CN103415391A - Multi-layer polymeric films and methods of forming same - Google Patents

Multi-layer polymeric films and methods of forming same Download PDF

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Publication number
CN103415391A
CN103415391A CN2012800127069A CN201280012706A CN103415391A CN 103415391 A CN103415391 A CN 103415391A CN 2012800127069 A CN2012800127069 A CN 2012800127069A CN 201280012706 A CN201280012706 A CN 201280012706A CN 103415391 A CN103415391 A CN 103415391A
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layer
polymer
inclusion
film
volume
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Inventor
H·J·奥唐纳利
D·C·佩克
P·卡鲁索
B·E·怀斯
J·J·小蒂
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Priority claimed from US13/084,630 external-priority patent/US20120263924A1/en
Application filed by Procter and Gamble Ltd filed Critical Procter and Gamble Ltd
Publication of CN103415391A publication Critical patent/CN103415391A/en
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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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B7/022—Mechanical 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/06—Vegetal particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • 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
    • 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
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
    • 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
    • B32B2555/00—Personal care

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

A multi-layer polymeric film having an A layer and a B layer. The "A" layer includes a first polymer and a first inclusion substantially disposed therein. The first inclusion is a first material that has a higher elastic modulus than the first polymer. The "B" layer includes a second polymer and a second inclusion substantially disposed therein. The second inclusion is a second material that has a higher elastic modulus than the second polymer. Methods of forming a multi-layer film are also provided.

Description

Multi-layer polymer film and forming method thereof
Technical field
The disclosure relates generally to multi-layer polymer film and forming method thereof.
Background technology
Now, the component of a lot of product requirement height through engineering approaches, but these product requirements are limited use or disposable article simultaneously.Limited use or disposable refer to product and/or component before abandoning, only use seldom number of times or may be only once.The example of this series products includes but not limited to personal care absorbent product such as diaper, training pants, incontinence clothing, sanitary napkin, bandage, cleaning piece etc., and as the product of packaging material, and other disposable products such as refuse bag and food bag.The product of these types can and utilize film really.When film is used for limited use and/or disposable products, maximum through engineering approaches performance, the motive force reduced costs simultaneously is high.
In the field of film, before attempted preparation and had the thickness of reduction and the multilayer film of some shading characteristic.For example, authorize the United States Patent (USP) 5,261,899 of Visscher and described the trilamellar membrane with intermediate layer, described intermediate layer form multilayer film gross thickness approximately 30% to 70%.An advantage that forms multilayer film is particular characteristic to be designed in film, and, by film is made to multilayer, more expensive composition can be transferred on the layer of most probable needs.This type of film also can comprise filler with for multiple purpose, comprises for example photomask.
By utilizing refractive index to be different from the anaclasis filler of polymeric material refractive index in rete, can produce photomask, and without film is stretched as the part of manufacture process.By filler refraction rather than by the film light scattering that the space that produces causes that stretches, produce color.Titanium dioxide, zinc oxide and zinc sulphide and polymeric material effectively form rete, and cause shading by anaclasis.Filled film also is disclosed in United States Patent (USP) 4,116, in 892.
Yet many in these films have performance limitations.By in the filler incorporation into membrane, may cause performance such as hot strength and yield stress to weaken.Therefore, continue to explore multi-layer polymer film improved and preparation method thereof.Particularly, expectation has more high-performance, multi-layer polymer film more cheaply.More high-performance comprises provides the multilayer film with lower basic weight and Geng Gao obscurity, and described film is non-friable and be difficult for tearing.
In addition, some consumers show buying the detest derived from the product of petroleum chemicals.In such cases, the consumer may be irresolute to buying the product of being made by limited non-renewable resources such as oil.Other consumer may have negative impression to the product derived from petroleum chemicals, thinks that it is that " non-natural " or environment are disagreeableness.
Therefore, expectation provides multi-layer polymer film, described film has lower basic weight, thereby reduced the use of oil and reduced cost, and may be able to afford and use non-petroleum source resin, wherein multi-layer polymer film has the Performance Characteristics of improvement, and has in some cases higher obscurity, to meet product and/or packing instructions.
Summary of the invention
The disclosure relates generally to multi-layer polymer film and forming method thereof.
Described multi-layer polymer film comprises ground floor (or " A " layer) and the second layer (or " B " layer)." A " layer comprises the first matrix polymer and basically is arranged on the first inclusion wherein.Described the first inclusion comprises the first material.Described the first material has the elastic modelling quantity higher than the first polymer." B " layer comprises the second matrix polymer and basically is arranged on the second inclusion wherein.Described the second inclusion comprises the second material.Described the second material has the elastic modelling quantity higher than the second polymer.Described film can comprise additional layer, and described extra play includes but not limited to top layer, and described top layer forms at least one outer surface of multi-layer polymer film.A plurality of layers of multilayer film can comprise any one or more suitable matrixes (or " matrix ") polymer, comprise the polymer that can recycle after bio-based polymers and/or consumption.
The first material and the second material can be the material of identical or different type, and can comprise unmixing rigid polymer, mineral, pottery or other inclusion material.For example, the first material and the second material can comprise the unmixing rigid polymer.In other embodiments, the first material and the second material can comprise mineral or pottery.In other embodiments, the first material can comprise the unmixing rigid polymer, and the second material can comprise mineral or pottery.In some cases, can select rigid polymer, make it will flow in structure, if during melt-processed, will in polymer substrate, formed the structure of strengthening body.Can select rigid polymer with elongation during melt-processed (for example during casting or blowing process, forming film), in rete, to produce the structure of high aspect ratio.
In certain embodiments, " A " layer and " B " layer can be adjacent, and difference aspect at least one in following: the first polymer and the second polymer are different; The first material and the second material are different; And/or in " A " layer in the volume % of the first material and " B " layer the volume % of the second material be different.In certain embodiments, in " A " layer, in volume % and " B " layer of the first inclusion, the ratio of the volume % of the second inclusion can be at about 1:1.2 to about 1:5 scope, or vice versa.
In certain embodiments, each in " A " layer and " B " layer can replace.In certain embodiments, multi-layer polymer film comprises at least two " A " layer and at least two " B " layer.In certain embodiments, A and B layer can form the paired layer of a plurality of repetitions.In certain embodiments, when multilayer film was stretched, performance was caused at least one the provided space in the first material and the second material.In some cases, when multilayer film was stretched, one of the first material and second material can provide space to cause performance, and when film was stretched, the another kind in the first and second materials was without providing space to cause performance.
The method that forms multi-layer polymer film also is provided.In one embodiment, described method comprises preparation the first composition, preparation the second composition and the first composition and the second composition is coextruded into to a plurality of layers that replace.Described the first composition comprises the first polymer and the first inclusion.Described the first inclusion is immiscible in the first polymer.The first inclusion comprises the first material.The first material has the elastic modelling quantity higher than the first polymer.The second composition comprises the second polymer and the second inclusion.The second inclusion is immiscible in the second polymer.The second inclusion comprises the second material.Described the second material has the elastic modelling quantity higher than the second polymer.After forming layer, the first inclusion is arranged in ground floor basically, and the second inclusion is arranged in the second layer basically.In certain embodiments, difference aspect at least one that each alternating layer can be in following: the first polymer and the second polymer are different; The first material and the second material are different; Perhaps there is difference in the concentration of the first and second materials in corresponding the first and second polymer.After forming film, if necessary, film can be stretched.Stretching can be used for multiple purpose, includes but not limited to cause microvoid, and/or improves the multiple performance of film, as obscurity.
