CN1596277A - Air and moisture vapor breathable biodegradable films and method of manufacture - Google Patents

Air and moisture vapor breathable biodegradable films and method of manufacture Download PDF

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Publication number
CN1596277A
CN1596277A CNA018193250A CN01819325A CN1596277A CN 1596277 A CN1596277 A CN 1596277A CN A018193250 A CNA018193250 A CN A018193250A CN 01819325 A CN01819325 A CN 01819325A CN 1596277 A CN1596277 A CN 1596277A
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China
Prior art keywords
film
lactic acid
biodegradable
air
composition
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CNA018193250A
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Chinese (zh)
Inventor
吴派川
托马斯·R.·赖尔
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Clopay Plastic Products Co Inc
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Clopay Plastic Products Co Inc
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Publication of CN1596277A publication Critical patent/CN1596277A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/20—Fibres of continuous length in the form of a non-woven mat
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
    • 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
    • B32B2307/716—Degradable
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state

Abstract

Biodegradable films permeable to moisture vapor and air which act as barriers to liquid are made by a high speed method. The films have high moisture vapor transmission rates (MVTRs) on the order of about 1000 to about 4500 g/m<2>/day according to ASTM E96E and air breathability of about 30 to about 2000 cc/cm<2>/min at 90 psi air pressure.

Description

Permeable biodegradable films of air and water vapour and manufacture method thereof
Related application
The application is application number US09/480, and the part of 374 (applications on January 10th, 2000) continues, and the latter is again application number US09/080,063 (on May 15th, 1998, application now was US6,013,151) and application number US09/395, the part in 627 (on September 14th, 1999) continues.
Be incorporated herein by reference at this full content above-mentioned application.
Technical field
The present invention relates to permeable biodegradable plastics film of air and water vapour and preparation method thereof.
Technical background
The preparation method of plastics film can recall many years.For example, before 30 years, be issued to people's such as Trounstine US3,484,835 (1968), this patent relates to and has desired processing characteristics and prepare useful article such as the embossed plastic film of diaper.From then on, many patents have been delivered in this field.US4,376,147 (1983) disclose horizontal (CD) and vertical (MD) film of embossing.US5,202,173 (1993) and 5,296,184 (1994) disclose a kind of surpassing-soft thermoplastic film, and this film makes by increasing progressively the stretching embossed film, and has formed the hole of obtaining ventilation property.Described film can comprise filler.The polymeric film of polycaprolactone (PCL) and starch polymer or polyvinyl alcohol (PVOH) also will produce the breathable product when increasing progressively stretching, as US5, and 200,247 and 5,407, described in 979.In recent years, US5,865,926 have delivered a kind of preparation method with cloth shape microporosity laminating material air and water vapour permeability and liquid barrier performance, the nonwoven web width of cloth and thermoplastic film.
The known more existing time of the manufacture method of microporous film products.For example, the US3 of Liu, 832,267 disclose the fusion-embossing of polyolefine before stretching or orientation that contains dispersive amorphous polymer phase, so that improve the gas and the water vapour permeability of film.According to No. 267 patents of Liu, at twin shaft before, at first the crystalline polyacrylic film with dispersive amorphous poly propylene phase is carried out embossing, so that produce orientation nonporous film with bigger ventilation property to drawing (stretching).Dispersive amorphous phase is used to provide micropore, so that improve the ventilation property of nonporous film, thereby improves moisture permeability (MVT).
1976, Schwarz has delivered one piece of article, described and be used for the polymer blend and composition (the Eckhard C.A.Schwartz (Biax-Fiberfilm) of production microporosity matrix, " New Fibrillated Film Structures; Manufacture and Uses ", Pap.Synth.Conf. (TAPPI), 1976, the 33-39 pages or leaves).According to this piece article, the film of two or more incompatible polymers, wherein, a kind of polymer formation external phase and the second polymer formation discontinuous phase, when stretching, will be separated in the film, make the porosity that produces the space in the polymeric matrix and increase film thus.Also can fill mineral filler such as clay in the continuous film matrix of crystallizable polymers, titanium dioxide, lime carbonate or the like is so that provide microporosity when strained polymer matrix.
