CA2329529A1 - High speed method of making microporous film products - Google Patents
High speed method of making microporous film products Download PDFInfo
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- CA2329529A1 CA2329529A1 CA002329529A CA2329529A CA2329529A1 CA 2329529 A1 CA2329529 A1 CA 2329529A1 CA 002329529 A CA002329529 A CA 002329529A CA 2329529 A CA2329529 A CA 2329529A CA 2329529 A1 CA2329529 A1 CA 2329529A1
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- styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- 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
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
-
- 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
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0625—LLDPE, i.e. linear low density polyethylene
-
- 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
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
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- 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
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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
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
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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
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/026—Porous
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Abstract
Microporous film products permeable to moisture vapor and which act as barriers to liquid are made by a high speed method. Such microporous products are made at speeds in the order of above 500 fpm to about 1200 fpm.
Thermoplastic polymers are melt blended to contain about 35 % to about 45 % by weight of a linear low density polyethylene, about 3 % to about 10 % by weight of a low density polyethylene; about 40 % to about 55 % by weight calcium carbonate filler particles, and about 2 % to about 6 % by weight of a triblock polymer of styrene.
Thermoplastic polymers are melt blended to contain about 35 % to about 45 % by weight of a linear low density polyethylene, about 3 % to about 10 % by weight of a low density polyethylene; about 40 % to about 55 % by weight calcium carbonate filler particles, and about 2 % to about 6 % by weight of a triblock polymer of styrene.
Description
_1_ HIGH SPEED METHOD OF MAKING MIC OPOR~OUS FILM~RODUCTS
BACKGROUND OF THE INVENTION
Methods of making microporous film products have been known for some time. For' example, U. S. Patent No. 3,832,2fi7, to Liu, teaches the melt-embossing of a polyolefin film containing a dispersed amorphous polymer phase prior to stretching or orientation to improve gas and moisture vapor transmission of the film. According to the Liu '2fi7 patent, a film of crystalline polypropylene having a dispersed amorphous polypropylene phase is first embossed prior to biaxially drawing (stretching) to produce an oriented imperforate film having greater permeability. The dispersed amorphous phase serves to provide microvoids to enhance the permeability of the otherwise imperforate film to improve moisture vapor transmission (MVT). The embossed film is preferably embossed and drawn sequentially.
In 1976, Schwarz published a paper which described polymer blends and compositions to produce microporous substrates (Eckhard C.A.
Schwartz (Biax-Fiberfilm), "New Fibrillated Film Structures, Manufacture WO 99/60050 ~ PCT/US99/10562 and Uses", Pap. Synth. C.anf. (TAPPI1, 1976, pages 33-39). According to this paper, a film of two or more incompatible polymers, where one polymer forms a continuous phase and a second polymer forms a discontinuous phase, upon being stretched will phase separate thereby leading to voids in the polymer matrix and increasing the porosity of the film. The continuous filrn matrix of a crystallizable polymer may also be filled with inorganic filller such as clay, titanium dioxide, calcium carbonate, etc., to provide microporosity in the stretched polymeric substrate.
Many other patents and publications disclose the phenomenon of making microporous thermoplastic film products. For example, European patent 141592 discloses the use of a polyolefin, particularly ethylene vinyl acetate (EVA) containing a dispersed polystyrene phase which, when stretched, produces a voided film which improves the moisture vapor permeability of the film. This EP '592 patent also discloses the sequential steps of embossing the EVA film with thick and thin areas faliowed by stretching to first provide a film having voids which, when further stretched, produces a net-tike product. U. S. Patents Nos. 4,452,845 and 4,596,738 also disclose stretched thermoplastic films where the dispersed phase may bs a polyethylene filled with calcium carbonate to provide the rnicrovoids upon stretching. Later U. S. Patents Nos. 4,777,073; 4,814,1:24; and 4,921,653 disclose the same processes described by the above-mentioned earlier publications involving the steps of first embossing a polyolefin film containing a filler and then stretching that film to provide a microporous product.
With reference to U. S. Patents Nos. 4,705,812 and 4,705,813, microporous films have been produced from a blend of linear low density polyethylene (LLDPE) and Low density polyethylene (LDPE) with barium sulfate as the inorganic filler having an average particle diameter of 0.1-7 microns. It is also known to modify blends of LLDPE
and LDPE with a thermoplastic rubber such as Kraton. Other patents, such as U. S. Patent No. 4,582,871, disclose the use of thermoplastic styrene block tripolymers in the production of microporous films with other incompatible polymers such as styrene. There are other general teachings in the art such as the disclosures in U. S. Patents Nos. 4,472,328 and 4,921,652.
Relevant patents regarding extrusion lamination of unstretched nonwoven webs include U. S. Patent Nos. 2,714,571;
3,058,868; 4,522,203; 4,614,679; 4,692,368; 4,753,840 and 5,035,941. The above '863 and '368 patents disclose stretching extruded polymeric films prior to laminating with unstretched nonwoven fibrous webs at pressuire roller nips. The '203 and '941 patents are directed to co-extruding multiple polymeric films with unstretched nonwoven webs at preasure roller nips. The '840 patent discloses preforming nonwoven polymeric fiber materials prior to extrusion laminating with films to improve bonding between the nonwoven fibers WO 99/60050 ' PCT/US99/10562 and films. More specifically, the '840 patent discloses conventional embossing techniques to form densified and undensified areas in nonwoven base plies prior to extrusion lamination to improve bonding between nonwoven fibrous webs and films by means of the densified fiber areas. The '941 patent also teaches that unstretched nonwoven webs that are extrusion laminsited to single ply polymeric films are susceptible to pinholes caused by fibers extending generally vertically from the plane of the fiber substrate and, accordingly, this patent discloses using multiple co-extruded film plies to prevent pinhole problems. Furthermore, methods for bonding loose nonwoven fibers to polymeric film are disclosed in U. S.
Patents Nos. 3,622,422; 4,379,197 and 4,725,473.
It has also been known to stretch nonwoven fibrous webs using intermeshing rollers to reduce basis weight and examples of patents in this area are U. S. Patents Nos. 4,153,664 and 4,517,714. The '664 patent discloses a method of incremental cross direction (CD) or machine direction fMD) stretching nonwoven fibrous webs using a pair of interdigitating rollers to strengthen and soften nonwoven webs. The '664 patent also discloses an alternative embodiment wherein the nonwoven fibrous web is laminated to the thermoplastic film prior to intermesh stretching.
efforts have also been made to make breathable non-woven composite barrier fabrics which are impervious to liquids, but which are permeable to water vapor. United States Patent No. 5,409,761 is an WO 99/60050 PCT/IlS99l10562 _5_ example of a fabricatian process from the patent art. According to this '761 patent, a nonwoven composite fabric is made by ultrasonically bonding a microporous thermoplastic film to a layer of nonwoven fibrous thermoplastic material. These methods and other methods of making breathable laminates of nonwoven and thermoplastic materials tend to involve expensive manufacturing techniques and/or expensive raw materials.
Notwithstanding the extensive development of the art for making breathable microporous films and laminates ~to provide air and moisture vapor permeabilities with liquid-barrier properties, further improvements are needed. In particular, improvements are desired for producing microporous film products and laminates on high-speed production machinery. It would be very desirable to produce microporous film products without undesirable pin holes and without draw resonance.
fn the past, attempts to increase production speeds have resulted in film breakage or film product, with inconsistent properties.
SUMMARY OF THE INV 'N
This invention is directed to a high speed method of making a microporous thermoplastic film. The microporous film is permeable to air and water vapor, but: is a harrier to liquid. Breathable laminates of microporous film with nonwoven substrates are also produced at high speeds according to the method of this invention.
~u-u4-~UUU ~, . _ U S 009910562 . . . . .. .. .. . .. ..
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The high speed method of this invention involves melt-blending a composition comprising (a) about 35 % to about 45 % by weight of a linear low density polyethylene, (b? about 3% to about 70% by weight of a low density polyethylene, (c) about 40% to about 55% by weight calcium carbonate filler particles, and (d1 about 2% to about 6% by weight of a triblock copolymer of styrene selected from the group consisting of styrene-butadiene-styrene, styrene-lsopre~e-styrene, and styrene-ethylene-butylene-styrene, and blends thereof.
T he melt-blended composition is extruded, preferably through a slot die, into a nip of rollers with an air knife to form a fifrn at a speed on the order ~a~ 9~4 ~0 6'o9G 4..~/s~
of at least about 550 fpm to about 1200 fpm~~n~ithout draw resonance.
C G' 096 vv.l.9, Speeds of at least about 750 fpmLto about 7 200 ferry, or greater, have been achieved without draw resonance. The use of theC.air knife to assist in the elimination of draw resonance is known, for exampEe, by reference to U. S. Patent No. 4,626,574. T hereafter, an incremental stretching f orce is applied to the filrn at the high speeds along lines substantially uniformalfy across the film and throughout its depth to provide a microporous fiirn. T hue, this invention provides a high speed anethod of AMENDED SHEET _ U5 00991 USbz 20-04-200 ~ -1 ~. _ .. .. .. . .. ...
i. .. .. . . v . v . . .
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- . . . . . . . . . . . .
