AU608169B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU608169B2 – Breathable microporous film and methods for making it
– Google Patents

AU608169B2 – Breathable microporous film and methods for making it
– Google Patents
Breathable microporous film and methods for making it

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Publication number
AU608169B2

AU608169B2
AU39034/89A
AU3903489A
AU608169B2
AU 608169 B2
AU608169 B2
AU 608169B2
AU 39034/89 A
AU39034/89 A
AU 39034/89A
AU 3903489 A
AU3903489 A
AU 3903489A
AU 608169 B2
AU608169 B2
AU 608169B2
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AU
Australia
Prior art keywords
weight
film
further characterized
microporous films
making
Prior art date
1988-07-27
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Ceased

Application number
AU39034/89A
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AU3903489A
(en

Inventor
Mitchell Kelly Antoon
David James Hill
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hercules LLC

Original Assignee
Hercules LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1988-07-27
Filing date
1989-07-27
Publication date
1991-03-21

1989-07-27
Application filed by Hercules LLC
filed
Critical
Hercules LLC

1990-02-01
Publication of AU3903489A
publication
Critical
patent/AU3903489A/en

1991-03-21
Application granted
granted
Critical

1991-03-21
Publication of AU608169B2
publication
Critical
patent/AU608169B2/en

2009-07-27
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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Classifications

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

C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

C08K3/013—Fillers, pigments or reinforcing additives

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS

A61F13/00—Bandages or dressings; Absorbent pads

A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators

A61F13/15577—Apparatus or processes for manufacturing

A61F13/15707—Mechanical treatment, e.g. notching, twisting, compressing, shaping

A61F13/15731—Treating webs, e.g. for giving them a fibrelike appearance, e.g. by embossing

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61F13/00—Bandages or dressings; Absorbent pads

A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators

A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers

A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin

A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties

A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable

A61F13/5146—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable having apertures of perforations

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61F13/00—Bandages or dressings; Absorbent pads

A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators

A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin

A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties

A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable

A61F13/51462—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable being defined by a value or parameter

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES

A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads

A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons

A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads

A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons

A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials

A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof

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

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

C08K7/00—Use of ingredients characterised by shape

C08K7/16—Solid spheres

C08K7/18—Solid spheres inorganic

C08K7/20—Glass

H—ELECTRICITY

H01—ELECTRIC ELEMENTS

H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY

H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells

H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells

H01M50/409—Separators, membranes or diaphragms characterised by the material

H01M50/411—Organic material

H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins

H01M50/417—Polyolefins

H—ELECTRICITY

H01—ELECTRIC ELEMENTS

H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY

H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells

H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells

H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties

A—HUMAN NECESSITIES

A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL

A47G—HOUSEHOLD OR TABLE EQUIPMENT

A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows

A47G2009/001—Anti-allergen; Anti-mite

A—HUMAN NECESSITIES

A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE

A61F13/00—Bandages or dressings; Absorbent pads

A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators

A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin

A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material

A61F2013/51409—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film

A61F2013/51411—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film being impervious to fluids but not for air or vapours

A61F2013/51415—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material being a film being impervious to fluids but not for air or vapours with pores

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

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

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation

Y02E60/10—Energy storage using batteries

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S264/00—Plastic and nonmetallic article shaping or treating: processes

