Filter uses wire gauze filter mostly, variation according to the shape of plain weave weave, twill weave, plain weave dishes served at a feast weave (flat Tatami Woven), twill dishes served at a feast weave weaves such as (Aya Tatami Woven), the rugosity of use therein line is different with stepped construction, and filter capacity or microminiaturization effect change.Comprise the type that be called as metal sintering filter different, roughly comprise the not braided metal of powder sintered type, nonwoven and so on and make its hard type with these wire gauze filters.The not braided metal of nonwoven and so on and to make its hard type be the product that the stacked equably sintering of stainless steel fibre of micron order (microorder) forms particularly, countless contacts between the fiber make between the metal engage integrated, mesh comes off few, have high filtration precision, and compare with other metallic filter materials, voidage is big, thereby pressure drop is little, compare with woven wire, metal powder sintered filter, foreign matter hold facility height is so begin recently to be used especially widely.If wire gauze filter is also improved weave, layered manner, its equal above performance also can appear, do not get rid of.Constantly selected, the melt viscosity height of alkene, so pressure drop is low, the filter capacity height is so especially preferably select.White point is not only lowered in the employing of this scheme, but also can show the inhibition effect that thickness spot described later lowers simultaneously.The thickness spot takes place under the big situation of pressure drop easily.This be because, owing to cut down the pressure of the molten resin that the filter extruding forms, so the insufficient pressure in the T die head, the mobile of the molten resin in the T die head becomes unstable, the result becomes the thickness spot sometimes.As previously mentioned, by using the low filter of pressure drop, can suppress this phenomenon.
The more preferably embodiment of described filtration is for carrying out with the multistage filtering method that 2 above filters are set.Utilize this multistage filtering method, filter or the raising of microminiaturization efficient, and the problem of described pressure drop also is enhanced.Under the situation of this multistage filtering method, also can use and filter the identical filter of precision, but and then the value of filtering precision be reduced along the flow direction of molten resin.
In addition, the polyvinyl resin of use preferably uses and carry out inert gas replacement, the polyvinyl resin that obtains after the drying when drying.Utilize the inert gas deoxidation, the oxidation Decomposition when adding fusion in the extruder is suppressed, and causes the attenuating of white point.In addition,, preferably use inert gas replacement, make it be in the non-oxidizing state of raw material in order not enter oxygen at the hopper of the extruder that is used for making film or the silo that adds raw material.This method also has inhibition oxygen and sneaks into the effect of extruder with material resin, generates thereby suppress gel.The employing of this scheme not only can suppress gel and generate, but also has the effect of the generation of the analyte that suppresses stink or influence the sense of taste.Inert gas as using comprises the rare gas dvielement, for example can enumerate 6 kinds of elements of helium, neon, argon, krypton, xenon, radon, but owing to be high price, so unrealistic.The nitrogen of preferred cheap and easy acquisition.
Polyethylene-based laminate film of the present invention the thickness spot preferable width of the width of film in 1000mm be 7% with interior, more preferably in 6%, and then in preferred 5%.In addition, the described thickness spot among the present invention is more than the 400mm and film length is to satisfy in the roller more than the 1000m at thin-film width preferably.By this reply, under the effect of taking up phenomenon that takes place under the situation that film is preserved with the roller shape, the thickness spot of film can cause problems such as relaxing of film.So, under the situation of the film that the thickness spot is big, for example as under the stacked raw-material situation, when stepped construction under the lax effect that waits distortion, can suppress because the generation of bad order such as the gauffer of the generation of gauffer or being involved in of air and the goods that the process operation reduction obtains in addition, speculum or stacked intensity change etc.
The inhibition of described thickness spot can realize by satisfying described formation of the present invention, but and then preferably carries out reply as described below.
For example, because die head ambient air flow direction has influence on the thickness spot of film, so preferably carry out optimization.As the molten resin sheet material that relatively comes out from die head is the wind that flows of vertical air, and it is very important that such wind is disappeared.This is because if accept vertical wind under molten condition, then the molten resin sheet material vibrates, thereby the cooling spot of the varied in thickness or the part of this oscillating component takes place, and causes the thickness spot.As one of its countermeasure, can enumerate with around the making die heads such as sheet material, plate, surround with fence, make die head exit not have described preferred wind.And then, the flowing of the wind of the also preferred movement disorder of making the molten resin sheet material that does not make die head exit on one's own initiative.