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making microporous filnns and laminates with nonwoven substrates of uniform gauge. The problem of draw resonance which has heretofore resulted in irregular gauge or thickness in the film products is avoided, g~ - ~O ~og~O w~!
even though line speeds of about 750-1200 fprn~are achieved.
The bland of LLDPE and LDPE within the approximate ranges of components enables the production of film without breakage and pin holes when balanced wiith the prescribed amount of calcium carbonate.
In particular, the LLDPE is present in an amount of about 35% to about 45°~o by weight in order to provide a sufficient amount of matrix to carry the calcium carbonate filler particles thereby enabling the film to be handled and stretched without pin holing and breakage. T he LDPE in an amount of about 3% to ,about 1 D% by weight also contributes to the production of film without pin holing and enables the high speed production without draw resonance. T he polymeric matrix is balanced with an amount o~ about 40°!° to about 55% by weight of calcium carbonate particles havino an average particle diameter of preferably about 1 micron to achieves sufficient MVT in the range of about '! 000 gmsirn2Jday to 4000 gmsim2iday. Furthermore, the melt-blended composition requires a triblock polymer in an amount of about 2°/o to about fi% by weight to facilitate stretching in high-speed production without breakage. An incremental stretching force is appiied infine to the f ormed film under ambi=,:nt conditions or at an elevated temperature at speeds of at least about ;~50 p~m to a'aout 1200 fp or more; along Lines AMENDED SHEET _ _g_ substantially uniformly across the film and throughout it depth to provide a microporous film.
The method of this invention also involves lamination of the microporous-formable thermoplastic film to a nonwoven fibrous web during extrusion. The extrusion lamination is conducted at the same high speeds where a nonwoven fibrous web is introduced into the nip of rollers along with the microporous-formable thermoplastic extrudate. The compressive force between the fibrous web and the extrudate is controlled to bond one surface of the web to the film and form a laminate.
The laminate is then incrementally stretched along fines substantially uniformly across the laminate and throughout its depth in one direction to render the film microporous. The laminate may be stretched in both the cross direction and the machine direction to provide breathable cloth-like liquid barriers capable of transmitting moisture vapor and air.
Other benefits, advantages and objectives of this invention will be further understood with reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
It is the primary objective of this invention to produce a microporous film and laminated products thereof with nonwoven fibrous webs on high-speed prodiuction machinery. It is the further objective of the method to produce such microporous film products of regular gauge, uniform porosity and without breakage.
20-04-20~~0 -~ ~ US 009910b62 .. .. .. . ..
~i~ i ~ ~ . . ~ . . . ~ ~ ~ ~ .
i ~ . ~ 1 . . ~ ~ . ~ ~ ~ .
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__9_ A. Materials for the Method As developed above, these and other objectives are achieved in a preferred form of the: invention by first melt blending a composition of b (a) ~ about 3b% to about 45% by weight of a linear low density polyethylene, (b) about 3% to about 10% by weight of a low density polyethylene, (c) about 40% to about 5b% by weight calcium carbonate filler particles, and fd) about 2% to about o% by weight of a triblock copolymer of styrene selected from tha group consisting of styrene-butadiene-styrene, styrenE-isoprene-styrene, and styrene-ethylene-butylene-1 b styrene, and blends thereof, extruding said melt blendsd composition into a nip of rollers to form a film at a speed on the order of at least about 5~0 fpm to about (~ ~ g ~ 4- t~ 6 . c~ 9 c ~,.~-~ s~
7 200 fpm'wi hoot draw resonance, and applying an iincremsntal stretching force to said film at said speed along fines substantially uniformly across said film and throughout its depth to provide a microporous film.
More particularly, in a preferred form, the melt-blended composition consists essentially of about 42°/o by weight LLDP~, about AMENDED SHEET -20-04-2000 -~ US 009910562 ~.
_ ~ ~ ~ ~ ~ ~ ~ ~ ~ 1 ~ : ~1-~
.s!- ~i i ~ ~ ~ ~ ~ ~ ~ 1 ~ 1 1 ~ n' H i~ ~ ~ ~ ~ ~ ~ 1 1 ~ ~ ~ ~ ~
~ 1 ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ ~ ~ ~ ~ ~ ~ 1 ~ 1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ t ~ ~ ~
4% by weight LDPE, about 44% by weight calcium carbonate filler particles having an average particle site of about 1 micron, and about 3 % by weight triblock polymer, especially styrene-butadiene-styrene. If desired, the stiffness properties of the microporous film products may be controlled by including high density polyethylene on the order of about 0-5% by weight and including 0-4% by weight titanium dioxide.
Typically, processing aid such as a flurocarbon polymer in an amount of about 0.1 % to about C>.2% by weight is added, as exemplified by 1-propene,1,1,2,3,3,3-he:xaffuoro copolymer with 1,1-difiuoroethylene.
The triblock polymer may also be blended with oil, hydrocarbon, antioxidant and stabilizer. Antioxidants include tetrakis (methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane trade name is lrganox 1010), and tris(2.,4-di-tert-butylphenyl)phosphite (trade name is irgafos 168) at a total of 500-4000 ppm (parts per miliion).
Both embossed and flat films may be produced according to the principles of this invention. In the csse of an embossed nim, the nip of rollers comprises a mfaal embossing roller and a rubber roller. The compressive force between the rollers forms an embossed film of desired la - ~ b ~ 5 4~,w,.~
thickness on the .order of about 0.5 to about 10 mil. It has also been found that rollers which provide a polished chrome surface form a flat film. lNhether the film is an embossed film or a flat film, upon incremental stretching, at high speeds, microporous film products are produced having high moisture vapor transmission rats lf~I~R) within the acceptable range AMENDED SHEET -20-04-2000 ~ US 009910562 . . . .. .. .. . .. ..:
f .i i ~ ~ ~ . 1 . . ~ ~ ~ ~
t. i~ ~ ~ 1 ~ ~ . ~ ~ ~ ~ ~ ~ .
. . ~ ~ ~ . i . 1 ~ ~ ~ ~ ~ ~ ~ ~
- . ~ 1 ~ t . ~ 1 ~ ~ ~ .
. ~ ~~~~ ~~ .. ~ ~1 !.
of about 1000 to 4000 c~mslm~/day. It has been found that fiat film can be incrementally stretched more uniformly than embossed film. The process may be conducted at ambient or room temperature or at elevated temperatures. As described above, laminates of the microporous film rnay be obtained with nonwoven fibrous webs.
The nonwoven fibrous web may comprise fibers of polyethylene, polypropylene, polyesters, rayon, cellulose, nylon, and blends of such fibers. A number of definitions have been proposed for nonwoven fibrous webs. The fibers are usually staple fibers or continuous filaments. T he nonwove:ns are usually referred to as spunbond, carded, meltblown, and the like. Thn fibers or filaments may be bicomponent to f acilitate bonding. For example, a fiber having a sheath and core of different polymers such as-polyethylene (PE) and polypropylene (PP) may be used; or mixtures of PE and PP fibers may be used. As used herein ~ 5 "nonwoven fibrous web" is used in its generic sense to den'ne a generally planar structure that is relatively flat, flexible and porous, and is composed Of staple 1'IberS Or COntinu061S filaments. For a detailed description of nonwovens, see "Nonwov°n Fabric primer and Reference Sampler" by c. A. Vaughn, Association of the Nonwoven Fabrics Industry, 3d edition (1992).
In a preferred form, the microporous laminate employs a film tb ~ 3 5 to a 5~.~ur..,) having a gauge or a thickness between about 0.25 and 10 milsLand, depending upon use, the film thickness will vary and, most preferably, in -. -1 ~ ~~ ~1 .. . ~~ . .i~
:i .~ i . ~ : . . a ~ : ~
V : 1 ~ ~ 1 ~ . i ~ ~ . . ~ .
. ~ ~ 1 . . . . ~.~~ i ~ 1 . .
. ~ ~ ~ . . ~ . . i . .
. . .~~~ .1 .. . .. ~~
~Co ~ 3 5 I'o 6° ' $~"~~
disposable applications is the order of about 0.25 to 2 milsLin thickness.
The nonwoven fibrous webs of the laminated sheet normally have a ~5 -9g t~ 89 ~ ~o~lw.z>
weight of about 5 gmslyd2 to 75 gms/yd~ preferably about 20 to about - (~a~9a ~ y~~s4~L,..z G.-~
40 gms/yd~ The. composite or laminate can be incrementally stretched in the cross direction (CD} to form a CD stretched composite.
Furthermore, CD stretching may be followed by stretching in the machine direction (MD} to form a composite which is stretched in both CD and MD
directions. As indicated above, the microporous film or laminate may be used in many different applications such as baby diapers, baby training pants, catamenial pads and garments, and the like where moisture vapor and air transmission properties, as well as fluid barrier properties, are needed. , B. Stretchers for the Microporous Film and Laminates A number of different stretchers and techniques may be employed to stretch the film or laminate of a nonwoven fibrous web and microporous-formable film. T hesa laminates of nonwoven carded fibrous webs of staple fibers or nonwoven spun-bonded fibrous webs may be stretched with the stretclhers and techniques described as foliov~~s:
'1. Diagonal int~errneshino Stretcher T he diagona'I intermeshing stretcher consists of a pair of left hand and rioht hand helical gear-Like elements on parallel shafts. T he shafts are disposed between two machine side plates, the lower shaft being located in fixed b~arincs and the upper shaft being aocated in CA 02329529 2000-10-17 AMENDED SHEET _ bearings in vertically slidable members. The slidable members are adjustable in the vertical direction by wedge shaped elements operable by adjusting screws. Screwing the wedges out or in will move the vertically slidable member respectively down or up to further engage or disengage the gear-like teeth of the upper intermeshing roll with the lower intermeshing roll. Micrometers mounted to the side frames are operable to indicate the depth of engagement of the teeth of the intermeshing roll.