Y10S264/06—Molding microballoons and binder

Description

_I S F Ref: 103140 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION 0 8 6 9
(ORIGINAL)
FOR OFFICE USE: Class Int Class 3, 0 Complete Specification Lodged: Accepted: Published: Priority: This document contains the ,amendments made under Section 49 and is correct for printing.
Related Art: 0 0o Name and Address of Applicant: Address for Service: Hercules Incorporated 1313 N. Market Street Hercules Plaza Wilmington Delaware 19894 UNITED STATES OF AMERICA Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia
CC
O C IC Complete Specification for the invention entitled: Breathable Microporous Film and Methods for Making It The following statement is a full description of this invention, including the best method of perforing it known to me/us 5845/3 0 8 1 8 p Antoon and Hill Case 1 BREATHABLE MICROPOROUS FILM AND A METHOD FOR MAKING IT Abstract of the Disclosure 0040 o0o A method for making soft, flexible, microporous films 0 o0 having high tensile strength and high breathability levels 0 0 for air and water vapor and high hydrostatic resistance to 0o» penetration by liquid water, in which a film fabricated by o 0 «0 blending a mixture of a polymer or copolymer of an alpha- S olefin with 60 to 75% by weight of an inorganic filler or glass beads having particle sizes within the range of 10 to micrometers and calcium stearate as a processing aid is ,0 biaxially stretched from about 1.5 to about 7 times in each cr c C cc direction at a temperature of from about 20° to about 160 0
C,
S and the moisture level in the blended composition is 0,00 maintained below 700 parts per million before fabricating 4 00 the film; the film so made having a Gurley porosity of from 0.1 to 20 seconds; and its use in disposable items such as panty liners, diapers, bed sheets, and hospital gowns, or, C c if the ‘filler consists, of glass beads, its use as a battery Sseparator.
This invention relates to methods for making soft, flexible, microporous films having high tensile strength and good permeance or ‘»breathability» levels for air and water vapor and high hydrostatic resistance to penetration by liquid water, to films made by the said methods, and to the uses of such films.
It is well known that thermoplastic polymers can be filled with inert fillers, cast into sheets, and stretched to form an oriented microporous thermoplastic film that provides a desired level of gas or vapor permeance. Methods for making such films are described, for example, in U.S.
Patents 3,903,234 and 4,698,372, in UK Patent Specification 2,151,538, and in European published Patent Application 272,026, the latter disclosing films of homopolymers, 0015 copolymers, or blends of alpha-monoolefins having 2 to oo carbons having an oxygen and carbon dioxide permeance beoo 2 0 tween about 77,500 and 155,000,000 cc/m -day-atmosphere.
o0 U. S. Patent No. 4,698,372 discloses microporous o 0 .0 polymeric films for use as substitutes for textiles and 0 0 oo 20 having good water vapor transmission rates and hydrostatic o»o0 resistance to water penetration; the films may consist of 0 0 certain ethylene copolymers and have a filler loading of about 25-35 volume of inorganic fillers such as calcium 00co carbonate; they use a processing aid such as stearic acid o 0 25 that is referred to as an «antagonizer» and is said to 0 00 0 00 0 00 0 00
C
C C C C St L 2 ooo
Q
o000 0000 0 0 0 0 0 0 o 00oooo 0000 0 6 0 0 0a0 00 00 oo S 0 C o0 0 O O0 00 J 000: 0 0 00 reduce the effective surface tension of the filler to the approximate level of that of the matrix polymer. U.S.
Patent No. 3,903,234 discloses gas-permeable biaxially oriented film prepared from C 2
-C
1 0 alpha-monoolefin polymers containing 26-50% by weight of inorganic filler particles. UK Patent Specification 2,151,538 discloses a method for making water-vapor-permeable oriented films from polyolefins containing 33-83% by weight of barium sulfate filler, for use as a leakproof sheet in disposable diapers and sanitary napkins.