In addition, the temperature spots around the die head also has influence on the thickness spot, also is very important so reduce temperature spots as far as possible.For example, around described die head, set up fence also can improve this phenomenon, so can recommend as preferred implementation.The state of heating under the state that improves humidity can make temperature spots diminish in addition, so be preferred embodiment.
In addition, the molten resin sheet material of extruding from die head also is the major reason that improves film thickness precision to the improvement of the adhesion method of chill roll.For example, as the method that itself and chill roll are adhered to, air nozzle method, air chamber method or squeegee method and vacuum chamber method are extensively popularized but described 3 kinds of methods are played a role.Promptly, at the molten resin sheet material when chill roll adheres to, with the fixing two ends of air nozzle method, utilize air chamber method or squeegee method to carry out overall width the pushing of molten resin sheet material to chill roll, the vacuum chamber method is played a role, by preventing between molten resin sheet material and chill roll, to be involved in air, thereby lower the thickness spot.In the method, to make the wind facies of squeegee or air chamber be the Attraction Degree of the air quantity of air of the attraction of homogeneous and disorder of not flowing when blowing and the vacuum chamber apparatus structure, installation site, squeegee or the air chamber that become homogeneous at width and flow direction or direction, vacuum chamber or to attract direction etc. also be very important to the molten resin sheet material to optimization.Like this, can reduce the vibration of molten resin sheet material, thickness precision be improved, so be recommended as one of effective means.
The air chamber method in the described adhesion method and the selection of squeegee method, by and the relation that is provided with between the performance of the spatial volume in place of this device or vacuum chamber suitably select to get final product.
Embodiment
Below utilize embodiment to the detailed description of the invention, but do not limited by these embodiment.Wherein, utilize following method to measure, estimate the characteristic that in each embodiment, obtains.
(1) resin density
According to JIS K7112:1999, estimate density.
(2) average grain diameter of inorganic particulate
According to the laser diffraction formula particle size distribution method of JIS K1150 record, measure.Use Leeds﹠amp; The Northrup corporate system, form: Microtrac HRA model 9320-X100 measures.
(3) white point
At area 1000cm 2Film in, the above gelling material of visual counting 0.2mm Φ.In addition, in microscopical amplification was observed, the judgement of poly gelling material except can clearly being judged as foreign matter (fibrous, carbide), was judged as gelling material.
(4) molecular weight distribution
Use gel permeation chromatography (GPC), with following assay method determining molecular weight distribution (Mw/Mn).Assay method is as described below.
Determinator: Waters 150CV
2 of post: AT-806MS
The adjustment of sample: under 145 ℃, make sample dissolution in solvent (o-dichlorohenzene adds BHT0.3%), prepare concentration 1mg/ml.
Condition determination: under the flow velocity that solvent (o-dichlorohenzene), 145 ℃ of temperature, 1.0ml/ divide, 0.4ml solution is imported in the post, measure the sample concentration in the solution that separates with post with differential refractometer.Molecular weight makes general inspection amount line with the polystyrene standard sample, uses the value of K=0.7, α=4.2E-4, obtains the molecular weight distribution (Mw/Mn) of polystyrene conversion.
(5) thickness spot
Estimate according to JIS K7130.Below describe the different part of part method in detail.Measuring environment is that 23 ℃ * 50%RH is indoor.Mensuration respectively cuts 5cm with the two ends of film, will cut sample 40 five equilibriums at these two ends at width, makes a mark locating.Carry out with amesdial in place in the position of this mark to the part of removing mark.Detection is at film roll MD direction 15cm, the whole width of TD direction, beginning to roll up the part of shelling 2 circles from the non-wrinkled part of skin section and having rolled up stripping 2 from core and enclosed 2 of non-wrinkled part, gets 3 samples respectively, tries to achieve the mean value of these 6 samples.The minimum read value of the detector that uses is 0.001mm.Precision is the equal above precision of the amesdial of JIS B7503:1997 regulation.Represent the thickness spot with following formula.
Mean value * 100 of thickness spot (%)=6 samples of (maximum ga(u)ge-minimum thickness) ÷
(6) lubricity
In the angle of friction analyzer (friction angle tester) that constitutes by inclination angle and hammer (Japan's smart machine corporate system model: A-211402803),, place (set) to hammer (heavy 1kg) and inclined plane in order to contact with the pellicular front of measuring.Improve the angle (2.7 °/second of speed) on inclined plane lentamente, measure the angle that the hammer beginning is slided on the inclined plane.The tan θ of this angle θ is a sliding.To same sample determination 3 times, represent with mean value.