Air cylinders are employed to hold the siidable members in their lower engaged position firmly against the adjusting wedges to oppose the upward force Exerted by the material being stretched. These cylinders may also be retracted to disengage the upper and lower intermeshing rolls from each other for purposes of threading material through the intermeshing equipment or in conjunction with a safety circuit which would open all the machine nip points when activated.
A drive means is typically utilized to drive the stationery intermeshing roll. If the upper intermeshing rol! is to be disengageable for purposes of machine threading or safety, it is preferable to use an antibacklash gearing arrangement between the upper and lower intermeshing rolls to assure that upon reengagement the teeth of one ?0 intermeshing roll always fall between the teeth of the other intermeshing roll and potentially damaging physical contact between addenda of intermeshing teeth is avoided. !f the intermeshing rolls are to remain in constant engagement, the upper intermeshing roll typically need not be 20-04-20~~0 . US 009910562 , . ~ : , .. .. .: . ..
- ~:~ .. ..- .. . . .. . .-.
,. : . . .. . . .. . . ..
. . . . .... . . . .
. , . . . . . . . . ..
~14- ~ .... .. .. . .. ..
driven. Drive may be accomplished by the driven intermeshing roll through the material being stretched.
The interm=ahing rolls closely resemble fine pitch helical ~I5 ~o~5c....., gears. In the preferred ernbodiment, the rolls have 5.935" diamete~ 45°
w ~.25~+ cw~) helix angle, a 0.100"~no~rmal pitch, 30 diametral pitch, 14'/2°
pressure angle, and are basically a long addendum topped gear. This produces a to-~~~6c~~, narrow, deep tooth pronle which allows up to about 0.090"~ of Ca - 4 ~ ~~ c,.,.,) intermeshing engagement: and about 0.005"fclearance on the sides of the tooth for material thickness. The teeth are not designed to transmit rotational torque and do not contact metal-to-metal in normal intermeshing stretching operation.
BACKGROUND OF THE INVENTION
Methods of making microporous film products have been known for some time. For' example, U. S. Patent No. 3,832,2fi7, to Liu, teaches the melt-embossing of a polyolefin film containing a dispersed amorphous polymer phase prior to stretching or orientation to improve gas and moisture vapor transmission of the film. According to the Liu '2fi7 patent, a film of crystalline polypropylene having a dispersed amorphous polypropylene phase is first embossed prior to biaxially drawing (stretching) to produce an oriented imperforate film having greater permeability. The dispersed amorphous phase serves to provide microvoids to enhance the permeability of the otherwise imperforate film to improve moisture vapor transmission (MVT). The embossed film is preferably embossed and drawn sequentially.
In 1976, Schwarz published a paper which described polymer blends and compositions to produce microporous substrates (Eckhard C.A.
Schwartz (Biax-Fiberfilm), "New Fibrillated Film Structures, Manufacture WO 99/60050 ~ PCT/US99/10562 and Uses", Pap. Synth. C.anf. (TAPPI1, 1976, pages 33-39). According to this paper, a film of two or more incompatible polymers, where one polymer forms a continuous phase and a second polymer forms a discontinuous phase, upon being stretched will phase separate thereby leading to voids in the polymer matrix and increasing the porosity of the film. The continuous filrn matrix of a crystallizable polymer may also be filled with inorganic filller such as clay, titanium dioxide, calcium carbonate, etc., to provide microporosity in the stretched polymeric substrate.
Many other patents and publications disclose the phenomenon of making microporous thermoplastic film products. For example, European patent 141592 discloses the use of a polyolefin, particularly ethylene vinyl acetate (EVA) containing a dispersed polystyrene phase which, when stretched, produces a voided film which improves the moisture vapor permeability of the film. This EP '592 patent also discloses the sequential steps of embossing the EVA film with thick and thin areas faliowed by stretching to first provide a film having voids which, when further stretched, produces a net-tike product. U. S. Patents Nos. 4,452,845 and 4,596,738 also disclose stretched thermoplastic films where the dispersed phase may bs a polyethylene filled with calcium carbonate to provide the rnicrovoids upon stretching. Later U. S. Patents Nos. 4,777,073; 4,814,1:24; and 4,921,653 disclose the same processes described by the above-mentioned earlier publications involving the steps of first embossing a polyolefin film containing a filler and then stretching that film to provide a microporous product.
With reference to U. S. Patents Nos. 4,705,812 and 4,705,813, microporous films have been produced from a blend of linear low density polyethylene (LLDPE) and Low density polyethylene (LDPE) with barium sulfate as the inorganic filler having an average particle diameter of 0.1-7 microns. It is also known to modify blends of LLDPE
and LDPE with a thermoplastic rubber such as Kraton. Other patents, such as U. S. Patent No. 4,582,871, disclose the use of thermoplastic styrene block tripolymers in the production of microporous films with other incompatible polymers such as styrene. There are other general teachings in the art such as the disclosures in U. S. Patents Nos. 4,472,328 and 4,921,652.
Relevant patents regarding extrusion lamination of unstretched nonwoven webs include U. S. Patent Nos. 2,714,571;
3,058,868; 4,522,203; 4,614,679; 4,692,368; 4,753,840 and 5,035,941. The above '863 and '368 patents disclose stretching extruded polymeric films prior to laminating with unstretched nonwoven fibrous webs at pressuire roller nips. The '203 and '941 patents are directed to co-extruding multiple polymeric films with unstretched nonwoven webs at preasure roller nips. The '840 patent discloses preforming nonwoven polymeric fiber materials prior to extrusion laminating with films to improve bonding between the nonwoven fibers WO 99/60050 ' PCT/US99/10562 and films. More specifically, the '840 patent discloses conventional embossing techniques to form densified and undensified areas in nonwoven base plies prior to extrusion lamination to improve bonding between nonwoven fibrous webs and films by means of the densified fiber areas. The '941 patent also teaches that unstretched nonwoven webs that are extrusion laminsited to single ply polymeric films are susceptible to pinholes caused by fibers extending generally vertically from the plane of the fiber substrate and, accordingly, this patent discloses using multiple co-extruded film plies to prevent pinhole problems. Furthermore, methods for bonding loose nonwoven fibers to polymeric film are disclosed in U. S.
Patents Nos. 3,622,422; 4,379,197 and 4,725,473.
It has also been known to stretch nonwoven fibrous webs using intermeshing rollers to reduce basis weight and examples of patents in this area are U. S. Patents Nos. 4,153,664 and 4,517,714. The '664 patent discloses a method of incremental cross direction (CD) or machine direction fMD) stretching nonwoven fibrous webs using a pair of interdigitating rollers to strengthen and soften nonwoven webs. The '664 patent also discloses an alternative embodiment wherein the nonwoven fibrous web is laminated to the thermoplastic film prior to intermesh stretching.
efforts have also been made to make breathable non-woven composite barrier fabrics which are impervious to liquids, but which are permeable to water vapor. United States Patent No. 5,409,761 is an WO 99/60050 PCT/IlS99l10562 _5_ example of a fabricatian process from the patent art. According to this '761 patent, a nonwoven composite fabric is made by ultrasonically bonding a microporous thermoplastic film to a layer of nonwoven fibrous thermoplastic material. These methods and other methods of making breathable laminates of nonwoven and thermoplastic materials tend to involve expensive manufacturing techniques and/or expensive raw materials.
Notwithstanding the extensive development of the art for making breathable microporous films and laminates ~to provide air and moisture vapor permeabilities with liquid-barrier properties, further improvements are needed. In particular, improvements are desired for producing microporous film products and laminates on high-speed production machinery. It would be very desirable to produce microporous film products without undesirable pin holes and without draw resonance.
fn the past, attempts to increase production speeds have resulted in film breakage or film product, with inconsistent properties.
SUMMARY OF THE INV 'N
This invention is directed to a high speed method of making a microporous thermoplastic film. The microporous film is permeable to air and water vapor, but: is a harrier to liquid. Breathable laminates of microporous film with nonwoven substrates are also produced at high speeds according to the method of this invention.
~u-u4-~UUU ~, . _ U S 009910562 . . . . .. .. .. . .. ..
.. . . .. , , y. . . . .
. . . .. . . .. . . ..
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- . . . . . . . . . ..
. 6- . .... .. .. . .. ..
The high speed method of this invention involves melt-blending a composition comprising (a) about 35 % to about 45 % by weight of a linear low density polyethylene, (b? about 3% to about 70% by weight of a low density polyethylene, (c) about 40% to about 55% by weight calcium carbonate filler particles, and (d1 about 2% to about 6% by weight of a triblock copolymer of styrene selected from the group consisting of styrene-butadiene-styrene, styrene-lsopre~e-styrene, and styrene-ethylene-butylene-styrene, and blends thereof.