The accompanying drawing explanation
Fig. 1 is the representational view with two-layer multi-layer polymer film.
Fig. 2 is the representational view with multi-layer polymer film of " n " layer, and wherein every layer also comprises the inclusion material.
Fig. 3 is the microphoto of taking from atomic force microscope images, and it illustrates in some layer the profile of the inactive multi-layer polymer film with inclusion material.
Fig. 4 A is the microphoto of taking from atomic force microscope images, and it illustrates from vertically checking film, has the profile of inactive multi-layer polymer film of at least some inclusion materials in every layer.
Fig. 4 B is for certainly laterally checking the profile that is shown in the film in Fig. 4 shown in film.
Fig. 5 A is the microphoto of taking from atomic force microscope images, and it illustrates in some layer the profile of the multi-layer polymer film of the activation with inclusion material.
Fig. 5 B is the zoomed-in view of the part of Fig. 5 A.
Although provide after specification, particularly point out and claimed claims of the present invention clearly, it is believed that by following description and also can understand more completely the present invention by reference to the accompanying drawings.In order to show more clearly other element, some figures may be simplified by omitting selected element.In any exemplary embodiment, except in corresponding explanatory note book, describing, in some figure, this type of omission of element might not indicate concrete element not exist undoubtedly.Accompanying drawing may not be drawn in proportion.
The specific embodiment
I. definition
As used herein, following term will have the implication of hereinafter appointment:
" bio-based content " refer to as in the determined material of ASTM D6866-10 method B from the carbon content of renewable resource, as the mass percent of all organic carbons in material.Notice, during bio-based content, do not comprise any carbon from inorganic source such as calcium carbonate in determining material.
" air pocket " refers to activation due to film/stretching, forms space in one or more layers of film.
" rigid polymer " refers to the polymer had than the elastic modelling quantity of the elastic modelling quantity height at least 30% of corresponding matrix polymer.
" renewable resource " refers to the natural resources that can supplement again within the time limit of 100 years.Described resource can be supplemented natively or by agricultural technology again.Renewable resource comprises plant, animal, fish, bacterium, fungi and forestry products.They can be naturally occurring, hybridization or genetically engineered organism.The natural resources such as crude oil, coal and the peat that need cost to form than 100 years longer time are not considered to renewable resource.
In context of the present disclosure, " immiscible " and/or " inconsistent " refers to microsegregation and distinct polymeric solid phase.Distinct microcosmic solid phase the time has difference as strain in drawing process in distortion, thereby produces microvoid or air pocket between phase, and the obscurity of guaranteeing not contain the composition of bulking agent increases.
As used herein, phrase " basically is arranged on wherein " and comprises that inclusion wherein is positioned at the structure of layer fully, and wherein inclusion can extend to those in a contiguous layer or a plurality of layers at least in part.
Except as otherwise noted, when this paper described the percentage of the layer occupied by inclusion, described percentage referred to volume % or volume fraction.With normal method, by normal temperature density of fraction (ρ i) and mass fraction (m i) volume fraction of Calculating material.For example, when preparation two components system (by component 1 and 2) under normal temperature, available following formula calculates the volume fraction of component 1:
Figure BDA0000380185680000051
As used herein, term " standard conditions " or " normal temperature " refer to temperature and 50% relative humidity of 77 ℉ (25 ℃).When the formula non-availability, can calculate by the two-dimensional cross sectional consecutive image of Application standard stereo measuring technology of image average film the volume fraction of film, as C.Maestrini, M.Merlotti, " Second phase volume fraction and rubber particle size determinations in rubber-toughened polymers:A simple stereological approach and its application to the case of high impact polystyrene " (Journal of Materials Science of M.Vighi and E.Malaguti, 27 (22), 5994-6016).
The present invention relates to multilayer film and preparation method thereof.Described film can have the mechanical performance of the basic weight lower than some other film, improvement and/or higher obscurity, for example by same combination, made but without those of inclusion described herein, and/or make but have those of still less total number of plies by same material.
Referring to Fig. 1, the present invention includes multilayer film 20, described multilayer film comprises at least " A " layer and " B " layer.A and B layer can relative to each other be arranged (for example Fig. 1) or arrange (for example Fig. 2) with a plurality of repeat layer with the relation of layering.As shown in Figure 2, multi-layer polymer film can comprise the number of plies of A and the B layer of " n ".In various embodiments, described film can comprise two, three or more to repeat continuous A/B layer right, and it can be set to many arrangements, includes but not limited to: spread all over total; The part that spreads all over film thickness; Or be distributed in film with many repetition continuous stands.In certain embodiments, A and B layer are capable of being combined with at least 40% of the cross section that forms overall multi-layer polymer film.With respect to the description shown in Fig. 1 and 2, the multi-layer polymer film of this paper imagination can comprise additional layer.For example, neither " A " layer also the extra play (for example film " C " layer) of non-" B " layer can be included in multi-layer polymer film.One or more C layers can consist of fluoropolymer resin or vistanex, and can be involved with for any suitable purpose, comprise the further film properties that improves.
Although Fig. 1 and 2 generality shows the multiple layer of multi-layer polymer film and arranges, and should be appreciated that this type of multi-layer polymer film can comprise approximately 4 layers to approximately 1,000 layer; Approximately 5 layers to approximately 200 layers in certain embodiments; And approximately 7 layers to approximately 100 layers in certain embodiments.
The multi-layer polymer film of this paper imagination can have approximately 4 microns to approximately 100 microns, or approximately 4 microns to approximately 50 microns, or about 6 microns extremely about thickness of 20 microns.Each in each " A " layer and " B " layer can have any suitable thickness, include but not limited to be more than or equal to approximately 50,100,200 or 300 nanometers and be less than or equal to approximately 1,2,2.5 or 5 micron or larger thickness, or any thickness range between in these numerical value two.Therefore, in some cases, described film can be considered to microlayer film.Should be appreciated that " A " layer and " B " layer can have substantially the same or different thickness.In certain embodiments, the thickness of " A " layer can be at about 1:4 to the ratio ranges of about 4:1 with the thickness of " B " layer.Multilayer film can have about 4gsm to about 100gsm, or about 4gsm is to about 30gsm, or about 6gsm is to the basic weight of about 18gsm.
" A " of multi-layer polymer film layer and " B " but layer each self-contained matrix or matrix polymer.Matrix polymer can be configured as film, and will form the matrix of the inclusion that wherein distributes.Some matrix polymer comprises polyolefin, especially polyethylene, polypropylene, polybutadiene, polypropylene-ethylene EVA and have the copolymer of at least a olefinic component and their any mixture.Some polyolefin can comprise LLDPE (LLDPE), low density polyethylene (LDPE) (LDPE), intermediate density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), isotactic polypropylene, atactic polypropylene copolymer, impact-resistant modified polypropylene copolymer and other polyolefin, and they are described in PCT patent application WO99/20664, WO2006/047374 and WO2008/086539.Other matrix polymer can be also suitable, as polyester, nylon, polyhydroxyalkanoatefrom (or PHA), their copolymer and the combination of any aforementioned substances.In addition, polyolefin plastomers and elastomer also can be used for forming multi-layer polymer film.This type of suitable polyolefins plastic body and elastomeric example are described in United States Patent (USP) 6,258,308; U.S. Patent Publication 2010/0159167A1; And in PCT patent application WO2006/047374 and WO2006/017518.In one embodiment, this type of polyolefin plastomers and/or elastomer can form the 25 volume % at the most of multi-layer polymer film.Other available polymer comprises poly-alpha-olefin, those if described in PCT patent application WO99/20664 and wherein said list of references.