(7) resistance to blocking
In hot press (テ ス one industry corporate system form: SA-303), the sample that overlaps between the mensuration face is carried out size 7cm * 7cm, 50 ℃ of temperature, pressure 1400Pa, the pressurized treatments of 15 minutes time.(Shimadzu Seisakusho Ltd. system form: (diameter 6mm, material: aluminium oxide), analyzing rod is with the power of speed (200m/ branch) when peeling off setting section UA-3122) sample of finalizing the design with this pressurized treatments and bar to be installed to autoplotter.In this case, prerequisite is that bar and release surface are level.To same sample determination 4 times, represent with mean value.
(8) volume gauffer
Can placing 1 all thickness down at 40 ℃ be the film roll with 1000mm width coiling 2000m of 40 μ m, judge the gauffer that use Visual Confirmation roller top layer then.
(9) gasproof permeability
Film cut off become to indulge 300mm * horizontal 200mm, use ゲ Le ボ Off レ Star Network ス analyzer (テ ス one industry corporate system form: band thermostat ゲ Le ボ Off レ Star Network ス テ ス one), according to ASTM F329, under 5 ℃, measure and twist with the fingers 3000 (reverse speeds: 40rpm, 400 ° of windup-degrees) stomatal number that takes place the time to same sample determination 3 times, is represented with mean value.
(embodiment 1)
The polyethylene-based composition of layer laminate (A)
Hybrid resin density 930kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV407) 90% with resin density 960kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (プ ラ イ system Port リ マ one (strain), 0408G) 10% composition.
The polyethylene-based composition in intermediate layer (C)
Resin density 925kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV405) 100% composition.
The polyethylene-based composition of hot sealing layer (B)
Relative resin density 925kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV405) 100%, (SHIN-ETSU HANTOTAI's chemistry (strain): KMP120-10) (Mitsui mine metal (strain): White Filler) (Japan changes into (strain): ダ イ ヤ ミ Star De L-200) (Japan changes into (strain) to 200ppm and the fusing point organic lubricant more than 115 ℃ to the non-spherical inorganic particulate of 12000ppm and 5 μ m: the composition of 1000ppm ス リ パ Star Network ス O) less than 115 ℃ organic lubricant for 5000ppm and fusing point to mix the spherical inorganic particulate of 10 μ m.
The B layer uses the 3 loading bench-type list multiple screw extruders of screw diameter 200mm with the polyethylene-based resin composition, the polyethylene-based resin composition of A layer usefulness and C layer usefulness uses the 3 loading bench-type list multiple screw extruders of 2 screw diameter 100mm respectively, make flat areas (プ レ ラ Application De) become 2 stages with width 3000mm, and to making the difference of height shape become curve-like for the mobile homogeneous that makes molten resin, in order to import A layer/C layer/B layer successively in T seam (slot) pattern head that makes the mobile 3 layers of type that become homogeneous and design in the die head, be 220 ℃ of extruding with the outlet temperature of die head.The lip spacing is 1.6mm.With filter is that serial connection connect to be filtered 2 grades of filtration methods that the filter of precision 100 μ m and 50 μ m forms and supplied with to die head.This filter is arranged on whole lines of A～C layer.From the molten resin sheet material that die head comes out, obtain the polyethylene-based laminate film that bed thickness 12/36/12 (μ m) constitutes that constitutes of A layer/C layer/B layer with 30 ℃ chill roll coolings.In addition, also carry out nitrogen replacement to the supply of described extruder with silo or hopper.When cooling off with chill roll, with the fixing two ends of the film on the chill roll of air nozzle, push the whole width of molten resin sheet material to chill roll with squeegee, vacuum chamber is played a role, prevent that air is involved in between molten resin sheet material and chill roll.The equal tandem in the two ends of air nozzle is arranged at the film direction of advance.In addition, the direction of advance of the sheet material that is extruded relatively of the wind direction of squeegee is 45 degree.In addition, make the direction of attraction mouth of vacuum chamber consistent with the direction of advance of the sheet material that is extruded.And then, around sheet material encirclement die head, do not dry to the molten resin sheet material.Film speed is divided enforcement with 100m/.The result who obtains is as shown in table 1.
(embodiment 2)
Recovery resin to the C layer uses 20wt%, in addition, carries out similarly to Example 1, obtains film.The result who obtains is as shown in table 1.