T he melt-blended composition is extruded, preferably through a slot die, into a nip of rollers with an air knife to form a fifrn at a speed on the order ~a~ 9~4 ~0 6'o9G 4..~/s~
of at least about 550 fpm to about 1200 fpm~~n~ithout draw resonance.
C G' 096 vv.l.9, Speeds of at least about 750 fpmLto about 7 200 ferry, or greater, have been achieved without draw resonance. The use of theC.air knife to assist in the elimination of draw resonance is known, for exampEe, by reference to U. S. Patent No. 4,626,574. T hereafter, an incremental stretching f orce is applied to the filrn at the high speeds along lines substantially uniformalfy across the film and throughout its depth to provide a microporous fiirn. T hue, this invention provides a high speed anethod of AMENDED SHEET _ U5 00991 USbz 20-04-200 ~ -1 ~. _ .. .. .. . .. ...
i. .. .. . . v . v . . .
. . . . . . . . . . . .
. . . ~ . . . . v .... . . . . .
- . . . . . . . . . . . .
. . .... .. .. . .. ..
making microporous filnns and laminates with nonwoven substrates of uniform gauge. The problem of draw resonance which has heretofore resulted in irregular gauge or thickness in the film products is avoided, g~ - ~O ~og~O w~!
even though line speeds of about 750-1200 fprn~are achieved.
The bland of LLDPE and LDPE within the approximate ranges of components enables the production of film without breakage and pin holes when balanced wiith the prescribed amount of calcium carbonate.
In particular, the LLDPE is present in an amount of about 35% to about 45°~o by weight in order to provide a sufficient amount of matrix to carry the calcium carbonate filler particles thereby enabling the film to be handled and stretched without pin holing and breakage. T he LDPE in an amount of about 3% to ,about 1 D% by weight also contributes to the production of film without pin holing and enables the high speed production without draw resonance. T he polymeric matrix is balanced with an amount o~ about 40°!° to about 55% by weight of calcium carbonate particles havino an average particle diameter of preferably about 1 micron to achieves sufficient MVT in the range of about '! 000 gmsirn2Jday to 4000 gmsim2iday. Furthermore, the melt-blended composition requires a triblock polymer in an amount of about 2°/o to about fi% by weight to facilitate stretching in high-speed production without breakage. An incremental stretching force is appiied infine to the f ormed film under ambi=,:nt conditions or at an elevated temperature at speeds of at least about ;~50 p~m to a'aout 1200 fp or more; along Lines AMENDED SHEET _ _g_ substantially uniformly across the film and throughout it depth to provide a microporous film.
The method of this invention also involves lamination of the microporous-formable thermoplastic film to a nonwoven fibrous web during extrusion. The extrusion lamination is conducted at the same high speeds where a nonwoven fibrous web is introduced into the nip of rollers along with the microporous-formable thermoplastic extrudate. The compressive force between the fibrous web and the extrudate is controlled to bond one surface of the web to the film and form a laminate.
The laminate is then incrementally stretched along fines substantially uniformly across the laminate and throughout its depth in one direction to render the film microporous. The laminate may be stretched in both the cross direction and the machine direction to provide breathable cloth-like liquid barriers capable of transmitting moisture vapor and air.
Other benefits, advantages and objectives of this invention will be further understood with reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
It is the primary objective of this invention to produce a microporous film and laminated products thereof with nonwoven fibrous webs on high-speed prodiuction machinery. It is the further objective of the method to produce such microporous film products of regular gauge, uniform porosity and without breakage.
20-04-20~~0 -~ ~ US 009910b62 .. .. .. . ..
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. 1 ~ . . . . . ~ ~ ~ . . ~ . . .
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. ~ .~.. .~ .~ ~ .~ ..
__9_ A. Materials for the Method As developed above, these and other objectives are achieved in a preferred form of the: invention by first melt blending a composition of b (a) ~ about 3b% to about 45% by weight of a linear low density polyethylene, (b) about 3% to about 10% by weight of a low density polyethylene, (c) about 40% to about 5b% by weight calcium carbonate filler particles, and fd) about 2% to about o% by weight of a triblock copolymer of styrene selected from tha group consisting of styrene-butadiene-styrene, styrenE-isoprene-styrene, and styrene-ethylene-butylene-1 b styrene, and blends thereof, extruding said melt blendsd composition into a nip of rollers to form a film at a speed on the order of at least about 5~0 fpm to about (~ ~ g ~ 4- t~ 6 . c~ 9 c ~,.~-~ s~
7 200 fpm'wi hoot draw resonance, and applying an iincremsntal stretching force to said film at said speed along fines substantially uniformly across said film and throughout its depth to provide a microporous film.
More particularly, in a preferred form, the melt-blended composition consists essentially of about 42°/o by weight LLDP~, about AMENDED SHEET -20-04-2000 -~ US 009910562 ~.
_ ~ ~ ~ ~ ~ ~ ~ ~ ~ 1 ~ : ~1-~
.s!- ~i i ~ ~ ~ ~ ~ ~ ~ 1 ~ 1 1 ~ n' H i~ ~ ~ ~ ~ ~ ~ 1 1 ~ ~ ~ ~ ~
~ 1 ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ ~ ~ ~ ~ ~ ~ 1 ~ 1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ t ~ ~ ~
4% by weight LDPE, about 44% by weight calcium carbonate filler particles having an average particle site of about 1 micron, and about 3 % by weight triblock polymer, especially styrene-butadiene-styrene. If desired, the stiffness properties of the microporous film products may be controlled by including high density polyethylene on the order of about 0-5% by weight and including 0-4% by weight titanium dioxide.
Typically, processing aid such as a flurocarbon polymer in an amount of about 0.1 % to about C>.2% by weight is added, as exemplified by 1-propene,1,1,2,3,3,3-he:xaffuoro copolymer with 1,1-difiuoroethylene.
The triblock polymer may also be blended with oil, hydrocarbon, antioxidant and stabilizer. Antioxidants include tetrakis (methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane trade name is lrganox 1010), and tris(2.,4-di-tert-butylphenyl)phosphite (trade name is irgafos 168) at a total of 500-4000 ppm (parts per miliion).
Both embossed and flat films may be produced according to the principles of this invention. In the csse of an embossed nim, the nip of rollers comprises a mfaal embossing roller and a rubber roller. The compressive force between the rollers forms an embossed film of desired la - ~ b ~ 5 4~,w,.~
thickness on the .order of about 0.5 to about 10 mil. It has also been found that rollers which provide a polished chrome surface form a flat film. lNhether the film is an embossed film or a flat film, upon incremental stretching, at high speeds, microporous film products are produced having high moisture vapor transmission rats lf~I~R) within the acceptable range AMENDED SHEET -20-04-2000 ~ US 009910562 . . . .. .. .. . .. ..:
f .i i ~ ~ ~ . 1 . . ~ ~ ~ ~
t. i~ ~ ~ 1 ~ ~ . ~ ~ ~ ~ ~ ~ .
. . ~ ~ ~ . i . 1 ~ ~ ~ ~ ~ ~ ~ ~
- . ~ 1 ~ t . ~ 1 ~ ~ ~ .
. ~ ~~~~ ~~ .. ~ ~1 !.
of about 1000 to 4000 c~mslm~/day. It has been found that fiat film can be incrementally stretched more uniformly than embossed film. The process may be conducted at ambient or room temperature or at elevated temperatures. As described above, laminates of the microporous film rnay be obtained with nonwoven fibrous webs.
The nonwoven fibrous web may comprise fibers of polyethylene, polypropylene, polyesters, rayon, cellulose, nylon, and blends of such fibers. A number of definitions have been proposed for nonwoven fibrous webs. The fibers are usually staple fibers or continuous filaments. T he nonwove:ns are usually referred to as spunbond, carded, meltblown, and the like. Thn fibers or filaments may be bicomponent to f acilitate bonding. For example, a fiber having a sheath and core of different polymers such as-polyethylene (PE) and polypropylene (PP) may be used; or mixtures of PE and PP fibers may be used. As used herein ~ 5 "nonwoven fibrous web" is used in its generic sense to den'ne a generally planar structure that is relatively flat, flexible and porous, and is composed Of staple 1'IberS Or COntinu061S filaments. For a detailed description of nonwovens, see "Nonwov°n Fabric primer and Reference Sampler" by c. A. Vaughn, Association of the Nonwoven Fabrics Industry, 3d edition (1992).
In a preferred form, the microporous laminate employs a film tb ~ 3 5 to a 5~.~ur..,) having a gauge or a thickness between about 0.25 and 10 milsLand, depending upon use, the film thickness will vary and, most preferably, in -. -1 ~ ~~ ~1 .. . ~~ . .i~
:i .~ i . ~ : . . a ~ : ~
V : 1 ~ ~ 1 ~ . i ~ ~ . . ~ .
. ~ ~ 1 . . . . ~.~~ i ~ 1 . .
. ~ ~ ~ . . ~ . . i . .