In general, the available liquid-barrier films that have an appreciable level of «breathability», for instance, those sold as diaper liners or covers for panty liners, do not reach desirable levels of breathability. This can be evaluated quantitatively in term of Gurley porosity numbers, which are measured in seconds by ASTM D-726, Method A or Method B. (Theoretically, Gurley numbers measured by Method o A are 25 times larger than Gurley numbers measured by Method B, and Method B numbers will be used in the following de- 20 scription and claims). Method B of ASTM D- 3 measures the o time (in seconds) for ten milliliters of air to pass through one square inch of microporo.s film under a pressure of 12.2 o inches of water. (Method A of ASTM D-726 measures the time 0a (in seconds) for 100 milliliters of air to pass through one 25 square inch of microporous film under a pressure of 4.9 inches of water). A low Gurley number signifies that a microporoua film offers little resistance to the passage of air (or humid air). Thus, Gurley numbers, also known as 0 Gurley porosity numbers, are effective measures of 30 «breathability».
0 The generally available films have Gurley numbers up to 100 seconds and usually above 10 to 20 seconds. The unavailability of soft, flexible, microporous liquid-barrier o o films having high tensile strength and a higher level of 0 0 0 0 0 0 3 «breathability», at a reasonable cost, indicates that there is a need, particularly in the hygienic product industry, for such films. They are needed, for example, in the fabrication of disposable products such as feminine panty liners, diapers, bed sheets, and hospital gowns that are cool and comfortable for the wearer. There is also a need for such permeable films, which have an ion-exchange function, for use as battery separators.
According to a first embodiment of the present invention there is provided, a method for making soft, flexible, microporous films having high tensile strength and good permeance or «breathability» levels for air and water vapor and high hydrostatic resistance to penetration by liquid water, o including the steps of melt-blending a mixture of a polymer or copolymer of o000 0o0 0 an alpha-olefin, a particulate filler, and calcium stearate as a processing 0 0 S aid, fabricating a film, and biaxially stretching the film, is 0ooo S 15 characterized in that the mixture contains 60 to 75% by weight of an 0000oo inorganic filler or glass beads having particle sizes within the range of 0 0O o° 10 to 25 micrometers in mean diameter, the moisture level in the blended o» oo composition is maintained below 700 ppm prior to fabricating the film, and o0 0 the film is stretched in two directions from about 1.5 to about 7 times in each direction at a temperature range of from about 20″ to about 160’C.
0o00 According to a second embodiment of the present invention there is 0000 provided a biaxially oriented microporous films comprising a polymer or 0000 o00° 0 copolymer of an alpha-olefin, a particulate filler, and calcium stearate, o characterized in that it is made by the method as claimed in the first 000 0 25 embodiment and further characterized in that it has a Gurley porosity, based on method B, ASTM D-726, of 0.1 second to 20 seconds so that the film S has good air and water vapor transmission rates but is substantially i mpenetrable by liquid water.
Unless the moisture level in the composition prior to fabricating the film is maintained below 700 ppm, the film cannot be stretched uniformly, using the amount of filler required according to the invention.
Preferably, the moisture level in the blended composition is maintained below 300 ppm.
Also according to the invention, a soft, flexible, microporous film having high tensile strength and good permeance of «breathability» levels for air and water vapor and high hydrostatic resistance to penetration by liquid
^TMS/
^m ‘z.
k i l-ll-l-i-lll–LLiPi~L~ 4 water, and made by the said method according to the invention, is zurther characterized in that it comprises: to 37% by weight of a polymer or copolymer of an alpha-olefin having 1-8 carbon atoms, 60 to 75% by weight of an inorganic filler or glass beads having particle sizes within the range of of 10 to micrometers in mean diameter, and 0.1 to 3% by weight of calcium stearate, and has a Gurley porosity, based on method B, ASTM D-726, of 0.1 second to 20 seconds.
Preferably the film according to the invention, contains 0 to 2% by weight of a stabilizer.
«Microporous» means that the film contains numerous open pores or channels leading from one surface to the opposite surface, such pores being of a size to permit air and water vapor to pass through the film while having good resistance to the penetration of liquid water. Their porosity or breathability in Gurley porosity numbers can be expressed in terms of permeance by by dividing the constant oo° 20 44.64 x 10 seconds by the Gurley number (Method B) to o o give the permeance in cc/m -day-atmosphere. The permeance 0°o of the microporous film of this invention is greater than 0 o 00 44.64 x 109 seconds- cc/m -day-atmosphere divided by So o seconds, namely 2.232 x 10 or 2,232,000,000 cc/m 2 0 O O o 25 day-atmosphere.