(comparative example 1)
The molecular weight distribution of A～C layer is 3.8, in addition, carries out similarly to Example 1, obtains film.The result who obtains is as shown in table 1.The white point of the film that obtains in this comparative example is poor.
(comparative example 2)
The density of A layer is 933kg/m 3, molecular weight distribution is 2.8, in addition, carries out similarly to Example 1, obtains film.The result who obtains is as shown in table 1.The thickness precision of the film that obtains in this comparative example is poor.
(comparative example 3)
The molecular weight distribution of A～C layer is 3.8, and the density of A layer is 933kg/m 3, in addition, carry out similarly to Example 1, obtain film.The result who obtains is as shown in table 1.The white point of the film that obtains in this comparative example is poor.
[table 1]
Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2 Comparative example 3
Bed thickness (μ m) [outer/in/interior] 12/36/12 12/36/12 12/36/12 12/36/12 12/36/12
Layer is than (%) [outer/in/interior] 20/60/20 20/60/20 20/60/20 20/60/20 20/60/20
Layer laminate (A layer) Density (kg/m 3) 930/960 930/960 930/960 933 933
Molecular weight distribution 2.8/2.8 2.8/2.8 3.8/3.8 2.8 3.8
Match ratio (wt%) 90∶10 90∶10 90∶10 100 100
Averag density (kg/m 3) 933 933 933 933 933
Intermediate layer (C layer) LL density (kg/m 3) 925 925 925 925 925
Molecular weight distribution 2.8 2.8 3.8 2.8 3.8
Match ratio (wt%) 100 80 100 100 100
Reclaim resin than (wt%) 0 20 0 0 0
Hot sealing layer (B layer) LL density (kg/m 3) 925 925 925 925 925
Match ratio (wt%) 100 100 100 100 100
Molecular weight distribution 2.8 2.8 3.8 2.8 3.8
Organic lubricant (ppm) 1200 1200 1200 1200 1200
Inorganic particulate (ppm) 17000 17000 17000 17000 17000
White point is (individual/1000cm 2) 3 ○ 3 ○ 6 × 4 ○ 7 ×
Thickness spot (%) 5 ○ 5 ○ 5 ○ 8 × 5 ○
Lubricity (tan θ) 0.15 ○ 0.15 ○ 0.15 ○ 0.15 ○ 0.15 ○
Resistance to blocking (mN/70mm) 50 ○ 50 ○ 50 ○ 50 ○ 50 ○
(embodiment 3)
Use the following polyvinyl resin of forming.
(1) the polyethylene-based composition of layer laminate (A)
Hybrid resin density 930kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV407) 90% with resin density 960kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (プ ラ イ system Port リ マ one (strain), 0408G) 10% composition.
(2) the polyethylene-based composition of intermediate layer (C)
Resin density 925kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV405) 100% composition.
(3) the polyethylene-based composition of hot sealing layer (B)
Relative resin density 925kg/m 3And the polyvinyl resin of molecular weight distribution 2.8 (Sumitomo Chemical (strain), FV405) 100%, (spherical silicon dioxide: KMP120-10) (diatomite: White Filler) 5000ppm and fusing point are less than 115 ℃ organic lubricant (erucyl amide: 200ppm and the fusing point organic lubricant (ethylenebisoleaamide: the composition of 1000ppm ス リ パ Star Network ス O) more than 115 ℃ ダ イ ヤ ミ Star De L-200) for the non-spherical inorganic particulate of 12000ppm and 5 μ m to mix the spherical inorganic particulate of 10 μ m.