Matrix polymer also can comprise the material that bio-based content is provided to film.Materials includes but not limited at least part of material derived from renewable resource.Materials comprises directly or indirectly by the polymer of one or more midbody compounds derived from renewable resource.Appropriate intermediate compound derived from renewable resource comprises sugar (comprising monose, disaccharides, trisaccharide and compound sugar).Sugar comprises sucrose, glucose, fructose and maltose, and derived from other agricultural product such as starch or cellulosic those.Derived from other suitable midbody compound of renewable resource, comprise such as the monofunctional alcohol of methyl alcohol or ethanol and such as the polyfunctional alcohol of glycerine.Other midbody compound derived from renewable resource comprises organic acid (such as citric acid, lactic acid, alginic acid, amino acid etc.), aldehyde (such as acetaldehyde) and ester (such as cetin, methyl stearate, methyl oleate, monoglyceride, diglyceride and triglycerides etc.).
Additional intermediates compound such as methane and carbon monoxide also can pass through fermentation and/or method for oxidation derived from renewable resource.
Midbody compound derived from renewable resource can directly be transformed into polymer (for example lactic acid is transformed into PLA), perhaps they also can be transformed into other midbody compound in reaction path, and final acquisition of described reaction path can be used for the polymer in multilayer film.Midbody compound can be produced more than a kind of less important midbody compound.Similarly, depend on the reaction scheme utilized, concrete midbody compound can be derived from many different precursors.
Especially the intermediate of expectation comprises alkene.Alkene such as ethene and propylene also can be derived from renewable resource.For example, the methyl alcohol of biomass derived fermentation can be transformed into ethene and/or propylene, and wherein both are suitable monomeric compound, as United States Patent (USP) 4,296, and 266 and 4,083, described in 889.Ethanol derived from the renewable resource fermentation can be transformed into vinyl compound monomer via dehydration, as United States Patent (USP) 4,423, described in 270.Similarly, the monomeric compound that can dewater to obtain propylene derived from propyl alcohol or the isopropyl alcohol of renewable resource, as United States Patent (USP) 5,475, example shown in 183.Propyl alcohol is the key component of fusel oil, described fusel oil be potato or fermented grain while producing ethanol by some amino acids formed accessory substance.
It (is CO+H that the charcoal of biomass derived can be used for producing synthesis gas 2), by described synthesis gas, can make hydrocarbon such as ethane and propane (fischer-tropsch process).Can be by ethane and dehydrogenating propane to obtain the monomeric compound of ethene and propylene.
Other material source that forms polymer comprises the material that can recycle after consumption.The material source that can recycle after consumption can comprise the plasticity bottle, for example pop bottle, plastic membrane, plastic packaging material, plasticity bag and other similar material of comprising the synthetic material that can recycle.
After the materials of the film with bio-based content and consumption can be provided, the material that can recycle was described in the U.S. Patent application sequence 13/084,630 of submitting on April 12nd, 2011.
One or more (if layer comprises the blend more than a kind of polymer) matrix polymers for equivalent layer can have any suitable elastic modelling quantity.In certain embodiments, expectation wherein has the elastic modelling quantity that is more than or equal to approximately following any value: 150MPa, 160MPa, 170MPa, 175MPa, 180MPa, 190MPa, 200MPa or larger without a kind of matrix polymer (or multiple polymers) of inclusion.
In a plurality of embodiment described herein, for a kind of matrix polymer (or multiple polymers) of equivalent layer, can form any suitable percent by volume of equivalent layer, as the approximately 50 volume % of equivalent layer to about 97 volume %, or approximately 50 volume % to about 95 volume %, or approximately 60 volume % to about 90 volume %.If to given layer, comprise the mixture of two or more matrix polymers, the percent by volume in front sentence is applicable to the total amount of all substrates polymer in described layer.
In certain embodiments, can be substantially the same for the matrix polymer of corresponding contiguous rete.For example, " A " layer and " B " layer of being shown in Fig. 1 and 2 can comprise identical matrix polymer.Think that material such as LLDPE and MDPE comprise identical this paper matrix polymer, because they both comprise the poly modification of same polymer.In certain embodiments, LLDPE and MDPE matrix polymer can be made to casting films, described casting films has about 0.905g/cm 3To about 0.945g/cm 3, or about 0.910g/cm 3To about 0.935g/cm 3Density.The melt index of this type of casting films (for example LLDPE and MDPE) can be about 0.8g/10min to about 6g/10min, or about 1g/10min is to about 5g/10min.LLDPE and MDPE also can form blown film, and described blown film has about 0.4g/10min to the interior melt index of about 2g/10min scope.
In other embodiments, the matrix polymer for corresponding contiguous rete can be significantly different.This difference can polymer A and polymer B between bad mechanical property XOR chemical composition difference describe.For example, Fig. 1 and 2 " A " layer and " B " layer can comprise different matrix polymers, can comprise LLDPE as " A " layer, and " B " layer can comprise isotactic polypropylene.Know, with regard to polyolefin, comonomer type and molar content can significantly change mechanical performance and/or the polar interaction of their phase emergencing copolymers.Polyolefinic comonomer type comprises ethene, propylene, butylene, hexene, octene, styrene, vinyl acetate, methyl acrylate, acrylic acid, maleic anhydride.If polymeric layer is made to film and comparison modulus, significant difference can comprise 30% modulus difference.Significant difference also comprises % by mole difference that adopts at least 2 % by mole of the interior contained monomers of polyolefin polymer.Therefore, in certain embodiments, in polyolefin polymer, % by mole difference of contained monomer can be at least about 5 % by mole.
In addition, during the matrix polymer of the elected equivalent layer of selecting multi-layer polymer film, this type of layer can the compatible with each other and autoadhesion of layer, to prevent joining basically two or more layers in continuous integrated, multi-level polymer film problem.
In addition or alternatively, change for matrix polymer alternately and contiguous rete, corresponding rete also can comprise the inclusion material so that the Performance Characteristics of improvement to be provided to multi-layer polymer film.Each comprised inclusion material in " A " layer and " B " layer for example, is shown as in Fig. 2.These inclusion material imaginations have the elastic modelling quantity higher than the elastic modelling quantity of corresponding matrix polymer.In certain embodiments, described inclusion material can have than the elastic modelling quantity of the elastic modelling quantity height of corresponding matrix polymer 30%, 50%, 100% or 200% at least.These inclusion materials can form the major part of multi-layer polymer film.In certain embodiments, the approximately 3 volume % that the inclusion material in rete can form described layer are to about 50 volume %, or approximately 10 volume % are to about 50 volume %, and approximately 10 volume % are to about 40 volume %, or approximately 15 volume % to about 30 volume %.In certain embodiments, in " A " layer, the elastic modelling quantity of the first inclusion can be greater than the elastic modelling quantity of the second inclusion in (or being less than) " B " layer.In various embodiments, the first and second inclusions can any above-mentioned percentage exceed the elastic modelling quantity of their corresponding matrix polymer, and their elastic modelling quantity exceed the percentage of their corresponding matrix polymer elasticity modulus can be different.