0 0o0 So° The particle size of the filler determines the pore size of the microporous films of this invention. As would be expected, smaller particle sizes produce smaller pores o»o than larger particle sizes. There is no theoretical limio °530 tation on the size of the filler particles that may be used o0 0 in the practice of this invention. However, practical considerations impose effective limitations. Preferably, the 0 00 particle size of the fillers should range from 10 to micrometers in mean diameter, and preferably the filler is *I i calcium carbonate and the particle size is about 12.5 micrometers in mean diameter.
Filler-loading determines to a great extent how far the casting must be stretched to attain a given degree of overall porosity. Below the lower end of the loading range, 60% by weight, where the pores are less numerous, they are less interconnected, and the film is insufficiently permeable at the maximum draw ratio of about 7 times in each direction according to the invention. Above the higher end of the loading range, 75% by weight, either the materials will not blend uniformly or the casting made from the composition will not stretch the minimum according to the invention, namely, 1.5 times. Although other inorganic fillers may be used, calcium 0 0 oo carbonate is preferred. However, if the films are to be used as battery 0o 0o 0 separators the filler is inert to the liquid contained in the battery and 0 0 0 0 glass beads are preferred.
0 ,15 The calcium stearate processing aid coats the filler particles, thus ooo assisting in the uniform dispersion of the filler particles, and allowing 0000oo° the composition to be stretched to the required degree of orientation.
0 a A variety of alpha-olefinic polymeric materials having up to 8 carbon atoms can be used as matrix polymers. Any such alpha-olefin that exhibits sufficient tensile yielding and some permanent deformation may be used.
00 The selection the polymeric material will be based on the desired properties of the microporous film, as for example, temperature resistance 0ooo 0°oo° or elastic recovery. Preferred homopolymers are polypropylene (PP), 0 0 polyethylene (PE) (particularly linear low-density polyethylene (LLDPE), 0 «25 and polybutylene Copolymers of ethylene with propylene or with an alpha-olefin of 4-8 carbon atoms may of course be used also. For ease in 8 X processing, a blend of linear low density polyethylene and polypropylene in 8 a ratio of 95 to 5, or polypropylene blended with ethylene- propylene copolymer, is
X
6 preferable to polypropylene alone as a matrix material.
The choice of the polymeric material in the matrix, and the choice of the filler-material influences the prefered amounts of the filler and the calcium stearate, the orientation temperature, and the extent of biaxial orientation.
With a polypropylene/calcium carbonate combination, the mixture preferably contains about 33% by weight of polypropylene, and the amount of the calcium carbonate filler preferably is about 65% by weight. The amount of calcium stearate preferably is about 0.5 to about and more preferably The biaxial orientation of the film preferably is in the range of from about 4 to about 7 times in each direction, more preferably about 5 times, with the orientation temperature preferably being from 130 to 150 0
C,
with about 130 0 C being most preferred.
With a polypropylene/glass beads combination, the mixture preferably contains about 33.5% by weight of polypropylene, the amount of the glass beads filler preferably being in the range of 55 to 65% by weight, more preferably 20 65%. The amount of calcium stearate preferably is about to about and most preferably 1 .5% 7 The biaxial orientation of the film preferably preferably is in the range of from about 4 to about 7 times in each direction, more preferably about 5 times, with the orientation temperature 25 preferably being from 130 to 150 0 C, with about 135 0 C being most preferred.