The 3 loading bench-type list multiple screw extruders of screw diameter 200mm are used in described intermediate layer (C) with the polyethylene-based resin composition, the polyethylene-based resin composition of layer laminate (A) usefulness and hot sealing layer (B) usefulness uses the 3 loading bench-type list multiple screw extruders of 2 screw diameter 100mm respectively, make flat areas (プ レ ラ Application De) become 2 stages with width 3000mm, and to making the difference of height shape become curve-like for the mobile homogeneous that makes molten resin, in order to import A layer/C layer/B layer in the die head that makes the mobile 3 layers of type that become homogeneous and design in the die head successively, be 240 ℃ of extruding with the outlet temperature of die head.The lip spacing is 1.6mm.With filter is that serial connection connect to be filtered 2 grades of filtration methods that the filter of precision 85 μ m and 40 μ m forms and supplied with to die head.This filter is arranged on whole lines of A～C layer.From the molten resin sheet material that die head comes out, obtain the polyethylene-based laminate film that bed thickness 24/72/24 (μ m) constitutes that constitutes of A layer/C layer/B layer with 30 ℃ chill roll coolings.In addition, also carry out nitrogen replacement to the supply of described extruder with silo or hopper.When cooling off with chill roll, with the fixing two ends of the film on the chill roll of air nozzle, push the whole width of molten resin sheet material to chill roll with squeegee, vacuum chamber is played a role, prevent that air is involved in between molten resin sheet material and chill roll.The equal tandem in the two ends of air nozzle is arranged at the film direction of advance.In addition, the direction of advance of the sheet material that is extruded relatively of the wind direction of squeegee is 45 degree.In addition, make the direction of attraction mouth of vacuum chamber consistent with the direction of advance of the sheet material that is extruded.And then, around sheet material encirclement die head, do not dry to the molten resin sheet material.Film speed is divided enforcement with 50m/.The result who obtains is as shown in table 2.
(embodiment 4)
In embodiment 3, use in the polyvinyl resin that in the C layer, uses and reclaim resin 20wt%, in addition, carry out similarly to Example 3, obtain film.The result who obtains is as shown in table 2.
(comparative example 4)
In embodiment 3, the density of the polyvinyl resin that uses in the A layer is 930kg/m 3, molecular weight distribution is 3.8, in addition, carries out similarly to Example 3, obtains film.The result who obtains is as shown in table 3.The independence container that obtains in this comparative example is poor with the white point of polyethylene-based film.
(comparative example 5)
In embodiment 3, the polyvinyl resin that uses in the A layer uses density to be 933kg/m separately 3, molecular weight distribution is 2.8 polyvinyl resin, in addition, carries out similarly to Example 3, obtains film.The result who obtains is as shown in table 2.The independence container that obtains in this comparative example is poor with the thickness spot of polyethylene-based film.
(comparative example 6)
In comparative example 5, as the inorganic particulate that in the B layer, uses, keep the interpolation of the spherical inorganic particulate of 10 μ m, only add the non-spherical inorganic particulate 17000ppm of 5 μ m, in addition, similarly carry out with comparative example 5, obtain film.The result who obtains is as shown in table 2.Except the problem of independence container with the polyethylene-based resin film that obtains in comparative example 5, resistance to blocking is also poor with polyethylene-based film for the independence container that obtains in this comparative example.
(comparative example 7)
In comparative example 5,, keep the interpolation have less than the organic lubricant of 115 ℃ fusing point as the organic lubricant that in the B layer, uses, only add organic lubricant 1200ppm with the fusing point more than 115 ℃, in addition, similarly carry out, obtain film with comparative example 5.The result who obtains is as shown in table 2.Except the problem of independence container with the polyethylene-based resin film that obtains in comparative example 5, lubricity is also poor with polyethylene-based film for the independence container that obtains in this comparative example.
[table 2]
Embodiment 3 Embodiment 4 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7
Bed thickness (μ m) [outer/in/interior] 24/72/24 24/72/24 24/72/24 24/72/24 24/72/24 24/72/24
Layer is than (%) [outer/in/interior] 20/60/20 20/60/20 20/60/20 20/60/20 20/60/20 20/60/20
Layer laminate (A layer) Density (kg/m 3) 930/960 930/960 930/960 933 933 933
Molecular weight distribution 2.8/2.8 2.8/2.8 3.8/2.8 2.8 2.8 2.8
Match ratio (wt%) 90∶10 90∶10 90∶10 100 100 100
Averag density (kg/m 3) 933 933 933 933 933 933