Many other patent and publications disclose the phenomenon of making microporosity thermoplastic film product.For example, EP141592 discloses the use polyolefine, particularly uses the ethene-vinyl acetate copolymer (EVA) that contains dispersive polystyrene phase to prepare the capillary film, will produce the space film that improves pellicular water steam permeability when stretching.These EP ' 592 patents also disclose: the eva film with thick and thin zone is carried out embossing, carry out the tensile consecutive steps then, so that the film with space at first is provided, it will produce net-shape product when further stretching.US4,452,845 and 4,596,738 also disclose the tensile thermoplastic film, and wherein, disperse phase can be calcium carbonate filled polyethylene, so that micropore is provided when stretching.US3,137,746; 4,777,073; 4,814,124; With 4,921,653 disclose the identical method of describing with above-mentioned publication, comprise at first the polyolefin film that contains filler is carried out embossing, then film are stretched so that micro porous product to be provided.Other the disclosed patent application that comprises WO98/23673 relates to the penetrating rate of the moisture with improvement and by copolyester resin having and mineral filler are mixed the thermoplasticity copolyester film that makes.
Product biodegradable and/or compost helps the protection of environmental resources and prevents to produce extra waste.Manufacturing firm and user recognize that it is limited that landfill and other are disposed the space in places, and seek energetically be better than the lifeless matter degradation capability and/or the product of the biodegradable and/or compost of the product of compost not.At product such as baby diaper disposable, that highly use, feminine hygiene products in hospital's coverlet or the like, is a particularly important to the needs of biological degradability and/or compostability.
Thermoplastic film biodegradable and/or compost is known in the prior art.Above-mentioned US5,407,979 disclose the biodegradable thermoplastic film of being made up of three components: alkanol polymkeric substance, modified starch, and ethylene copolymer.These components can be extruded and film can stretch to form air-permeating film.US5,200,247 disclose the biodegradable thermoplastic film that comprises alkyloyl polymkeric substance/polyvinyl alcohol (PVA) mixture.US5,196,247 disclose polymkeric substance composite sheet and the preparation or the compost method of compost.
Soft cloth shape matrix material totally biodegradable and/or compost is disclosed in US5, in 851,937.For a kind of texture of soft cloth shape is provided, this matrix material is to make by nonwoven fabric one or more layers totally biodegradable that little by little stretches and/or compost and plastics film.
But air-permeating film and the laminating material of producing liquid barrier layer still exist many shortcomings.Keeping biological degradability, in the time of air ventilation property and moisture permeability, be difficult to obtain the liquid obscures film of sufficient intensity.
Summary of the invention
The present invention relates to the biodegradable film that a kind of air and water vapour all can suck, this film still is the blocking layer of liquid.These films have greater than about 1000 grams/square metre/the penetrating rate of moisture (MVTRs) of every day and 100F, 95% relative humidity (RH) (according to ASTME96E), and under 90 air pressure greater than the ventilation property of about 30cc/cm2/min.
In above-mentioned number of patent application 09/080,063 and 09/480,374, disclose have high MVTRs, tensile film little by little.That these applications relate to little by little tensile embossing and the not improvement of the film of embossing, the MVTRs of described film preferably restrains at about 1200-4500/square metre/every day.The ventilative laminating material of these films and nonwoven matrix is also disclosed in addition.
The present invention relates to biodegradable film and laminating material and further improve, described material all is permeable for air and water vapour.In broad form of the present invention, biodegradable film comprises: the mixture of the mineral filler of biodegradable thermoplastic polymer and mechanical pore-forming material such as lime carbonate, silicon-dioxide and zeolite.Pore-forming material in film or laminating material will be activated when stretching, preferably in the stretching that increases progressively the time, to form the laminating material of microporous membrane or fibrous web and film.Be mixed with can film forming starch polymer or the biodegradable polymkeric substance of polyvinyl alcohol (PVA) be suitable as polycaprolactone (PCL).Other biodegradable polymkeric substance comprise polylactide (PLA), polyester and copolyester.