. . .~~~ .1 .. . .. ~~
~Co ~ 3 5 I'o 6° ' $~"~~
disposable applications is the order of about 0.25 to 2 milsLin thickness.
The nonwoven fibrous webs of the laminated sheet normally have a ~5 -9g t~ 89 ~ ~o~lw.z>
weight of about 5 gmslyd2 to 75 gms/yd~ preferably about 20 to about - (~a~9a ~ y~~s4~L,..z G.-~
40 gms/yd~ The. composite or laminate can be incrementally stretched in the cross direction (CD} to form a CD stretched composite.
Furthermore, CD stretching may be followed by stretching in the machine direction (MD} to form a composite which is stretched in both CD and MD
directions. As indicated above, the microporous film or laminate may be used in many different applications such as baby diapers, baby training pants, catamenial pads and garments, and the like where moisture vapor and air transmission properties, as well as fluid barrier properties, are needed. , B. Stretchers for the Microporous Film and Laminates A number of different stretchers and techniques may be employed to stretch the film or laminate of a nonwoven fibrous web and microporous-formable film. T hesa laminates of nonwoven carded fibrous webs of staple fibers or nonwoven spun-bonded fibrous webs may be stretched with the stretclhers and techniques described as foliov~~s:
'1. Diagonal int~errneshino Stretcher T he diagona'I intermeshing stretcher consists of a pair of left hand and rioht hand helical gear-Like elements on parallel shafts. T he shafts are disposed between two machine side plates, the lower shaft being located in fixed b~arincs and the upper shaft being aocated in CA 02329529 2000-10-17 AMENDED SHEET _ bearings in vertically slidable members. The slidable members are adjustable in the vertical direction by wedge shaped elements operable by adjusting screws. Screwing the wedges out or in will move the vertically slidable member respectively down or up to further engage or disengage the gear-like teeth of the upper intermeshing roll with the lower intermeshing roll. Micrometers mounted to the side frames are operable to indicate the depth of engagement of the teeth of the intermeshing roll.
Air cylinders are employed to hold the siidable members in their lower engaged position firmly against the adjusting wedges to oppose the upward force Exerted by the material being stretched. These cylinders may also be retracted to disengage the upper and lower intermeshing rolls from each other for purposes of threading material through the intermeshing equipment or in conjunction with a safety circuit which would open all the machine nip points when activated.
A drive means is typically utilized to drive the stationery intermeshing roll. If the upper intermeshing rol! is to be disengageable for purposes of machine threading or safety, it is preferable to use an antibacklash gearing arrangement between the upper and lower intermeshing rolls to assure that upon reengagement the teeth of one ?0 intermeshing roll always fall between the teeth of the other intermeshing roll and potentially damaging physical contact between addenda of intermeshing teeth is avoided. !f the intermeshing rolls are to remain in constant engagement, the upper intermeshing roll typically need not be 20-04-20~~0 . US 009910562 , . ~ : , .. .. .: . ..
- ~:~ .. ..- .. . . .. . .-.
,. : . . .. . . .. . . ..
. . . . .... . . . .
. , . . . . . . . . ..
~14- ~ .... .. .. . .. ..
driven. Drive may be accomplished by the driven intermeshing roll through the material being stretched.
The interm=ahing rolls closely resemble fine pitch helical ~I5 ~o~5c....., gears. In the preferred ernbodiment, the rolls have 5.935" diamete~ 45°
w ~.25~+ cw~) helix angle, a 0.100"~no~rmal pitch, 30 diametral pitch, 14'/2°
pressure angle, and are basically a long addendum topped gear. This produces a to-~~~6c~~, narrow, deep tooth pronle which allows up to about 0.090"~ of Ca - 4 ~ ~~ c,.,.,) intermeshing engagement: and about 0.005"fclearance on the sides of the tooth for material thickness. The teeth are not designed to transmit rotational torque and do not contact metal-to-metal in normal intermeshing stretching operation.
2. Cross Direction intermeshin4 Stretcher The CD intermeshing stretching equipment is identical to the diagonal intermeshing stretcher with differences in the design of the intermeshing rolls and other minor areas noted below. Since the CD
interrneshina elements ars capable or large engagement depths, it is important that the equipment incorporate a means of causing the shafts of the two intermeshing rolls to remain parallel when the top shaft is raising or lowering. T his is necessary to assure that the tenth of one intermeshing roll always fall between the teeth of the other intermeshing roll and potentially damaging physical contact between intermeshing teeth is avoided. T his parallel motion is assured by a rack and gear arrangement wherein a stationary gear rack is attached to sack side frame in 20-04-2000 ~ ~ U S 009910562 .. .~ .~ . ~~ , _;...
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juxtaposition to the vertically slidable members. A shaft traverses the side frames ~ and operates in a bearing _in each of the vertically slidable members. A gear resides on each end of this shaft and operates in engagement with.the racks to produce the desired parallel motion.
T he drive for the CD intermeshing stretcher must operate both upper and tower intermeshing rolls except in the case of intermeshing V
stretching of materials v~~ith a relatively high coefficient of friction. The drive need not be antib~scklash, however, because a small amount of machine direction misaiidnment or drive slippage will cause no problem.
The reason for this will become evident with a description of the CD
intermeshing elements. .
The CD ints~meshing el=rnents are machined from solid material but can best be described as an alternating stack of two differ~;~;
diameter disks. Jn the preferred embodiment, the intermeshing disks y5 ~a4c~) ~~ ~ d~8~c~,.~~~
would be 6" I in diameter, 0.031 " (thick, and have a full radius on their L L (t3~9~c,w.) edge. T he spacer disks separating the intermeshing disks would be 5 1 /2" L
~o ~~~53cw~) in diameter and O.Oc9 ~ in thickness. Two rolls of this configuration would a~ 5g~cw~
be able to be intermeshed up to 0.231C' leaving 0.019( cclearanc, a for material on all sides. As with the diagonal intermeshing stretcher, this CD
o ~~54c...~) imermeshing element configuration would have a 0.100 pitch.
_3. Machine Direction intermeshing StrPtr~,or T he MD intermeshing stretching equipment is identical to the aiagonal intermeshing streach except for the design of the intermeshing AMENDED SHEET
20-04-20~~0 , U S 009910562 ' : . .. .. .: . ... . .a~
y, ~. i . r ~s . ~ . . ~ a . .' i - : . : . 1 t . ~ . . ~ ~ . ~
a.
a . . . . . i ~~.~ i a . .
. ~ . . . . . i .
.s.. ~~ .. . ~. ..
rolls. The MD intermeshing rolls closely resemble fine pitch spur gears.
~ w ~ 6 c...-.J
In the preferred embodiment, the rolls have a 5.933"Ldiameter, 0.100"(o~ast~c~
pitch, 30 Diametral pitch, 14'/x° pressure angle, and are basically a Long addendum, topped gear. A second pass was taken on these rolls with the a ~0~54~.~
gear hob offset 0.010'Lto provide a narrowed tooth with more clearance.
~o ~ ~ a~$~ ~..,~
With about 0.090"L of engagement, this configuration will have about (o ~ o a s a ~~.~
0.010" clearance on the sides for material thickness.
4. Incremental Stretching Techniaue The above described diagonal, CD or MD intermeshing stretchers may be employed to produce the incrementally stretched film or laminate of nonwoverl fibrous web and microporous-formabfe film to form the microporous filrrE~ products of this invention. For example, T he stretching operation may be employed on an extrusion Iarninate of a nonwoven fibrous web of staple fibers or spun-bonded filaments and microporous-formable thermoplastic film. In one of the unique aspects of this invention a laminatf: of a nonwoven fibrous web of spun-bonded filaments may be incrementally stretched to provide a very soft fibrous flnl5h to tha laminats that looks like cloth. The laminate of nonwoven fibrous web and microporous-formable film is incrementally stretched using, for instance, the CD and!or MD intermeshing stretcher with one pass through the stretcher with a depth of roller engagement at about ~0°1!5?yr 1~ o~3a~gc..w.) ~2~39~. t~ ~ ~o96~Js, 0.080 inch to 0.120 inci~-at speeds from about 550 fpm to 1200 fpm~or aster. I he re5ultS Of SUC:h incremental or intermesh stretching produces laminates that have excellent breathability and liquid-barrier properties, yet provide superior bond strengths and soft cloth-Like textures.
The following examples illustrate the method of making microporous film and laminates of this invention. In fight of these examples and this further detailed description, it is apparent to a person of ordinary skill in the art that variations thereof may be made without departing from the scope of this invention.
BRIEF DESCRIPTION OF TAE DRAWINGS
The invention is further understood with reference to the drawings in which:
FIG. 1 is a schematic of an inline extrusiow lamination and incremental stretching apparatus for making the microporous laminate of this invention.
F1G. 2 is a cross sectional view taken along the line 2-2 of Fig. 1 illustrating the intermeshing rollers in diagrammatic form.
FIG. 3 is .a graph demonstrating the fine speeds for Examples 1-5.
FIG. 4 is a graph demonstrating the moisture vapor transmission properties of both embossed and flat microporous films.
FIG. 5 is ~a graph demonstrating the moisture vapor transmission rate can be adjusted by heating the precursor film.
20-04-20~~0 US 009910562 . . . .. .. .._ . .. : -:-.