Intermediate layer (C layer) Density (kg/m 3) 925 925/927 925/927 925/927 925/927 925/927
Match ratio (wt%) 100 80/20 80/20 80/20 80/20 80/20
Averag density (kg/m 3) 925 925 925 925 925 925
Hot sealing layer (B layer) LL density (kg/m 3) 925 925 925 925 925 925
Match ratio (wt%) 100 100 100 100 100 100
The spherical inorganic particulates of 10 μ m (ppm) 12000 12000 12000 12000 0 12000
The non-spherical inorganic particulates of 5 μ m (ppm) 5000 5000 5000 5000 17000 5000
Fusing point is less than 115 ℃ organic lubricant (ppm) 200 200 200 200 200 1200
Fusing point is the organic lubricant (ppm) more than 115 ℃ 1000 1000 1000 1000 1000 0
White point is (individual/1000cm 2) 3 ○ 3 ○ 6 × 3 ○ 3 ○ 3 ○
Thickness spot (%) 5 ○ 5 ○ 5 ○ 8 × 8 × 8 ×
Lubricity (tan θ) 0.18 ○ 0.18 ○ 0.18 ○ 0.18 ○ 0.18 ○ 0.40 △
Resistance to blocking (mN/70mm) 100 ○ 100 ○ 100 ○ 100 ○ 200 △ 100 ○
Utilizability on the industry
Polyethylenic resin laminated film of the present invention can obtain heat sealability, resistance to blocking and film rigidity balance and also white point is few and the thickness spot is few, so can be preferred in the purposes such as packaging for foodstuff. Thereby, very useful to industrial circle

Claims (9)

1. a polyethylenic resin laminated film is characterized in that, it is the polyethylenic resin laminated film that is made of layer laminate (A) and sealant (B) at least,
Satisfy condition as described below simultaneously, that is: layer laminate (A) is that the two or more density of cooperation are 900～970kg/m 3And molecular weight distribution (Mw/Mn) is that 2.0～3.5 the different polyvinyl resin of density forms, and the averag density of described layer laminate (A) is 920～945kg/m 3, sealant (B) is 900～930kg/m by density 3Polyvinyl resin constitute, and the averag density of layer laminate (A) is greater than the averag density of sealant (B).
2. polyethylenic resin laminated film according to claim 1 is characterized in that,
Maximum gauge is that the above white point of 0.2mm is 5/1000cm 2Below.
3. polyethylenic resin laminated film according to claim 1 is characterized in that,
The thickness spot of the width of described film is in 7%.
4. polyethylenic resin laminated film according to claim 1 is characterized in that,
Being provided with by averag density between the layer laminate (A) of described film and sealant (B) is 900～935kg/m 3The intermediate layer (C) that constitutes of polyvinyl resin form.
5. polyethylenic resin laminated film according to claim 1 is characterized in that,
The averag density of the polyvinyl resin of described each layer of described film is layer laminate (A)＞intermediate layer (C) 〉=sealant (B).
6. polyethylenic resin laminated film according to claim 1 is characterized in that,
Cooperating 10～30 quality % to reclaim resin in the intermediate layer of described film (C) forms.
7. polyethylenic resin laminated film according to claim 1 is characterized in that,
At least in the sealant (B) of described film, cooperate the spherical inorganic particulate of 0.5～1.5 quality % average grain diameter, 5～13 μ m and the non-spherical inorganic particulate of 0.1～1.0 quality % average grain diameter, 1～6 μ m to form.
8. polyethylenic resin laminated film according to claim 1 is characterized in that,
At least in the sealant (B) of described film, cooperate 100～500ppm to have to amount to 500～1500ppm and form less than the organic solvent of 115 ℃ fusing point and organic lubricant with the fusing point more than 115 ℃.
9. independence container polyethylenic resin laminated film, it is a polyethylenic resin laminated film according to claim 1, it is characterized in that,
The gross thickness of described film is 90～150 μ m.
CN200680023975XA 2005-06-29 2006-06-22 Polyethylenic resin laminated film Expired - Fee Related CN101213077B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP189273/2005 2005-06-29
JP2005189273 2005-06-29
JP288325/2005 2005-09-30
JP2005288325 2005-09-30
JP331281/2005 2005-11-16
JP331280/2005 2005-11-16
JP2005331280 2005-11-16
JP2005331281 2005-11-16
PCT/JP2006/312503 WO2007000932A1 (en) 2005-06-29 2006-06-22 Polyethylene resin laminate film

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CN101213077A true CN101213077A (en) 2008-07-02
CN101213077B CN101213077B (en) 2010-11-24

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TWI840544B (en) * 2019-04-26 2024-05-01 日商東洋紡股份有限公司 Polyethylene resin film, laminate and packaging bag using the same

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CN106240100A (en) * 2015-06-04 2016-12-21 余知荫 Middle level three layers of colored preservative film containing reclaiming resin and preparation method thereof
TWI840544B (en) * 2019-04-26 2024-05-01 日商東洋紡股份有限公司 Polyethylene resin film, laminate and packaging bag using the same

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CN101213077B (en) 2010-11-24
WO2007000932A1 (en) 2007-01-04
KR101172563B1 (en) 2012-08-08
KR20080022133A (en) 2008-03-10

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