Biodegradable film and laminating material can be used at the bottom of the diaper, toilet paper and sanitary belt, and other medical science, packing and clothes are used.Biodegradable film is because its ventilation property, and therefore water vapour permeability and watertightness are particularly suited for these and other similar application.The benefit of the biodegradable film of the present invention and character and preparation method thereof will further be understood with reference to following detailed description.
Detailed description of the invention
Main purpose of the present invention is: produce air and the permeable biodegradable film of water vapour, the ventilation property of this film under 90psi air pressure at least about 30cc/cm2/min, MVTR greater than about 1000 grams/square metre/every day, and 100F, 95% relative humidity (RH) (according to ASTME96E).Another object of the present invention is to: produce the biodegradable thermoplastic film of tensile gradually, this film has following penetrating characteristic: the thickness of rule, porosity and crack-free uniformly.
A. biodegradable film and laminating material
This biodegradable film composite can obtain by biodegradable thermoplastic polymer and suitable additive and pore-forming filler are prepared, so that extrudate or film to be provided.This film can carry out lamination with nonwoven fabric.Lime carbonate, barium sulfate, silicon-dioxide and zeolite granular are prevailing fillers.As mentioned above, when containing the biodegradable film of different polymer phases when stretching under envrionment temperature or room temperature, film will produce micropore, thus the ventilation property of providing and water-vapor transmission, and this has been known.These methods are described in US5, in 200,247 and 5,407,979.On the contrary, the present invention relates to adding, make biodegradable film possess high ventilation property and high MVTRs by mineral filler, and liquid obscures.
As mentioned above, the purpose of these and other will be achieved by the preferred mode of the present invention: the above-mentioned biodegradable polymkeric substance of the about 40-75% weight of at first melt blending (a), (b) mineral filler of about 25-60% weight, lime carbonate for example, zeolite, silicon-dioxide, talcum, barium sulfate, mica or the like; Then the composition of described melt blending is clamp-oned in the roll gap with other additive, thereby do not had to form film with speed under the situation of draw resonance at least about 550-1200fpm; And with described speed along basically and evenly across film and run through the drawing force that the line of its degree of depth will increase progressively and be applied on the described film, so that biodegradable microporous membrane to be provided.
More precisely, in a preferred form, the composition of melt blending mainly is made up of as the copolyester that is described in the aliphatic-aromatic among the WO98/23673 the polyester of about 60-75%, and at this its explanation is incorporated herein by reference.Particularly, these thermoplasticity copolyesters can comprise at least a aliphatic dicarboxylic acid, at least a aromatic dicarboxylic acid and at least aly have 4 aliphatic diols to about twelve carbon atom.In addition, the thermoplasticity copolyester can comprise at least a aromatic dicarboxylic acid, at least a aliphatic diol and polyalkylene ether.Aliphatic dicarboxylic acid is selected from: hexanodioic acid, and pentanedioic acid, cyclohexylenedinitrilotetraacetic acid (cyciohexanoic acid), and composition thereof; At least a of described aromatic dicarboxylic acid is selected from: terephthalic acid, and m-phthalic acid, naphthalene dicarboxylic acids, and composition thereof; And at least a of described aliphatic diol is selected from: 1, the 4-butyleneglycol, cyclohexanedimethanol is selected from poly-(ethylene glycol), poly-(butyleneglycol) and gather (propylene glycol), and composition thereof the polyalkylene ether compound.Within the scope of the invention, the thermoplasticity copolyester can comprise aromatic dicarboxylic acid, aliphatic diol, and the cycloaliphatic dicarboxylic acid, the various combination of polyalkylene ether or the like, described these all are described in the WO98/23673 publication with the example of copolyester.