'i i ._ . ~ ~ 1 . . . i s s . i i i ~ i ~ ~ . . . . . . . i .
i i i . . i . . . ..1. . . . . .
. . ~ . . . ~ . . i .
. . .~~. .. .. . .. ..
-18- . _ .
EXAMPLES 'I-5 Blends of LLDPE and LDPF having the compositions reported in the following TABLE 1 were extruded to form films and the films were then incrementally stretched to provide microporous films.
rormulation l 1 ' 2 ~ 3 I 4 ~ 5 (by wt.ll CaC03 ~ 4.4.2 44.2 4-4.2 4.4.2 4.4.2 ' LLDPS , 44.1 44.9 41.9 41.9 47.9 ~ I
LDPS I i .5 3.7 3.7 3.7 3.7 Others' I 10.2 10.2 10.2 10.2 10_2 ~ I
Screw A , 33 I 45 I 57 64 I 75 RPM ~
B , 33 . 45 57 64 75 Basis wt_ 45 I 45 I 45 I 45 45 (gmslm2) Gauge (mils) I 2 I 2 ( 2 I 2 2 ~~ ?5 . ~ fr uM
1 Line Speed ~ 550 I 700 900 1000 1200 ~ -5 (fpm) Air Knife ~ a-25 5-25 5-25 I 5-25 5-25 (cfmfinch) Web Stabiirty Poar Good gaug:: web control stability with drawwithout resonancedraw resonance -inner components include Z.b°~o by weight of a styrene-butadiene-styrene fSBS) triblock polymer, Shell Kraton 2122X, which is an SBS < 50°~o by wt. -mineral oil < 30% by wt., EVA
copolymer < 7 5 °~o by wt., polystyrene < 10% by wt., hydrocarbon resin < i 0°ro by wl:., antioxidani:s~abilizer < 1 °~ by v~r., and hydrated amflrphous silica < 1 °~o by wt.
i=ach of the formulations of 1-5 were extruded into films employing an extrusion apparatus as shown diagramatically in FIG. 'l . As shown, the apparatus may be employed for film extrusion with and without lamination. In the c2Se of Film extrusion, the formulations of ~xampfes 1-5 Were fed from an axtrud~r 1 through slot dig 2 to fc~rrn the 20-04-20~~0 -1. --~_ US 009910562 .. .~ .. . ., .. :.
.- :. .. .- .. . : .: : ..
:~. : .. . . .. . . ..
,. . . . .... . . . .
. . . . . . . . . ::
.... .. .: . .: ..
extrudate 6 into the nip of a rubber roll 5 and a metal roll 4 with an air knife 3. Where extrusion lamination is practiced, there is an incoming web of fibrous material 9 from roller 13 which is also introduced into the nip of the rubber roll 5 and rnfaai roll 4. In examples 1-5, the thermoplastic film was produced for subsequent incremental stretching to form the microporous film. As shovvn in TABLE 1, over speeds of about 550 fpm to 1200 f p , a polyethylene film 6 on the order of about 2 rri~s n g~~) L
thickness was made which is taken oft at roller 7. The air knife 3 has a ~3 ot,m $ c~.r~) ~p . a g 9 _ o . i 5 Z cw~, length of about 120 Land an opening of about 0.035"-0.060'Land air is 7 0 blown through the opening and against the extrudate 6 at about a cfmiinch to 25 cfmfnch.. The compressive force at the nip and the air knife are controlled such xhat the film is made without pin holing and without draw resonance ins the case of Examples 2-5. Where the LDPE
was included in the composition at a level of 1.5% by weight, draw ~~_~94 h.,Js) resonance was encountered at a fine speed of 550 fpm However, when the LDr E wes included in the formulation at a level of 3.7% by weight with the LLDPc at a level of 44.1-44.9% by weight, film production was able to be achieved at high speeds greater than 550 fpm up to 1200 fpm ~~ ' ~
~4 b 6 - 0 ~ r...l without draw resonance. The melt temperatures from the feed zone to .20 the screw tip of extruders .A and 3 were maintained at about 400-430°F (~oc~~4-~a3a~a) a.a~. ~ °~, with did temper atures of approximately 450°F~to extrude the precursor (5o.$r'w (,~
film around 2 mils'(45 gms/m2).
20-04-20~~0 ' ~ ~ _ US 009910562 .. .. .. . ... ' - :.
i f 1 1 . 1 .
1 .
. 1 1 .... .~ .. . .. ..
F1G. 3 is a graph demonstrating the fine speeds for Examples 1-5. Example 1, which contained only 1.5 °!° by wei ght of LDPE, resulted (n a poor film gauge control with draw resonance even with the air knife 3. However, when the LDPE was increased to about 3.7%
by weight, excellent web stability was achieved without draw resonance (~ .o96w.r~) even when line speeds were increased to about 1200 fprr4 This is shown diagramatically in FIG. 3.
FIG. 4 is a graph demonstrating the moisture vapor transmission properties of both embossed and flat films resulting from incrementally stretching the precursor films of Examples 2-~ under different temperatures and stretch roller engagement conditions. As shown schematically in IsIG. 1, where the incoming film 12 at ambient temperature was passed 7through temperature controlled rollers 20 and 2~
before CD and MD incremental stretching rollers ( 10 and 11, and 10' and 7'I'), the temperatures and the depths of engagements can be controlled.
Remarkably, the MVTR of the flat film exceeded the MVTR of the embossed film as shown in r=IG. 4. in brief, MVTRs for the embossed film on the order of about 12'.00-2400 gms/m2lday were achieved, whereas MV T Rs far the flat film on the order of about 1900-3200 gmslrn=/day were achieved. Unexpecl:ediy, as also shown in FIG. 5, the MVTR of the microporous film can also be controlled by the web temperature during the stretching. Fig. 5 shows the film when heated to different temperatures before CD stretching can result in different MV T Rs. T hn data-reported in 20-04-2000 "~ --., US 009910562 ' ~ ~ ~~_ ~.~ ~~ ~ ~~ = 'H
.. ~ ~ ~ ~ ~ 1 ~ ~ 1 ~ 1 ~ ~ 1 r t- ~ ~ ~ 1 ~ ~ 1 ~ ~ ~ 1 ~ ~
~ ~ i ~ ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ ~ ~
~ ~ 1 ~ ~ ~ 1 ~ ~ ~ t i 1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 1.
(o'IfoSJGw~) FIG. 5 was for a CD rolNers engagement dept of 0.065 Land MD rollers ~o~l o~Gc.r.) engagement depth of 0.040"L where the-temperature of roller 21 was maintained at ambient. The embossed film was made with a~ metal embossing roller having a rectangular engraving of CD and MD lines with - ~Gti.'9 6 -n~ ~ 1~ I mLO )cw~) about 166-300 Lines per inch This pattern is disclosed, for example, in U. S. Patent No. 4,376,147 which is incorporated herein by reference.
This micro pattern provides a matte finish to the film but is undetectable to the naked eye.
CA 02329529 2000-10-17 AMENDED SHEET .
interrneshina elements ars capable or large engagement depths, it is important that the equipment incorporate a means of causing the shafts of the two intermeshing rolls to remain parallel when the top shaft is raising or lowering. T his is necessary to assure that the tenth of one intermeshing roll always fall between the teeth of the other intermeshing roll and potentially damaging physical contact between intermeshing teeth is avoided. T his parallel motion is assured by a rack and gear arrangement wherein a stationary gear rack is attached to sack side frame in 20-04-2000 ~ ~ U S 009910562 .. .~ .~ . ~~ , _;...
'c i ~ ~ ~i. ~ ~ ~ . v ~ ~ ~ ~ :.
'i' ~ ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ Y
_ ~ ~ ~ ~ ~ . ~ ~ ~ ~ ~ ~ f 1 1 ~ i ~ ~ ~ ~ ~ ~ ~ ~
~15-. ~~~~ ~~ ~~ ~ ~~ ~~
juxtaposition to the vertically slidable members. A shaft traverses the side frames ~ and operates in a bearing _in each of the vertically slidable members. A gear resides on each end of this shaft and operates in engagement with.the racks to produce the desired parallel motion.
T he drive for the CD intermeshing stretcher must operate both upper and tower intermeshing rolls except in the case of intermeshing V
stretching of materials v~~ith a relatively high coefficient of friction. The drive need not be antib~scklash, however, because a small amount of machine direction misaiidnment or drive slippage will cause no problem.
The reason for this will become evident with a description of the CD
intermeshing elements. .
The CD ints~meshing el=rnents are machined from solid material but can best be described as an alternating stack of two differ~;~;
diameter disks. Jn the preferred embodiment, the intermeshing disks y5 ~a4c~) ~~ ~ d~8~c~,.~~~
would be 6" I in diameter, 0.031 " (thick, and have a full radius on their L L (t3~9~c,w.) edge. T he spacer disks separating the intermeshing disks would be 5 1 /2" L
~o ~~~53cw~) in diameter and O.Oc9 ~ in thickness. Two rolls of this configuration would a~ 5g~cw~
be able to be intermeshed up to 0.231C' leaving 0.019( cclearanc, a for material on all sides. As with the diagonal intermeshing stretcher, this CD
o ~~54c...~) imermeshing element configuration would have a 0.100 pitch.