The inclusion material can comprise the material of plurality of classes, comprises for example unmixing rigid polymer and/or mineral and/or pottery.The Performance Characteristics of improving in order to obtain multi-layer polymer film, may be desirably in corresponding contiguous rete and comprise different classes of inclusion material, or change the type of the inclusion material in each contiguous rete identical category.For example, in one embodiment, " A " layer can comprise the unmixing rigid polymer in its polymer substrate, and " B " layer can comprise mineral (or vice versa) in its polymer substrate.In alternative embodiment, " A " layer can comprise the first unmixing rigid polymer, and " B " layer can comprise the second unmixing rigid polymer, wherein the first and second unmixing rigid polymers are different.In another embodiment, " A " layer can comprise the first mineral, and " B " layer can comprise the second mineral, and wherein different aspect " A " layer and " B " at least one layer in following: the first and second mineral are different; And the first and second mineral show significantly different geometry or sizes; And/or the volumetric concentration difference of the first and second mineral in their equivalent layers, ratio is at least about 1:1.2.
Standard technique in ASTM D882 or the second method, if adopted the secant modulus of identical standard 2% time measurement, are measured the elastic modelling quantity of polymer.This second method is used for the material that wherein elastic modelling quantity is difficult to measure described in standard technique.Although use list of references as " Materials Science of Polymers for Engineers " (Osswald and Menges, Hanser Publishing, 1995) table 1 in appendix can obtain the valuation of elastic modelling quantity, but, with regard to the purpose of claims, should adopt the elastic modelling quantity of measuring polymer as the measurement of appointment in ASTM D882.Mineral and pottery generally have the modulus far above matrix vistanex described herein.Therefore, with regard to the purpose of claims, suppose that mineral and pottery have than the elastic modelling quantity of polymer elasticity modulus height 30% at least, and do not measure mineral and ceramic elastic modelling quantity.If still pay close attention to determining of mineral elastic modelling quantity, the elastic modelling quantity of different minerals is that every kind of mineral are exclusive.For example, with regard to kyanite, as the periodical list of references as " Fracture toughness; hardness; elastic modulus of kyanite investigated by a depth-sensing indentation technique ", American Mineralogist, 93, in 844-852 (2008), discuss, can directly or indirectly measure the mineral modulus.
The unmixing rigid polymer can include but not limited to: polystyrene, high impact polystyrene, polybutylene terephthalate (PBT), polytrimethylene-terephthalate, Merlon, PLA, polymethyl methacrylate, cellulose acetate, thermoplastic starch, polyhydroxyalkanoatefrom (or PHA) (precondition is polymer such as the PHA that described matrix polymer neither be identical) and their combination.Should be appreciated that other rigid polymer that can process together with polyolefin is also available, described polyolefin shows microvoid when suitable stretching.
Thermoplastic starch refers to the starch of height sex change and the combination of plasticizer.Native starch is generally granular, and not melting before its degraded, and it is non-thermoplastic therefore making it.Sex change is the process of starch granules characteristic of wherein significantly removing by the whole bag of tricks, and described method comprises by the use of thermal means and mechanical means, and relates generally to the utilization of water as denaturant.When the starch of significantly sex change mixed with suitable plasticizer, the behavior of starch/plasticiser system was similar thermoplastic, and is called thermoplastic starch.
Starch refers to any starch, comprises natural and/or chemical modification.Starch can derive from wheat, potato, rice, corn, tapioca starch, cassava and other source.Starch is polysaccharide, described polysaccharide comprise straight chain (amylose) and highly branched chain (amylopectin) both.The starch of chemical modification can react with different functional groups and/or is crosslinked.Hydroxyl in starch can be substituted, to form ester and the ether of different degree of substitution.Available optional member such as multiple proteins are expanded starch.
Plasticizer comprises glycerine, ethylene glycol, triethylene glycol, tripropylene glycol, PEG, PPG, 1-2 propane diols, 1-3 propane diols, 1-2 butanediol, 1-3 butanediol, 1-4 butanediol, 1-5 pentanediol, 1-6 hexylene glycol, 1,5 hexylene glycol, 1-2-6-hexanetriol, 1-3-5-hexanetriol, sorbierite, isobide and their various derivatives.Plasticizer also can comprise adipic acid and derivative thereof, benzoic acid and derivative thereof, citric acid and derivative thereof, phosphoric acid and derivative thereof and urea.Other plasticizer is possible, and this list is not detailed.Plasticizer exists with the content in the 1-40% scope usually.
Thermoplastic starch also can with the combination blend of another kind of thermoplastic polymer or thermoplastic polymer, to improve water-resistance, machinability or performance.Thermoplastic polymer can include but not limited to polyolefin (low density polyethylene (LDPE), LLDPE, high density polyethylene (HDPE), polyethylene and ethylene copolymers, polypropylene, polypropylene copolymer), polyester, copolyesters, polyamide, copolyamide, PBS, PHA, PLA etc.Thermoplastic starch/thermoplastic blend can comprise bulking agent to improve the interaction of bi-material, and is conducive to processing and/or improves performance.Bulking agent can comprise poly polar copolymer, as EVA, EAA, EMA, polyvinyl-maleic anhydride, polypropylene-maleic anhydride etc.
Should also be understood that and can strengthen mechanical performance with other material, especially comprise compatibilizing agent or polymer.Every layer of compatibilizing agent that can comprise between 0 volume % and 15 volume %.For example, olefinic block copolymer styrene block copolymer be generally used for making polyolefin and/or polystyrene series compatible, as Lin at " Journal of Applied Polymer Science " the 113rd volume, described in 1945-1952 (2009).With regard to PLA and polyolefin system, use as U.S. Patent application 2012/0035323A1 described in block copolymer or as disclosed reactive compatibilization in U.S. Patent application 2011/0195210A1, make increase-volume possible.By the amount of unmixing rigid polymer, type, bulking agent type or the Compatibilizer Content of unmixing rigid polymer, reach the significant difference of mechanical performance.In layer, at least 3% Compatibilizer Content changes the mechanical performance that can change layer.Should be appreciated that the relative rheological behavior of matrix and unmixing rigid polymer and shape that melt-processed condition type can affect contained rigid polymer and strengthening degree and the posterior drawing air pocket degree in operating.In certain embodiments, the ratio of polymer substrate viscosity and unmixing rigid polymer viscosity can be at about 3:1 to about 1:3 scope, to generate acceptable form.The example of suitable unmixing rigid polymer is described in United States Patent (USP) 4,377, in 616,4,632,869,5,264,548,5,288,548 and 6,528,155.
When selecting the unmixing rigid polymer, may expect to guarantee that it will flow in structure, if during melt-processed, formed in the substrate the structure of strengthening body.The example of this class formation can be band, fibril or sheet form.Can select the unmixing rigid polymer during melt-processed, to extend (for example during casting or blowing process, forming film), to produce the structure of high aspect ratio, if had, be more than or equal to approximately 2,5,10,15 or 20 at the most approximately 100 or those of higher aspect ratio.