Other polymkeric substance comprises ester-ether polyester (Hytrel and Armtel); Nylon-ether polyester (Pebax); Polyethylene terephthalate (PET); Polyvinyl alcohol (PVA); Polycaprolactone (PCL); Starch; Polylactide (PLA); Starch and PVA, PCL, or the mixture of PLA; Polyester as poly-hydroxyl (butyric ester) (PHB) gathers hydroxyl (valerate) (PHV); And composition thereof.Preferably, the median size of the about 25-40% of use is about the lime carbonate of 1-10 micron, silicon-dioxide, barium sulfate, or zeolite.
Biodegradable non-woven fabrics can be laminated on the described film, and preferably, and they comprise and be disclosed in US5, the fusion-stable lactide polymer in 539,081, i.e. polylactide non-woven fabrics (PLA).Polymkeric substance or mixture of polymers manufacturing that all long filaments of this non-woven fabrics are derived and obtained by lactic acid, described lactic acid is L lactic acid, D lactic acid, or the mixture of L and D lactic acid.Other non-woven fabrics biodegradable and/or compost comprise cotton nonwoven fabrics, cellulosic non-woven fabrics, and the copolyester of aliphatic-aromatic, and composition thereof.
In the aforesaid method, by the cooling zone that air knife provides, the composition of fusion-blending is extruded by slit die with form of fabric, enters then in the nip of roller, so that to form film at a high speed.Can produce (non-embossing) embossing or smooth film.As mentioned above, utilize air knife will help to eliminate draw resonance for known, for example with reference to US4,626,574.In addition, as pending trial US09/395,627 (applications on September 14th, 1999) are described, use cooling gas is imported the device of the cooling zone parallel with fabric face basically, are introduced into as a reference at this.For example, can use to be shown in US4, the device in 718,178 and 4,779,355, and also the full content of these patents is incorporated herein by reference at this.After cooling, with at a high speed along basically evenly across film and run through the line of its degree of depth, the drawing force that will increase progressively is applied on film or the laminating material, so that the tensile gradually with high MVTR and highly air-permeable, film embossing or smooth are provided.
According to principle of the present invention, after the nip of fabric being clamp-oned roller, form flat film, thereby produce flat film with polished chrome surface.When increasing progressively at a high speed when stretching, flat film will be produced the microporous film products that has greater than the high MVTR of 1000 grams/square metre/day.Have found that flat film can increase progressively stretching more equably than embossing film.As well known in the prior art, drawing process can be in envrionment temperature, room temperature, or carry out under the high temperature.Be known that also in prior art that in addition " environment " refers to: no matter around film, have which type of processing condition, envrionment temperature that may exist or atmosphere.As mentioned above, the laminating material of microporous membrane can utilize the fibrous web of nonwoven to obtain.
In preferred mode, the microporosity laminating material uses the film that has in about 0.25-10 mil thick, and according to the difference of purposes, film thickness will change, and most preferably, in disposable application, its thickness is about the 0.25-2 mil.The nonwoven web width of cloth of laminate has about 5-75g/yd usually 2, preferably about 20-40g/yd 2Weight.Matrix material or laminating material can increase progressively stretching at horizontal (CD), to form CD tensile matrix material.In addition, after stretching, CD can also carry out vertically (MD) stretching, to be formed on CD and MD direction tensile matrix material.As mentioned above, microporous membrane or laminating material can be used for many different purposes as wherein needing the baby diaper of penetrating characteristic of water vapour and air and liquid barrier performance, baby's training pants, menopad and clothes or the like.