_3. Machine Direction intermeshing StrPtr~,or T he MD intermeshing stretching equipment is identical to the aiagonal intermeshing streach except for the design of the intermeshing AMENDED SHEET
20-04-20~~0 , U S 009910562 ' : . .. .. .: . ... . .a~
y, ~. i . r ~s . ~ . . ~ a . .' i - : . : . 1 t . ~ . . ~ ~ . ~
a.
a . . . . . i ~~.~ i a . .
. ~ . . . . . i .
.s.. ~~ .. . ~. ..
rolls. The MD intermeshing rolls closely resemble fine pitch spur gears.
~ w ~ 6 c...-.J
In the preferred embodiment, the rolls have a 5.933"Ldiameter, 0.100"(o~ast~c~
pitch, 30 Diametral pitch, 14'/x° pressure angle, and are basically a Long addendum, topped gear. A second pass was taken on these rolls with the a ~0~54~.~
gear hob offset 0.010'Lto provide a narrowed tooth with more clearance.
~o ~ ~ a~$~ ~..,~
With about 0.090"L of engagement, this configuration will have about (o ~ o a s a ~~.~
0.010" clearance on the sides for material thickness.
4. Incremental Stretching Techniaue The above described diagonal, CD or MD intermeshing stretchers may be employed to produce the incrementally stretched film or laminate of nonwoverl fibrous web and microporous-formabfe film to form the microporous filrrE~ products of this invention. For example, T he stretching operation may be employed on an extrusion Iarninate of a nonwoven fibrous web of staple fibers or spun-bonded filaments and microporous-formable thermoplastic film. In one of the unique aspects of this invention a laminatf: of a nonwoven fibrous web of spun-bonded filaments may be incrementally stretched to provide a very soft fibrous flnl5h to tha laminats that looks like cloth. The laminate of nonwoven fibrous web and microporous-formable film is incrementally stretched using, for instance, the CD and!or MD intermeshing stretcher with one pass through the stretcher with a depth of roller engagement at about ~0°1!5?yr 1~ o~3a~gc..w.) ~2~39~. t~ ~ ~o96~Js, 0.080 inch to 0.120 inci~-at speeds from about 550 fpm to 1200 fpm~or aster. I he re5ultS Of SUC:h incremental or intermesh stretching produces laminates that have excellent breathability and liquid-barrier properties, yet provide superior bond strengths and soft cloth-Like textures.
The following examples illustrate the method of making microporous film and laminates of this invention. In fight of these examples and this further detailed description, it is apparent to a person of ordinary skill in the art that variations thereof may be made without departing from the scope of this invention.
BRIEF DESCRIPTION OF TAE DRAWINGS
The invention is further understood with reference to the drawings in which:
FIG. 1 is a schematic of an inline extrusiow lamination and incremental stretching apparatus for making the microporous laminate of this invention.
F1G. 2 is a cross sectional view taken along the line 2-2 of Fig. 1 illustrating the intermeshing rollers in diagrammatic form.
FIG. 3 is .a graph demonstrating the fine speeds for Examples 1-5.
FIG. 4 is a graph demonstrating the moisture vapor transmission properties of both embossed and flat microporous films.
FIG. 5 is ~a graph demonstrating the moisture vapor transmission rate can be adjusted by heating the precursor film.
20-04-20~~0 US 009910562 . . . .. .. .._ . .. : -:-.
'i i ._ . ~ ~ 1 . . . i s s . i i i ~ i ~ ~ . . . . . . . i .
i i i . . i . . . ..1. . . . . .
. . ~ . . . ~ . . i .
. . .~~. .. .. . .. ..
-18- . _ .
EXAMPLES 'I-5 Blends of LLDPE and LDPF having the compositions reported in the following TABLE 1 were extruded to form films and the films were then incrementally stretched to provide microporous films.
rormulation l 1 ' 2 ~ 3 I 4 ~ 5 (by wt.ll CaC03 ~ 4.4.2 44.2 4-4.2 4.4.2 4.4.2 ' LLDPS , 44.1 44.9 41.9 41.9 47.9 ~ I
LDPS I i .5 3.7 3.7 3.7 3.7 Others' I 10.2 10.2 10.2 10.2 10_2 ~ I
Screw A , 33 I 45 I 57 64 I 75 RPM ~
B , 33 . 45 57 64 75 Basis wt_ 45 I 45 I 45 I 45 45 (gmslm2) Gauge (mils) I 2 I 2 ( 2 I 2 2 ~~ ?5 . ~ fr uM
1 Line Speed ~ 550 I 700 900 1000 1200 ~ -5 (fpm) Air Knife ~ a-25 5-25 5-25 I 5-25 5-25 (cfmfinch) Web Stabiirty Poar Good gaug:: web control stability with drawwithout resonancedraw resonance -inner components include Z.b°~o by weight of a styrene-butadiene-styrene fSBS) triblock polymer, Shell Kraton 2122X, which is an SBS < 50°~o by wt. -mineral oil < 30% by wt., EVA
copolymer < 7 5 °~o by wt., polystyrene < 10% by wt., hydrocarbon resin < i 0°ro by wl:., antioxidani:s~abilizer < 1 °~ by v~r., and hydrated amflrphous silica < 1 °~o by wt.
i=ach of the formulations of 1-5 were extruded into films employing an extrusion apparatus as shown diagramatically in FIG. 'l . As shown, the apparatus may be employed for film extrusion with and without lamination. In the c2Se of Film extrusion, the formulations of ~xampfes 1-5 Were fed from an axtrud~r 1 through slot dig 2 to fc~rrn the 20-04-20~~0 -1. --~_ US 009910562 .. .~ .. . ., .. :.
.- :. .. .- .. . : .: : ..
:~. : .. . . .. . . ..
,. . . . .... . . . .
. . . . . . . . . ::
.... .. .: . .: ..
extrudate 6 into the nip of a rubber roll 5 and a metal roll 4 with an air knife 3. Where extrusion lamination is practiced, there is an incoming web of fibrous material 9 from roller 13 which is also introduced into the nip of the rubber roll 5 and rnfaai roll 4. In examples 1-5, the thermoplastic film was produced for subsequent incremental stretching to form the microporous film. As shovvn in TABLE 1, over speeds of about 550 fpm to 1200 f p , a polyethylene film 6 on the order of about 2 rri~s n g~~) L
thickness was made which is taken oft at roller 7. The air knife 3 has a ~3 ot,m $ c~.r~) ~p . a g 9 _ o . i 5 Z cw~, length of about 120 Land an opening of about 0.035"-0.060'Land air is 7 0 blown through the opening and against the extrudate 6 at about a cfmiinch to 25 cfmfnch.. The compressive force at the nip and the air knife are controlled such xhat the film is made without pin holing and without draw resonance ins the case of Examples 2-5. Where the LDPE
was included in the composition at a level of 1.5% by weight, draw ~~_~94 h.,Js) resonance was encountered at a fine speed of 550 fpm However, when the LDr E wes included in the formulation at a level of 3.7% by weight with the LLDPc at a level of 44.1-44.9% by weight, film production was able to be achieved at high speeds greater than 550 fpm up to 1200 fpm ~~ ' ~
~4 b 6 - 0 ~ r...l without draw resonance. The melt temperatures from the feed zone to .20 the screw tip of extruders .A and 3 were maintained at about 400-430°F (~oc~~4-~a3a~a) a.a~. ~ °~, with did temper atures of approximately 450°F~to extrude the precursor (5o.$r'w (,~
film around 2 mils'(45 gms/m2).
20-04-20~~0 ' ~ ~ _ US 009910562 .. .. .. . ... ' - :.
i f 1 1 . 1 .
1 .
. 1 1 .... .~ .. . .. ..
F1G. 3 is a graph demonstrating the fine speeds for Examples 1-5. Example 1, which contained only 1.5 °!° by wei ght of LDPE, resulted (n a poor film gauge control with draw resonance even with the air knife 3. However, when the LDPE was increased to about 3.7%
by weight, excellent web stability was achieved without draw resonance (~ .o96w.r~) even when line speeds were increased to about 1200 fprr4 This is shown diagramatically in FIG. 3.
FIG. 4 is a graph demonstrating the moisture vapor transmission properties of both embossed and flat films resulting from incrementally stretching the precursor films of Examples 2-~ under different temperatures and stretch roller engagement conditions. As shown schematically in IsIG. 1, where the incoming film 12 at ambient temperature was passed 7through temperature controlled rollers 20 and 2~
before CD and MD incremental stretching rollers ( 10 and 11, and 10' and 7'I'), the temperatures and the depths of engagements can be controlled.
Remarkably, the MVTR of the flat film exceeded the MVTR of the embossed film as shown in r=IG. 4. in brief, MVTRs for the embossed film on the order of about 12'.00-2400 gms/m2lday were achieved, whereas MV T Rs far the flat film on the order of about 1900-3200 gmslrn=/day were achieved. Unexpecl:ediy, as also shown in FIG. 5, the MVTR of the microporous film can also be controlled by the web temperature during the stretching. Fig. 5 shows the film when heated to different temperatures before CD stretching can result in different MV T Rs. T hn data-reported in 20-04-2000 "~ --., US 009910562 ' ~ ~ ~~_ ~.~ ~~ ~ ~~ = 'H
.. ~ ~ ~ ~ ~ 1 ~ ~ 1 ~ 1 ~ ~ 1 r t- ~ ~ ~ 1 ~ ~ 1 ~ ~ ~ 1 ~ ~
~ ~ i ~ ~ ~ ~ ~ ~ ~ 1 ~ ~ ~ ~ ~ ~
~ ~ 1 ~ ~ ~ 1 ~ ~ ~ t i 1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 1.