With a polybutylene/calcium carbonate combination, the mixture preferably contains about 65 to about 75% by weight of the filler, with about 70% being more preferred; in this 30 combination the amount of calcium stearate to be used should 0 o0000 o 0000oo oo o o 0 0 0 o o 0 o0 0 0 So 0 0000 0 0 0 0 0 0 0* 00 00 00 0 0 0 0 0 0000 0 0 0 0 00 0 0 00 0 0 00 0 00
C
i -I i ii -7 be in the range of about 0.2 to about 4% by weight, with about 2% being more preferred. This film should be biaxbiaxially oriented from about 1.5 to about 5 times, more preferably about 4 times, at a temperature range of about to about 105 0 C, about 100 0 C being more preferred.
With a polyethylene/calcium carbonate combination, the amount of filler preferably is in the range of about 60 to about 70% by weight, about 70% being more preferred. The amount of calcium stearate in this combination preferably is from about 0.1 to about about 0.5 to about 2% being more preferred. This film preferably is biaxially oriented about 1.5 to about 5 times, with about 4 times being more preferred, in a temperature range of about 20°C to about 110°C, with about 100°C being more preferred.
Preferably the mixture contains from about 0.1 to about 2% by weight of a stabilizer against degradation by exposure to UV light, oxygen, and heat; it is especially useful in the combinations with the polypropylene and the polyethylene.
After the film composition is prepared, it may be com- ‘0 20 pounded into the film of this invention by any known method 00,°°o suitable for the melt blending of thermoplastic polymers at o 0 temperatures at which the matrix polymers are processible.
0 0 0 High shear mixing, which can be achieved in a Banbury-type o°0°0 or another high intensity mixer or in continuous mixers such 0 o 25 as extruders, is preferred. There is no need to premix 00 00 0 ingredients, but this may be done without detriment to the 0 practice of this invention and may in certain instances offer improved performance.
oa0a After the ingredients of the composition of this inveno .030 tion have been melt blended., the moisture level of this S°°00 blend is then maintained below the critical level of 700 0 o oo parts per million (ppm) (more preferably below 300 ppm), preferably by simultaneously cooling and maintaining the moisture level of the blended and extruded composition by tc C RV-1 I a 8flowing air over it on a moving conveyor belt. This air-cooling method yields strands and pellets that have residual moisture levels far below the levels achieved by the process of cooling by immersion in a water bath that is conventionally used.
The strands were then pelletized using conventional techniques. To accurately achieve this moisture level, sensitive moisture measurement is required. For example, a Coulometric Karl Fischer titration method (using the Brinkman Model 652 RF Coulometer) can be used for evaluating the moisture level in the formulations.
After blending and establishing the moisture level, the composition is converted into any convenient form for processing into film, including pellets or sheets. The film fabrication can be accomplished by any conventional technique including extrusion casting, compression molding, flat film extrusion, or blown film extrusion.
After the film is fabricated into its desired form, it is then biaxially oriented by stretching by any of the well °o»o 20 known techniques in the art including, by hydraulics, by pinch rolls moving at different rates, or by tentering.
o° Biaxial stretching can be performed sequentially or simul- 0oo taneously. Sequential biaxial stretching is preferred when .o.O using the tentering operation.
o 25 Another process for maintaining the desired moisture 0 o level is to employ vacuum-drying in order to reduce the 0 moisture level in too-wet pellets to acceptable levels according to the invention, (below 700 ppm, and more preferably below 300 ppm). In this case, pellets composed of °000 30 polymer plus filler are made using the conventional water- 0o°0 bath-cooling process, which produces is excessive residual 00oo moisture levels. These too-wet pellets are subjected to a 0 s partial vacuum, preferably with some heating to speed the process, for a, period of time until the moisture content is
C
cct 9 within acceptable limits as defined above. This process is not preferred since the extra step of vacuum-drying is required.
Yet another process of maintaining the desired moisture level is by charging the hot melt directly to the extruder that extrudes the casting from a die. In this case, the molten composition is never exposed to water and has a low residual moisture level as defined above. Therefore, a smooth and highly-orientable casting uill be formed.