B. the drawing machine of microporous membrane and laminating material
Can adopt many different drawing machines and technology that the film or the laminating material of the nonwoven web width of cloth and microporosity-formable film are stretched.The fibrous web that the process combing machine for fur of the nonwoven of staple fibre was combed or these laminating materials of spun bonded fabric fibrous web can stretch with drawing machine as described below and technology:
1. diagonal lines meshes drawing machine
Diagonal lines engagement drawing machine is made up of a pair of left hand on the parallel transmission axle and right hand twisted spur gear-linear element.Described axle is arranged between two blocks of pusher side plates, and lower shaft is arranged in solid bearing and goes up axle and be arranged in the vertical slidably bearing of member.By by adjusting the exercisable wedge-like element of screw, slidably member can be adjusted in vertical direction.With the precession of wedge-like element or screw out and to make respectively slidably that member vertically moves downward or upward, thereby the nip roller and the gear-like tooth of following nip roller are meshed or disengaging.Be mounted to micrometer on the side frame and can be used for indicating the depth of engagement of the tooth of nip roller.
Use cylinder so that slidably member firmly remain on its position of engagement down facing to adjusting wedge so that antagonism is by upward force that material extending produced.These cylinders can also be withdrawn, and nip roller breaks away from each other so that make up and down, so that material becomes silk by this gearing apparatus, the safety circuit that will open all folder machine points during perhaps with activation links.
Usually use drive unit, to drive the immobilized nip roller.If for machine is worn silk or safety, last nip roller is departing words, the preferred use is arranged in the gapless transmission device between the nip roller up and down, always drop between the tooth of another nip roller with the tooth that guarantees a nip roller when engaging once more, and avoided the destructive directly contact of potential between the tooth top of engaging tooth.If nip roller keeps constant to engage, so, last nip roller needn't drive usually.By the stretching of material,, can finish driving by the driving engagement roller.
Nip roller is especially similar in appearance to the fine pitch twisted spur gear.In preferred embodiments, roller diameter is 5.935 inches, and helix angle is 45 degree, and normal pitch is 0.100 inch, and span is 30, pressure angle 141, and be the gear of long addendum butt shape basically.For material thickness, this will produce narrow, dark profile of tooth, and described profile of tooth allows about at the most 0.090 inch engagement to engage and about 0.005 inch gap on flank.Described tooth is not the moment of torsion that is used for transmitting rotation, and in the engagement stretched operation of standard contacting metal-metal not.
2. laterally mesh drawing machine
CD engagement stretching device is identical with diagonal lines engagement drawing machine, and is as follows in the difference of nip roller and the design of other secondary regions.Because the CD engaged element can have big depth of engagement, therefore, importantly, when apical axis promoted or reduce, this equipment comprised the device of the axle keeping parallelism that makes two nip rollers.What must guarantee is that the tooth of a nip roller always drops between the tooth of another nip roller, and has avoided the destructive directly contact of potential between engaging tooth.Guaranteed this parallel motion by the rack and pinion arrangement, wherein, stationary rack is connected on each side frame abreast with vertical slidably member.Axle crosses in side frame and the bearing in each vertical slidably member and turns round.Gear is stayed on each end of axle, and engages running with tooth bar, so that produce the parallel motion of wishing.
Except under the engagement tensile situation of relative high coefficient of friction material, the driving of CD engagement drawing machine must be handled nip roller up and down.Yet, drive and need not to be gapless, therefore a spot of vertical imbalance or driving slippage can not produce any problem.Utilize the explanation of CD engaged element, this reason will become apparent.
The CD engaged element is processed with solid materials, but two different diameter disks that preferably are referred to as to pile up alternately.In preferred embodiments, the diameter of engagement disk is 6 inches, and thickness is 0.031 inch, and has full radius on its edge.The diameter that separately meshes the interval disk of disk is 5.5 inches, and thickness is 0.069 inch.For the material on each face, two rollers of this structure can be engaged 0.231 inch, stays 0.019 inch gap.As diagonal lines engagement drawing machine situation, this CD engaged element configuration will have 0.100 inch pitch.
3. vertically mesh drawing machine
MD engagement stretching device is identical with diagonal lines engagement drawing machine, and different is the design of nip roller.The MD nip roller is especially similar in appearance to the fine pitch spurn wheel.