With regard to the unmixing rigid polymer for the amorphous glass shaped polymer, select to have the unmixing rigid polymer lower than the glass transition temperature of processing temperature, take and guarantee that unmixing rigid polymer stream is the melt-processed state.Also can select to have the glass transition temperature higher than the film serviceability temperature.Therefore, with regard to amorphous unmixing rigid polymer, the unmixing rigid polymer can have between approximately 70 ℃ and the about glass transition temperature between 230 ℃.With regard to the unmixing rigid polymer for semi-crystalline polymer, select the unmixing rigid polymer, make fusing point lower than processing temperature, take and guarantee that unmixing rigid polymer stream is the melt-processed state.With regard to hypocrystalline unmixing rigid polymer, the unmixing rigid polymer can have between approximately 70 ℃ and the about fusing point between 250 ℃.When adopt ASTM D882 laterally (or CD) stretch 100% the time, the unmixing rigid polymer of increase-volume does not show microvoid in soft matrix polymer film.
Mineral as the inclusion material can unrestrictedly comprise: calcium carbonate, magnesium carbonate, silica, aluminium oxide, zinc oxide, calcium sulfate, barium sulfate, sodium metasilicate, alumina silicate, mica, clay, talcum powder, diatomite and their combination.Should be appreciated that the size and dimension of mineral can affect intramatrical air pocket degree in the posterior drawing operation.In certain embodiments, for the mineral of air pocket agent, can be spherical or have approximately 1 to approximately 10 or larger aspect ratio non-spherical.The example of these type of suitable mineral is described in United States Patent (USP) 4,377, in 616,4,632,869 and 6,528,155.
In certain embodiments, the concentration of inclusion material can be different.For example, the inclusion material can be only in A or B layer.Alternatively, the volume % of the inclusion material in volume % and " B " layer of the inclusion material in " A " layer can be different.In this case, the ratio of the volume % of the inclusion material in volume % and " B " layer of the inclusion material in " A " layer can be at about 1:1.2 for example to about 1:5, or about 1:1.25 is to about 1:4, or about 1:1.5 is to about 1:2 scope, or vice versa.In this type of embodiment, multi-layer polymer film can demonstrate the characteristic as the improvement of planar film, and/or, when activation film as described herein, can demonstrate the characteristic of improvement.In certain embodiments, can add the amount of the inclusion material in the film designated layer can be at about 5 volume % to about 50 volume % scopes.In certain embodiments, can add the amount of the unmixing rigid polymer in the film designated layer can be at about 10 volume % to about 40 volume % scopes.In certain embodiments, can add the amount of the mineral in the film designated layer can be at about 10 volume % to about 50 volume % scopes.
Multi-layer polymer film also can comprise additional Opacifying pigment.This type of Opacifying pigment generally has the refractive index that is different from polymer substrate.For example, in " A " layer and " B " layer, one of at least also can comprise Opacifying pigment.This type of Opacifying pigment can comprise zinc oxide, iron oxide, carbon black, aluminium, aluminium oxide, titanium dioxide, talcum powder and their combination.The approximately 0.01 volume % that these Opacifying pigments can form multi-layer polymer film is to about 10 volume %, or approximately 0.3 volume % to about 7 volume %.Should be appreciated that and can use other suitable Opacifying pigment, and can multiple concentration use.The example of Opacifying pigment is described in United States Patent (USP) 6,653, in 523.
In addition, multi-layer polymer film for example can comprise additional material (such as additive), as other polymer (such as polypropylene, polyethylene, ethane-acetic acid ethyenyl ester, polymethylpentene, their any combination etc.), filler (such as glass, talcum powder, calcium carbonate etc.), nucleator, releasing agent, fire retardant, conductive agent, antistatic additive, pigment, antioxidant, impact modifier, stabilizing agent (ultra-violet absorber), wetting agent, dyestuff or their any combination.
Each layer as herein described has two relative surfaces.Layer surface is called as first in this article (or " on ") surface and second (or D score) surface.Yet be to be understood that, the term "up" and "down" refer to the multilayer film that is shown in for simplicity in figure towards, and if by the film upset, these layers will still keep identical relation each other, but upper strata can become lower floor after the film upset, and lower floor can become upper strata.Alignment layer, make at least one layer surface and another layer surface engagement.In certain embodiments, multilayer film 20 also can comprise at least one top layer or " S " layer.But if there is an outer surface of each self-forming multilayer film 20 of ，Ze top layer, top layer.
One or more top layer S can play any suitable function.This type of function can include but not limited to control the total concentration (making multilayer film have desired performance such as flexibility etc.) of inclusion material in multilayer film 20.One or more top layers provide stability during also being used in and extruding, and/or provide and have the multilayer film that improves performance, if be adhered to better other material.One or more top layers are polymer normally, and can comprise any material of matrix polymer in applicable work as herein described " A " or " B " layer.Therefore, top layer can consist of vistanex.Yet one or more top layers can be substantially free of, or do not contain the inclusion material fully.One or more top layers can have for the multiple layer polymer film thickness approximately 20% to about 60% gross thickness (if namely more than, being combination thickness).
When between adjacent layer, difference being arranged, with respect to the film that has the same matrix material compositions in adjacent layer, multi-layer polymer film can have the performance of improvement.This type of performance can comprise one or more in for example following: larger molecularly oriented; Higher obscurity, higher hot strength, higher tensile yield strength; Higher permeability (to steam and air); And better tear resistance.Yet, unless should be appreciated that in claims, indicating, the performance of this type of improvement is not that requirement exists.
A plurality of examples of multilayer film are shown in Fig. 3-5B.Fig. 3 illustrates from extruding direction or vertically watching, and has disactivation (non-stretching) polymer film of inclusion material.The multi-layer polymer film be shown in Fig. 3 has two alternating layers that form film, and wherein one deck comprises inclusion material (for example 50 % by weight polystyrene (100)), and another layer does not comprise the inclusion material.The inclusion of high concentration forms large main body in alternating layer, and is projected in adjacent layer.
Fig. 4 A and 4B illustrate inactive polymer film with inclusion material.The multi-layer polymer film be shown in Fig. 4 A and 4B has two alternating layers that form film, wherein one deck comprises the inclusion material of 40 % by weight (37 volume %) polystyrene (100) in 60 % by weight (63 volume %) matrix LLDPE matrix, and another layer comprises the inclusion material of 10 % by weight (8.8 volume %) polystyrene (100) in 90 % by weight (91.2 volume %) matrix LLDPE matrix.Fig. 4 A illustrates vertical view, i.e. the film direction of advancing between processing period wherein.Cross section illustrates large main body and little main body inclusion, and this has reflected the relative concentration in the layer.Different from Fig. 3, in film in Fig. 4 A and 4B, inclusion shows basically evenly and the pattern repeated, the layer that wherein has the high concentration polystyrene is had the layer separation of low concentration polystyrene slightly, thereby generate more uniformly, distribute, make in layer or the agglomeration of the inferior looks (inclusion) of interlayer minimizes.From the same film of the transverse observation of multi-layer polymer film, be shown in Fig. 4 B.The inclusion polymer extends, and is rendered as fibril and the band with high aspect ratio, estimates that described aspect ratio is between 2 and 100.