(o'IfoSJGw~) FIG. 5 was for a CD rolNers engagement dept of 0.065 Land MD rollers ~o~l o~Gc.r.) engagement depth of 0.040"L where the-temperature of roller 21 was maintained at ambient. The embossed film was made with a~ metal embossing roller having a rectangular engraving of CD and MD lines with - ~Gti.'9 6 -n~ ~ 1~ I mLO )cw~) about 166-300 Lines per inch This pattern is disclosed, for example, in U. S. Patent No. 4,376,147 which is incorporated herein by reference.
This micro pattern provides a matte finish to the film but is undetectable to the naked eye.
CA 02329529 2000-10-17 AMENDED SHEET .
Claims (18)
1. A high speed method of making a microporous thermoplastic film comprising melt blending a composition comprising (a) about 35% to about 45% by weight of a linear low density polyethylene, (b) about 3% to about 10% by weight of a low density polyethylene, (c) about 40% to about 55% by weight calcium carbonate filler particles, and (d) about 2% to about 6% by weight of a triblock copolymer of styrene selected from the group consisting of styrene-butadiene-styrene, styrene-isoprene-styrene, and styrene-ethylene-butylene-styrene, and blends thereof, extruding said melt blended composition into a nip of rollers with an air knife to form a film at a speed on the order of at least 550 fpm to 1200 fpm, (2.794 to 6.096 m/s) without draw resonance, and applying an incremental stretching force obtained by using intermeshing rollers to said film at said speed along lines substantially uniformly across said film and throughout its depth to provide a microporous film.
2. The high speed method of claim 1 wherein said melt blended composition consists essentially of about 42% by weight linear low density polyethylene, about 4% by weight low density polyethylene, about 44% calcium carbonate filler particles, and about 3% by weight triblock polymer.
3. The high speed method of claim 1 wherein said melt blended composition further comprises about 0-5% by weight high density polyethylene, about 0-4% by weight titanium dioxide, and about 0.1% to about 0.2% by weight processing aid.
4. The high speed method of claim 3 wherein said melt blended composition comprises about 4% by weight high density polyethylene, about 3% by weight titanium dioxide, and about 0.1% by weight fluorocarbon polymer processing aid.
5. The high speed method of claim 4 wherein said fluorocarbon polymer processing aid is 1-propene,1,1,2,3,3,3-hexafluoro copolymer with 1,1-difluoroethylene.
6. The high speed method of any preceding claim wherein said triblock polymer is preblended with oil, hydrocarbon, antioxidant and stabilizer.
7. The high speed method of any preceding claim wherein said nip of rollers comprises a metal embossing roller having an engraving of CD and MD lines within 165-300 line/inch (64.96 -118.11 lines/cm) and a rubber roller and the compressive force between said rollers is controlled to form an embossed film.
8. The high speed method of any one of Claims 1 to 7 wherein said rollers provide a polished chrome surface to form a flat film.
9. The high speed method of any preceding claim comprising introducing a nonwoven fibrous web into said nip of rollers and controlling the compressive force between the web and the film at the nip to bond the surface of the web to the film to form a laminated microporous sheet.
10. The high speed method of claim 9 wherein said fibrous web comprises polyolefin fiber's.
11. The high speed method of claim 10 wherein said fibers are selected from the group consisting of polypropylene, polyethylene, polyesters, cellulose, rayon, nylon and blends or coextrusions of two or more such fibers.
12. The high speed method of any one of Claims 9 to 11 wherein the fibrous web has a weight of from 5-to 70 gms/yd2 (5.98 to 83.72 g/m2) and the microporous film has a thickness on the order of 0.25 to 10 mils (6.35 to 245µm).
13. The high speed method of any one of Claims 9 to 12 wherein said web is formed from staple fibers or filaments.
14. The high speed method of any preceding claim wherein said incremental stretching step is conducted at ambient temperature.
15. The high speed method of Claim 14 wherein the melt blend composition is slot die extruded into said nip of rollers and wherein the film is cooled to ambient temperature before incremental stretching.
16. The high speed method of any one of Claims 1 to 13 wherein said incremental stretching step is conducted at an elevated temperature.
17. The high speed method of any preceding claim wherein said film is travelling in a machine direction and incremental stretching force is applied across the machine direction of the travelling film and by application of a stretching force in the machine direction of the travelling film to provide the microporous film.
18. The product of the method of any preceding claim.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/080,063 US6013151A (en) | 1998-05-15 | 1998-05-15 | High speed method of making microporous film products |
| US09/080,063 | 1998-05-15 | ||
| PCT/US1999/010562 WO1999060050A1 (en) | 1998-05-15 | 1999-05-13 | High speed method of making microporous film products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2329529A1 true CA2329529A1 (en) | 1999-11-25 |
Family
ID=22155027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002329529A Abandoned CA2329529A1 (en) | 1998-05-15 | 1999-05-13 | High speed method of making microporous film products |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US6013151A (en) |
| EP (2) | EP1078013B1 (en) |
| JP (1) | JP2002515367A (en) |
| KR (2) | KR100583548B1 (en) |
| CN (1) | CN1300305A (en) |
| AR (1) | AR015777A1 (en) |
| AT (1) | ATE301154T1 (en) |
| AU (1) | AU739260B2 (en) |
| BR (1) | BR9910040A (en) |
| CA (1) | CA2329529A1 (en) |
| CZ (1) | CZ298026B6 (en) |
| DE (1) | DE69926497T2 (en) |
| ES (1) | ES2244195T3 (en) |
| HU (1) | HU226496B1 (en) |
| NO (1) | NO20005689D0 (en) |
| NZ (1) | NZ507461A (en) |
| PL (1) | PL201500B1 (en) |
| RU (1) | RU2224772C2 (en) |
| TW (2) | TWI239978B (en) |
| WO (1) | WO1999060050A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9604429B2 (en) | 2010-11-16 | 2017-03-28 | The Glad Products Company | Ribbed film structures with pigment created visual characteristics |
| US9566760B2 (en) | 2010-11-16 | 2017-02-14 | The Glad Products Company | Ribbed film structures with voiding agent created visual characteristics |
| US8865294B2 (en) | 2012-10-25 | 2014-10-21 | The Glad Products Company | Thermoplastic multi-ply film with metallic appearance |
| US8734016B2 (en) | 2012-03-28 | 2014-05-27 | The Glad Products Company | Incrementally-stretched thermoplastic films with enhanced look and feel and methods for making the same |
| US9486977B2 (en) | 2012-07-18 | 2016-11-08 | The Glad Products Company | Multi-ply puckered films formed by discontinuous lamination of films having different rebound ratios |
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- 1999-05-12 TW TW088107700A patent/TWI239978B/en not_active IP Right Cessation
- 1999-05-12 TW TW094108528A patent/TWI252858B/en not_active IP Right Cessation
- 1999-05-13 CZ CZ20004041A patent/CZ298026B6/en not_active IP Right Cessation
- 1999-05-13 EP EP99923008A patent/EP1078013B1/en not_active Expired - Lifetime
- 1999-05-13 PL PL343906A patent/PL201500B1/en not_active IP Right Cessation
- 1999-05-13 EP EP04077292A patent/EP1482005A3/en not_active Withdrawn
- 1999-05-13 AU AU39877/99A patent/AU739260B2/en not_active Ceased
- 1999-05-13 BR BR9910040-1A patent/BR9910040A/en not_active IP Right Cessation
- 1999-05-13 CN CN99805984A patent/CN1300305A/en active Pending
- 1999-05-13 NZ NZ507461A patent/NZ507461A/en unknown
- 1999-05-13 WO PCT/US1999/010562 patent/WO1999060050A1/en active IP Right Grant
- 1999-05-13 CA CA002329529A patent/CA2329529A1/en not_active Abandoned
- 1999-05-13 JP JP2000549665A patent/JP2002515367A/en active Pending
- 1999-05-13 HU HU0102654A patent/HU226496B1/en not_active IP Right Cessation
- 1999-05-13 ES ES99923008T patent/ES2244195T3/en not_active Expired - Lifetime
- 1999-05-13 RU RU2000128113/04A patent/RU2224772C2/en active
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- 1999-05-13 KR KR1020067001225A patent/KR100704513B1/en not_active IP Right Cessation
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2000
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| AR015777A1 (en) | 2001-05-16 |
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| AU3987799A (en) | 1999-12-06 |
| TWI252858B (en) | 2006-04-11 |
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| AU739260B2 (en) | 2001-10-11 |
| KR20060012052A (en) | 2006-02-06 |
| CZ20004041A3 (en) | 2001-04-11 |
| PL343906A1 (en) | 2001-09-10 |
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| EEER | Examination request | ||
| FZDE | Discontinued |