In preferred embodiments, roller diameter is 5.933 inches, 0.100 inch of pitch, and span is 30,14.5 ° of pressure angles, and be the gear of long addendum butt shape basically.Be to get second passage on these rollers of 0.010 inch in the gear hob side-play amount, so that the narrow tooth that has bigger gap is provided.When engaging for about 0.090 inch, this configuration will have about 0.010 inch gap on each face of material thickness.
4. the stretching technique that increases progressively
Can adopt above-mentioned diagonal lines, CD or MD engagement drawing machine, so as to produce the nonwoven web width of cloth and microporosity-formable film increase progressively tensile film or laminating material, thereby form microporous film products of the present invention.For example, can or spin-glue the nonwoven web width of cloth of long filament to staple fibre and the laminating material of extruding of microporosity-shapable thermoplastic film carries out stretched operation.The aspect of a uniqueness of the present invention is can be incrementally the laminating material of the nonwoven web width of cloth that spins-glue long filament to be stretched, so that utmost point flexible fibre is coated in like on the laminating material of cloth.For example utilize CD and/or MD engagement drawing machine that the laminating material of the nonwoven web width of cloth and microporosity-formable film is increased progressively stretching, wherein once pass through drawing machine, about 0.060 inch to 0.120 inch of roller depth of engagement with about 550fpm to 1200fpm or faster speed.Increasing progressively or meshing the tensile result like this has the laminating material of excellent breathability and liquid-barrier properties with generation, but also possesses excellent adhesion strength and soft cloth shape texture.
Following examples will be illustrated the preparation method of microporous membrane of the present invention and laminating material.According to these embodiment and further describe in detail, it will be apparent to those skilled in the art that not breaking away under the scope of the invention and can carry out various changes.
Summary of drawings
Fig. 1 is that the film surface of embodiment 1 amplifies 1000 times Photomicrograph.
Fig. 2 is that embodiment 1A film cross section amplifies 2000 times Photomicrograph.
Fig. 3 is owing to the Photomicrograph of 1000 times of the film surface amplifications of the not stretch zones that forms of engagement among the embodiment 1B.
Fig. 4 is owing to the stretch Photomicrograph of 1000 times of film surface amplifications of the stretch zones forms of engagement among the embodiment 1B.
Fig. 5 is that the film cross section by the stretching surf zone amplifies 2000 times Photomicrograph among the embodiment 1B.
Embodiment 1A and 1B
Use the biodegradable copolyester of aromatic-aliphatic type in these embodiments, as in WO98/23673, fully describing.More precisely, that those of ordinary skills know by using, conventional slot cast film extrusion process, extrude the film that contains the representational biodegradable copolyester of describing among the described disclosed embodiment, it comprises zeolite or the lime carbonate of about 25-40%.Particularly, under the melt temperature of about 425F-475F, extrude the film that thickness is about 2 mils (50 gram/square metre).The Photomicrograph of such film surface is shown among Fig. 1, and cross section is shown among Fig. 2.This film is tested, be found that not to be gas-pervious, but according to ASTM E96E test method, its MVTR (the penetrating rate of moisture) is 939 grams/square metre/day.
Utilize about 0.070 inch CD to engage under the temperature at about 72F, utilize about 0.050 inch MD to engage then, when increasing progressively stretching with above-described device, the film of embodiment 1A will become the penetrating rate of air moisture that can suck and that have increase.MVTR increases to 2350 gram/square metre/day (embodiment 1B) from 939 gram/square metre/day (embodiment 1A).Under 90psi air pressure, the air penetrability that is initially the film of zero air penetrability (embodiment 1A) becomes 570 cc of air/square metre/minute (embodiment 1B).
The Photomicrograph of embodiment 1A and 1B film surface and cross section shows the inorganic particle (referring to Fig. 1-5) that includes really.When increasing progressively stretching, penetrating rate of high humidity of the present invention and gas-pervious biodegradable films have pore to form (referring to Figure 4 and 5) really around inorganic particle.Yet stretch zones does not demonstrate pore and forms (referring to Fig. 3).The cross section (referring to Fig. 5) of embodiment 1B film clearly illustrates that: the hole is communicated with, and air can circulate.(referring to Fig. 2, cross section) do not have foraminous to be communicated with so that air is flow through in the film of embodiment 1A.