For obtaining this type of improvement and Performance Characteristics expectation, can make multi-layer polymer film stretch, elongate or activate by mechanically deform.The stretching of ring roller, machine-direction oriented stretching (MDO), horizontal orientation (CDO), mechanically deform, tentering machine frame or their any combination be can adopt, this type of stretching or the activation of multi-layer polymer film reached.The example that wherein activates these class methods of film is described in United States Patent (USP) 3,241, and 662,3,324,218,3,832,267,4,116,892,4,153,751,4,289,832,4,704,238,5,691,035 and 5,723,087; U.S. Patent Publication 2010/0055429A1; In European patent and patent application EP963292A1, EP1007329A1 and EP1803772B1.
In one embodiment, multi-layer polymer film experience is less than approximately 50% stretching, and in another embodiment, and the multi-layer polymer film experience is between approximately 10% to the approximately stretching between 30%.Should be appreciated that and can adopt multiple suitable stretching technique with the activation multi-layer polymer film, as the combination of machine-direction oriented, horizontal orientation and annealing.A kind of this type of combination is described in United States Patent (USP) 7,442, in 332.In addition, may expect repeatedly to activate multi-layer polymer film, to obtain the optimum relevant to the Performance Characteristics of improving.In addition, when according to ASTM D882-95A and constriction described herein test test, may expect that the multilayer film experience is greater than 5%, or be greater than 25%, or be greater than 30% constriction.The activation of multilayer film can improve at least 5% by obscurity in some cases, and makes basic weight not descend at least 20% from activating the multilayer film basic weight.For example, manufacture multi-layer polymer film and described film is stretched to the basic weight that is less than about 15gsm and comprises and be less than the approximately expensive light scattering titanium dioxide of 7 % by weight, can provide and have at least 60% obscurity; And the film of at least 70% obscurity in certain embodiments.
As used herein, term " obscurity " is that basidigitale or printed substrates are hidden or covered with respect to point of observation and be placed on the character that the object of base substrate rear surface is not observed it.Obscurity can be reported as to the ratio meaned with %, the serve as reasons ratio of diffuse reflectance and the diffuse reflectance of same substrate by the lean type institute backing with 89% absolute reflectance of substrate of black matrix institute backing with 0.5% reflectivity of described ratio.The obscurity that this paper relates to such as ASTM D589-97 " Standard Test Method for Opacity of Paper (15
Figure BDA0000380185680000151
/ Diffuse Illuminant A, 89%Reflectance Backing and Paper Backing) " described in, measure.The substrate that obscurity is high will not allow many (if any) light to pass this substrate.Substrate with low obscurity will allow many (if not most words) light to pass this substrate.Obscurity can be in the 0-100% scope.As used herein, term " low obscurity " is that basidigitale or printed substrates have and be less than 50% obscurity.As used herein, term " high obscurity " is that basidigitale or printed substrates have and be more than or equal to 50% obscurity.
In certain embodiments, the activation of film can generate space (for example air pocket), as shown in Figure 5 A.For example, when in film, the polymer stretching is greater than inclusion material (mineral), this type of space can form, and can be called as the micropore that stretches and produce or air pocket produces.The space formed during film cavitation measuring instrument as shown in Figure 5A and 5B (for example 300) can provide the multi-layer polymer film of the performance characteristic (for example higher obscurity or higher moisture (or steam) permeability) with enhancing.In some other embodiment, can, based on the character of selected matrix polymer and/or due to layer inner boundary activating agent, make inclusion incompatible.For example, incompatible for forcing between polyethylene and polypropylene, can use polybutene as interfacial agent, as United States Patent (USP) 5,500,265 or the open WO99/52972 of PCT described in.
Multi-layer polymer film described herein can be used in multiple application, include but not limited to personal care absorbent product such as diaper, training pants, incontinence clothing, sanitary napkin and other hygienic articles, bandage, cleaning piece etc., and as the product of packaging material, and other disposable products such as refuse bag and food bag.For example, multi-layer polymer film can be used as the impermeable egative film of liquid on disposable absorbent article and/or intercepts hoop.In a kind of this type of application, multi-layer polymer film can be used as hygiene film.For example, this type of hygiene film can have two-layer at least, is respectively " A " layer and " B " layer, and they form with repeat patterns, and the thickness of each equivalent layer can be less than approximately 2 microns.As described herein, multi-layer polymer film can engage to form with other film the layered product structure.Therefore, should be appreciated that in certain embodiments, hygiene film (hygiene film as described herein) can engage to form laminate structure with non-woven material, is particularly useful for those in the health related application.
Aforementioned multi-layer polymer film can be made by any suitable method.With regard to cast membrane, a kind of method can comprise that adopting the height that uses a plurality of extruders to export high speed casting extrudes line.Processing conditions will depend on material therefor, process equipment and desired film properties.Multilayer film described herein also can and form as " tentering machine frame " method by the more complicated technology of employing by the simple blown film of routine or casting extruding technology.The disclosure also relates to the method for preparing the multi-layer polymer film layered structure.Usually use plane casting or plane sheets or annular blown film method, make multi-layer polymer film by known coextrusion processes.The casting films of coextrusion or sheet structure have 3 to 5 layers usually; Yet, known casting films or the sheet structure that comprises hundreds of layers.In preparing a kind of method of multilayer film, can make number of plies multiplication by operative installations, as United States Patent (USP) 3,759, described in 647.Other method also is described in United States Patent (USP) 5,094, in 788 and 6,413,595.Herein, discrete overlapping layer first-class that comprises one or more materials is divided into a plurality of tributaries, these tributary changed courses or change position, and expand symmetrically separately and shrink, the independent resistance of regulating the equipment that flows through, thereby the independent flow of regulating each tributary, and tributary reconfigures to form second with overlapping relation, described second has the more discrete overlapping layer of one or more materials of big figure, and described material distributes with regulation gradient or other.In certain embodiments, can on the spirality channel plate, form thin layer, and these layers can flow in the central annular passage, wherein microbedding connects microbedding and can be stacked on subsequently in traditional thick-layer.This type of example is described in U.S. Patent Publication US2010/0072655A1.Can in blown film, form by several different methods a plurality of layers.In US2010/0072655A1, make two or more enter diverting flow and introduce in the passage with a plurality of microbeddings alternately with circular pattern, described microbedding is surrounded by the index bed polymer flow, with formation, comprises the blown film in microbedding zone.With regard to ring mould, by the fluid by the first polymer flow, be distributed in each odd internal microbedding, and the fluid of the second polymer flow is distributed in each even number microbedding, obtain the known microbedding method that produces a plurality of alternating layers.Then this microbedding group is introduced between the polymer flow passage of standard thickness.The layer doubling technology of casting films is by company such as Extrusion Dies Industries, and Inc. (Chippewa Falls, WI) and Cloeren Inc. (Orange, TX) are commercially available.The microbedding of blown film and nanometer layer technology are commercially available by BBS Corporation (Simpsonville, SC).
For example, early stage multilayer technology and structure are shown in United States Patent (USP) 3,565,985; 3,557,265; With 3,884, in 606.The open WO2008/008875 of PCT discloses and has formed the alternately method of the sandwich construction of type, the alternating layer of described structure has many (for example 50 to hundreds of) foams and film.