The mechanical property of embodiment 1A film is as follows:
Embodiment A Embodiment B The 1A/1B ratio
Total ground mass (GSM) ????50 ????35 ????0.7
90psi downstream cc/cm 2/min ????0 ????570 ????∞
MVTR (gram/square metre/day) ASTM E96E ????939 ????2350 ????2.5
The final tension force of MD (gram/inch) ????1116 ????885
The final tension force of CD (gram/inch) ????756 ????661
MD stretching (%) during fracture ????707 ????494
CD stretching (%) during fracture ????539 ????436
The biodegradable films of embodiment 1B is applicable to: for nursing skin and comfortable and easy to wear, need air flowing (ventilation), the diaper backing of high humidity permeability and liquid barrier performance, the purposes of toilet paper and health care clothes.
Embodiment 2A-2H
In these embodiments, use similar mode, the aromatic-aliphatic type copolyester that embodiment 1A is used is extruded into film.The film of embodiment 2A-2H at room temperature carries out CD and/or MD and stretches, thereby becomes air and the permeable biodegradable films of water vapour, and is as follows.
Embodiment Engagement stretching (inch) 90psi downstream cc/cm 2/min The penetrating rate E96E gm of moisture 2/ day Ground mass (GSM) Stretch ratio (before/afterwards)
??CD ??MD
1A (reference) ??0 ??0 ????0 ????939 ????50 ????0
??2A ??0.040 ??0 ????50 ????1365 ????48 ????1.05
??2B ??0.040 ??0.040 ????110 ????1665 ????45 ????1.11
??2C ??0.050 ??0 ????140 ????1665 ????45 ????1.11
??2D ??0.050 ??0.050 ????280 ????2122 ????39 ????1.28
??2E ??0.060 ??0 ????200 ????1895 ????40 ????1.25
??2F ??0.060 ??0.060 ????490 ????2350 ????33 ????1.51
??2G ??0.070 ??0 ????310 ????2122 ????36 ????1.39
??2H ??0.070 ??0.070 ????720 ????2652 ????29 ????1.72
According to top description, other biodegradable polymkeric substance such as polylactide, polycaprolactone, starch, polyvinyl alcohol, polyester, and copolyester can be handled with inorganic filler particle, with the film that provides air and moisture to suck.
Consider top detailed description, should be understood that, use principle of the present invention,, can carry out various changes according to material and the condition that those of ordinary skills can understand.

Claims (21)

1. air and the permeable biodegradable thermoplastic film of moisture comprise:
The biodegradable thermoplastic polymer that contains the inorganic filler particle disperse phase, the stretch zones of described film has the impermeable thickness of liquid, so that microporosity is provided in film, according to ASTM E96E, the penetrating rate MVTR of the moisture of this film is greater than about 1000 grams/square metre/day, and the air ventilation property under 90psi air pressure is greater than about 30cc/cm 2/ min.
2. the film of claim 1, wherein, biodegradable thermoplastic polymer is selected from polycaprolactone, starch, polyvinyl alcohol, polylactide, polyester, and copolyester, and composition thereof.
3. the film of claim 1, wherein, described filler is selected from lime carbonate, silicon-dioxide, talcum, barium sulfate, zeolite, and mica, and composition thereof.
4. be laminated to the film of the claim 1 on the biodegradable fibrous web.
5. the film of claim 4, wherein, the fiber of described fibrous web is selected from: cellulose polymer compound, polyester, copolyester, the polymkeric substance of L lactic acid fully, the polymkeric substance of complete D lactic acid, the multipolymer of L lactic acid and D lactic acid, and the mixture of polymers of L lactic acid and D lactic acid.
6. the film of claim 1, wherein, biodegradable thermoplastic polymer is selected from: polyvinyl alcohol (PVA), polycaprolactone (PCL), polylactide (PLA), starch, starch and PVA, the mixture of PCL or PLA, poly-hydroxyl (butyric ester) (PHB), gather hydroxyl (valerate) (PHV), and aliphatic-Aromatic copolyesters, and composition thereof.
7. the film of claim 1, wherein, the thickness of microporous membrane is about the 0.25-10 mil.
8. the film of claim 1, wherein, the thickness of microporous membrane is about the 0.25-2 mil.
9. the film of claim 1, wherein, according to ASTM E96E, the penetrating rate of its moisture (MVTR) be about the 2000-4500 gram/square metre/every day, and air penetrability is about 200-1600cc/min/cm under 90psi air pressure 2
10. the film of claim 1, wherein, described mineral filler is selected from lime carbonate, barium sulfate, mica, talcum, silicon-dioxide, and zeolite.
11. a high speed production has the method for liquid barrier performance, air and moisture permeability, biodegradable thermoplastic film, comprising:
The biodegradable thermoplastic polymer of the about 40-75% weight of melt blending and the inorganic filler particle of about 25-60% weight, thus biodegradable thermoplastic polymer composition formed;
By slit die the net width of cloth of described molten thermoplastic composition is extruded,, entered in the roll gap, thereby, under speed, form the film of the about 0.25-10 mil of thickness at least about 550-1200fpm not having under the draw resonance by the cooling zone;
Under described speed, along basically and evenly across described film and run through the line of its degree of depth, the drawing force that will increase progressively is applied on the described film, thereby the E96E according to ASTM is provided, MVTR greater than about 1000 the gram/square metre/day and under 90psi air pressure the air ventilation property greater than about 30cc/cm 2The biodegradable microporous membrane of/min.
12. the method for claim 11, wherein, according to ASTM E96E, MVTR be about 2000-4500 gram/square metre/every day, and air penetrability is about 200-1600cc/min/cm under 90psi air pressure 2
13. the method for claim 11 comprises the biodegradable nonwoven web width of cloth is introduced in the described roll gap, and controls force of compression so that the net width of cloth is bonded on the described film, and stretches to form laminated biodegradable film.
14. the method for claim 11, wherein, biodegradable thermoplastic polymer is selected from polycaprolactone, starch, and polyvinyl alcohol, polylactide, polyester, and copolyester, and composition thereof.
15. the method for claim 11, wherein said filler is selected from lime carbonate, silicon-dioxide, and talcum, barium sulfate, zeolite, and mica, and composition thereof.
16. the method for claim 11, wherein, the fiber of described fibrous web is selected from: cellulose polymer compound, polyester, copolyester, the polymkeric substance of L lactic acid fully, the polymkeric substance of complete D lactic acid, the multipolymer of L lactic acid and D lactic acid, and the mixture of polymers of L lactic acid and D lactic acid.
17. the method for claim 11, wherein, biodegradable thermoplastic polymer is selected from: polyvinyl alcohol (PVA), polycaprolactone (PCL), polylactide (PLA), starch, starch and PVA, the mixture of PCL or PLA, poly-hydroxyl (butyric ester) (PHB), gather hydroxyl (valerate) (PHV), and aliphatic-Aromatic copolyesters, and composition thereof.
18. the method for claim 11, wherein, the thickness of microporous membrane is about the 0.25-10 mil.
19. the method for claim 11, wherein, the thickness of microporous membrane is about the 0.25-2 mil.
20. the method for claim 11, wherein, according to ASTM E96E, the penetrating rate of moisture (MVTR) is about 2000-4500 gram/square metre/day.
21. the method for claim 11, wherein, the about 1-10 micron of the mean particle size of described mineral filler, and be selected from lime carbonate, barium sulfate, silicon-dioxide and zeolite.
CNA018193250A 2000-11-22 2001-06-26 Air and moisture vapor breathable biodegradable films and method of manufacture Pending CN1596277A (en)

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