Other is manufactured option and comprises simple blown film (foam) method, as " The Encyclopedia of Chemical Technology " (Kirk-Othmer, the third edition, John Wiley& Sons, New York, 1981) described in the 16th volume 416-417 page and the 18th volume 191-192 page.The method of manufacturing the biax orientation film is described in United States Patent (USP) 3,456 as " two foam " method, and in 044 (Pahlke), and other appropriate method for preparing biaxial stretch-formed or alignment films is described in United States Patent (USP) 4,865,902 people such as () Golike; 4,352,849 (Mueller); 4,820,557 (Warren); 4,927,708 (people such as Herran); 4,963,419 (people such as Lustig); With 4,952, in 451 (Mueller).Also can described in tentering machine frame technology, make membrane structure, as the tentering machine frame technology for oriented polypropylene.
Other multi-layer polymer film manufacturing technology for the packaging for foodstuff application is described in " Packaging Foods With Plastics " (1991) the 19-27 pages of Wilmer A.Jenkins and James P.Harrington and " Coextrusion Basics " (Film Extrusion Manual:Process of Thomas I.Butler, Materials, Properties) in 1-80 page (announcing (1992) by TAPPI Press).
Can in the second operation, multi-layer polymer film be laminated on another or a plurality of layer, those described in " the Coextrusion For Barrier Packaging " of those described in Wilmer A.Jenkins and James P.Harrington " Packaging Foods With Plastics " (1991) or W.J.Schrenk and C.R.Finch (Society of Plastics Engineers RETEC Proceedings, Jun.15-17 (1981)) 211-229 page.If as K.R.Osborn and W.A.Jenkins at " Plastic Films; Technology and Packaging Applications " (Technomic Publishing Co., Inc. (1992)) described in via tubular film (being the blown film technology) or plane mould (being casting films) manufacture order tunic layer, described film must experience extrusion step after additional adhesive, or extruding layer is pressed onto on other packing timber bed of material to form multilayer film.If described film is the coextrusion thing (also being described by Osborn and Jenkins) of two-layer or multilayer, described film still can be laminated to the additional packing timber bed of material, and this depends on other physics requirement of telolemma." the Laminations vs.Coextrusion " of D.Dumbleton (Converting Magazine (in September, 1992)) also discussed lamination to coextrusion.The multi-layer polymer film of this paper imagination also can experience other rear extruding technology, as biaxial orientation technique.
Example
Example 1: form 2 layer multi-layer films (sample X) and two 32 layer multi-layer films (sample Y and Z) with identical relative composition, each in the latter has alternately and contiguous a plurality of " A " and " B " layer in film.At Extrusion Dies Technologies Inc. (Chippewa Falls, WI), adopt theirs
Figure BDA0000380185680000181
Feedblock, all have and do not have a layer doubling technology, makes these materials.Microbedding feedblock with 0,1 or 2 four-way plug-in unit can make 2,8 or 32 tunics by the A/B First structure of coating layer.Average linear velocity be 150 feet (fpm) per minute (46m/min), and the average film basic weight is 18gsm.The composition of each membrane sample is shown in following table 1.In each film, " A " layer and " B " each self-contained matrix polymer of layer and inclusion material.Matrix polymer is with trade name DOWLEX by Dow Chemical (Midland, MI) TMThe LLDPE that 2047G sells, and the inclusion material is by Heritage Plastic (Picayune, MS, U.S.A.) calcium carbonate of supplying with T97813 grade masterbatch, and comprise 70% levigate calcium carbonate and 30% polyethylene support resin (levigate calcium carbonate masterbatch or " GCC MB ").In addition, each layer comprises the Opacifying pigment titanium dioxide with the supply of 110313-C grade masterbatch by Ampacet (Tarrytown, NY, U.S.A.), and it has 70% titanium dioxide and 30% polyethylene support resin (TiO 2MB)." A " layer thickness is 1:1 with the ratio of " B " layer thickness.
Adopt known analytical technology to measure the crucial mechanical performance (for example hot strength and tear resistance) of film.Adopt ASTM method D882 to implement extension test.Adopt ASTM D1922 to implement Elmendorf and tear test.Adopt ASTM D5733 to implement trapezoidal (trap) and tear test.Use 610 to take advantage of large stretch of film of 150mm to measure the web modulus, if disclosed in U.S. Patent application 2003/0105443A1 people such as () Ohnishi, described large stretch of film is reeled, paved, and test stretcher strain.As shown in following table 1 and 2, sample Y and Z with 32 layers of structure show the Performance Characteristics of enhancing than the two-layer structure of sample X.
In the two membranes of extruding, observe hole, and two membranes has the not good white uniformity.In 32 tunics, do not have described hole, and white is uniform.
Table 1--sample X-Z forms
Figure BDA0000380185680000191
The mechanical performance of table 2-sample X-Z
Figure BDA0000380185680000192
Example 2: adopt the method described in example 1, form 2 layer multi-layer films and two 32 layer multi-layer films with identical relative composition, each in the latter has alternately and contiguous a plurality of " A " and " B " layer in film.The composition of each membrane sample is shown in following table 3.The material that is used to form multi-layer polymer film comprises LLDPE (DOWLEX TM2047G), HIPS (high impact polystyrene, Ineos473KG, League City, TX, U.S.A.) and titanium dioxide (Ampacet110313-C).At Werner& In Pfeiderer ZSK-30 dual-screw-stem machine, (9Kg/h) mix the HIPS of 60 % by weight (60 % by weight) and the LLDPE (being called " c " in table 3) of 40 % by weight (40 % by weight) with 20lb/h (or pph).This masterbatch material is classified HIPS MB as, and provides less HIPS phase size when time in the introducing film.Use 32 inches (81.3cm) wide casting films mould, make three samples (sample 1-3).Extruding datum speed is 150fpm (46m/min), and nominal basis weight is 14gsm.
Table 3-sample 1-3 forms
Figure BDA0000380185680000193
Figure BDA0000380185680000201
The mechanical performance of the gained film of sample 1-3 is shown in following table 4.
The mechanical performance of table 4-sample 1-5
Figure BDA0000380185680000202
Example 3: at vertically (MD), horizontal (CD) or both direction activation identical composition and the film of layer structure in having the sample 1-3 with example 2.It is cold drawn that described film stands the MD of lower 8 inches (20cm) spans of 300fpm (92m/min), and/or the CD looping mill rolling carried out immediately after machine-direction oriented (" pitch (1.5mm) (the CD tooth is to space of teeth (or ridge is to ridge interval)) that grovved roll has 0.060.Term " looping mill rolling " refers to the technique of using deformation element, described deformation element comprises reverse roll, comprises intermeshing band or the intermeshing plate of continuous ridge and groove, wherein the intermeshing ridge of deformation element and groove engagement and the intervenient web that stretches.The example of looping mill rolling equipment is shown in United States Patent (USP) 7,819, in Fig. 5 of 853B2.The Three Estate of take is implemented activation: A and is the 20%CD activation; B is 20%MD and 20%CD activation; And C is the 30%CD activation.Be made as on 18 inches (46cm) diameter warm-up mills of 60 ℃, making film lax immediately with 180 degree contact angles.Results of property is shown in hereinafter.Should be noted that, after any appointment drawing process, the obscurity in 32 tunics is higher than two membranes.
The mechanical performance of sample after table 5-stretches
Figure BDA0000380185680000203
Figure BDA0000380185680000211
Size disclosed herein and numerical value should not be understood to be strictly limited to described exact numerical values recited.On the contrary, except as otherwise noted, each above-mentioned size is intended to mean described value and around the scope be equal on the function of this value.For example, disclosed size " 40mm " is intended to mean " about 40mm ".
Should be appreciated that each higher limit provided in this manual comprises each lower limit, is also clearly meaned in this article as this lower limit.Each the minimum value limit provided in this specification will comprise each higher numerical value limit, clearly be meaned in this article as this higher numerical value limit.Each number range provided in this specification will comprise each the narrower number range fallen in this type of wider number range, write out clearly in this article as this type of narrower number range.
The All Files of quoting in the specific embodiment all is incorporated herein by reference in relevant portion; Quoting of any document may not be interpreted as its approval as prior art of the present invention.When any implication of same term in any implication of term in the literature or definition and the document be incorporated to way of reference or define while conflicting, will be as the criterion with implication or the definition of giving that term in the literature.
Although with specific embodiment, illustrated and described the present invention, those be it will be apparent to those skilled in the art that in the situation that do not deviate from the spirit and scope of the present invention and can make many other change and modifications.Therefore, the claims of enclosing are intended to contain all these changes and the modification in the scope of the invention.

Claims (14)

1. multi-layer polymer film is characterised in that it comprises:
A) " A " layer, described " A " layer comprises the first polymer with elastic modelling quantity and basically is arranged on the first inclusion wherein, wherein said the first inclusion comprises the first material, and described the first material has than the higher elastic modelling quantity of described the first polymer; With
B) " B " layer, described " B " layer comprises the second polymer with elastic modelling quantity and basically is arranged on the second inclusion wherein, wherein said the second inclusion comprises the second material, described the second material has than the higher elastic modelling quantity of described the second polymer, wherein said " A " layer and described " B " layer are adjacent, and difference aspect at least one in following:
I) described the first polymer and described the second polymer are different;
Ii) described the first material and described the second material are different; With
Iii) the volume % of the second inclusion in volume % and described " B " layer of the first inclusion in described " A " layer is different,
Wherein described A layer and B layer are bonded together and to combine to form the A/B layer right, and described multilayer film comprises at least two pairs of A/B layers, wherein the A layer in a pair of A/B layer contacts the B layer in the A/B layer with another.
2. multi-layer polymer film according to claim 1, wherein said the first polymer and described the second polymer form respectively 50 volume % to 95 volume % of described A layer and B layer, preferably 60 volume % to 90 volume %.
3. according to multi-layer polymer film in any one of the preceding claims wherein, wherein said the first inclusion and described the second inclusion form respectively 5 volume % to 50 volume % of described A layer and B layer, preferably 10 volume % to 40 volume %.
4. according to multi-layer polymer film in any one of the preceding claims wherein, each in wherein said the first polymer and described the second polymer is selected from: the polyolefin that can recycle after polyolefin, polypropylene, low density polyethylene (LDPE), LLDPE, linear medium density polyethylene, high density polyethylene (HDPE), polypropylene-ethylene EVA, polyhydroxyalkanoatefrom, consumption and their mixture.
5. according to multi-layer polymer film in any one of the preceding claims wherein, comprise bio-based materials, wherein as ASTM D6886-10 method B, determine, the bio-based content of described film is at least 10%.
6. according to multi-layer polymer film in any one of the preceding claims wherein, wherein said the first polymer and described the second polymer comprise polyolefin, and described polyolefinic amount forms respectively at least 50 volume % of described A layer and described B layer.
7. according to multi-layer polymer film in any one of the preceding claims wherein, wherein said the first material comprises the first unmixing rigid polymer, and described the second material comprises the second unmixing rigid polymer, each in wherein said the first unmixing rigid polymer and described the second unmixing rigid polymer is selected from polystyrene, high impact polystyrene, polybutylene terephthalate (PBT), PLA, polyhydroxyalkanoatefrom and their combination.
8. according to the described multi-layer polymer film of any one in claim 1-6, wherein said the first material comprises the unmixing rigid polymer, and described the second material comprises at least a in mineral and pottery, and wherein said unmixing rigid polymer is selected from polystyrene, high impact polystyrene, polybutylene terephthalate (PBT), PLA and their combination; And described mineral are selected from calcium carbonate, brium carbonate, diatomite and their combination.
9. according to the described multi-layer polymer film of any one in claim 1-6, wherein said the first material comprises at least a in the first mineral and pottery, and described the second material comprises at least a in the second mineral and pottery, and each in wherein said the first mineral and described the second mineral is selected from calcium carbonate, brium carbonate and their combination.
10. according to multi-layer polymer film in any one of the preceding claims wherein, described multi-layer polymer film has at least 60% obscurity when activation.
11. according to multi-layer polymer film in any one of the preceding claims wherein, described multi-layer polymer film has two outer surfaces, and comprise at least one polymeric surface layer, described polymeric surface layer joins one of described " A " layer and " B " layer to, makes top layer form at least one outer surface of described multi-layer polymer film.
12. a multi-layer polymer film is characterised in that it comprises:
A) at least three layers " A " layer, each " A " layer comprises the first polymer with elastic modelling quantity and basically is arranged on the first inclusion wherein, wherein said the first polymer forms at least 50 volume % of described " A " layer, wherein said the first inclusion comprises the first material, described the first material has than the elastic modelling quantity of described the first polymerization object height 50% at least, and wherein said the first material forms at least 10 volume % of described " A " layer; With
B) at least three layers " B " layer, each " B " layer comprises the second polymer with elastic modelling quantity and basically is arranged on the second inclusion wherein, wherein said the second polymer forms at least 50 volume % of described " B " layer, wherein said the second inclusion comprises the second material, described the second material has than the elastic modelling quantity of described the second polymerization object height 50% at least, wherein said the second material forms at least 10 volume % of described " B " layer
Alternately, each in wherein said the first material and described the second material has space initiation performance to each in wherein said " A " layer and described " B " layer, and wherein each layer has and be not more than the thickness of 5 microns.
13. a method that forms multi-layer polymer film, described method is characterised in that it comprises:
A) prepare the first composition, described the first composition comprises the first polymer and the first inclusion with elastic modelling quantity, described the first inclusion is immiscible in described the first polymer, described the first inclusion comprises the first material, and wherein said the first material has than the higher elastic modelling quantity of described the first polymer;
B) prepare the second composition, described the second composition comprises the second polymer and the second inclusion with elastic modelling quantity, described the second inclusion is immiscible in described the second polymer, described the second inclusion comprises the second material, and wherein said the second material has than the higher elastic modelling quantity of described the second polymer; And
C) described the first composition and described the second composition are coextruded into to a plurality of " A " that replace and " B " layer, wherein said the first composition forms described " A " layer, and described the second composition forms described " B " layer, each alternating layer has and is less than the thickness of 2 microns, to form multi-layer polymer film, and wherein each alternating layer with respect to difference aspect at least one in following of adjacent layer:
I) described the first polymer and described the second polymer are different;
Ii) described the first material and described the second material are different;
Iii) the volume % of described the first inclusion is different from the volume % of described the second inclusion;
Iv) described the first composition and described the second composition are different; With
V) the volume % of the first and second materials in their corresponding " A " and " B " layers is different.
14. the method for formation multi-layer polymer film according to claim 13, also comprise the steps d of the multi-layer polymer film of the described coextrusion that stretches).
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