The stretch ratio of at least two times the original forming dimensions is significant to producing a film having at least 30% of pores resulting in relatively high density films. However, to produce relatively low density films, it is preferred that the film be stretched to at least 3 to 8 times its original forming dimensions in mutually perpendicular directions, resulting in a film having about 40 to pores.
Stretching is of course effected above the glass transition temperature of the matrix polymer (preferably at o»o 0 3 20 least 20°C above) and below the melting temperature of the 0000 oo ooo matrix polymer, especially within 10 0 C of that temperature, o depending to some degree on the rate of stretching. Differ- 0000 0 S ent polymers and compositions thereof exhibit different 000oo :ooo_ elastic and viscoelastic behavior. Thus, different amounts o( 25 of stretching must be imposed on different samples in order 00 00 g to obtain the same permeability properties. Obviously, the 0 film must be stretched beyond its yield point in order to attain the permanent deformation necessary for the formation 000oo of porosity.
0 0 0 0 30 For a given composition, a greater degree of stretch 00oo results in greater overall porosity. Higher overall poroso oo ity can be attained by adding more filler and stretching the 0 same amount or possibly less.
00 0 0000 0 0 00 0 ao o :1 Y i_ i I 10 In the following examples, all parts, :portions, and percentages are by weight unless otherwise indicated.
In Examples 1-8, the ingredients (listed in Table 1A) were blended at room temperature and compounded in a twinscrew extruder; strands were extruded at in a temperature range of 2430 to 265 0 C. The strands were then air cooled (except that in Examples 6-8 they were water cooled) and pelletized. The pellets were vacuum dried for 24 hours at 0 C. (except that Examples 7 and 8 they were vacuum dried for 8 hours at Using a melt temperature of 278 to 282 0 C (478 to 5400F), the pellets were extruded by a single screw extruder through a six inch wide slit die onto a casting roll maintained at about 65 0 C (except Examples 6-8 were maintained at about 18-24 0 C) so as to form a 15 mil thick casting. Using a T.M. Long stretcher, square pieces having the dimensions 2 x 2 inches from the casting were biaxially oriented by stretching 4 times in the machine direction and 4 times in the transverse direction (except that in Example 8 it was stretched 2x by 2x) at 100 0 C, producing the product 0o»° 20 as set forth in the following Table 1.
0oo oo The ingredients for Examples 9-14 are listed in Table 1 Sso B. In Examples 9 and 10, the ingredients were blended O0 together on a 2-roll mill at 200 0 this blend was comoOO pression molded at 215″C. to yield 30 mil thick plaques.
o 25 Two inch by two inch portions of the plaques were biaxially °a o o S° oriented by stretching 5 times in the machine direction and times in the transverse direction on a T. M. Long stretcher at 140°C. to make the film as described in Table B., oooo In Examples 11 and 14, the ingredients were compounded o0° 30 in a twin screw extruder at 225-250 0 the extrudate was o 0 00 pelletized and cast on a casting extruder at 180 0 -230 0
C.
0 o00 For Example 11 since much strand breakage and non-uniformity So was observed during the pelletizing step, the casting could not be stretched at 1400°C on the T. M. Long stretcher; the 0 0 0 0 Co °ooC 11 casting was too brittle. For Example 14, 2 X 2 inch portions of the casting were stretched 4.5X by 4.5X at 140 0
C.
on the T. M. Long stretcher.
In Example 12 and 13, the ingredients were blended by a twin-screw extruder and were extruded by a single screw extruder and slit die to form a 30 mil casting; the casting was stretched 5X by 5X on a T. M. Long stretcher to form the film.
ooo 0 a 00 r 0° o 0 00 oof* 00o a t L I 0 0 o00 o 0 0 0 0 0 ~0 00 0 0 00 0 0’t C C 0 0 0) 00 0 0 00 la b.c.
POLYMER LLDPE 00) 28.5
CALCIUM
STEARATE 1.5 CaCOj(%) 70
STABILIZER
G LAS S BEADS lapb~c.
ORIENTA- a 4xby4.
TION/TEMPIC /1001C b 3xby3x c 2xby2x /1001C 2
LLDPE
33.25 1 .75 65 TABLE 1 A 3 Com 4 LLDPE LLDPE 38.0 29.4 -5- L LOP E/ Pf 27.0/1.5 -6-
PB
28.5 Com
PB
50.0 Com 8 2.0 0.6 1.5 60 70 70 1.5 0 70 PRODUCT PROPERTIES 23 Com 4 5- ‘,xby4x 4xby4x Mat’ls.4xby4x /1001C /100’C would /1001C not mix well 4xby4x /1001C Corn 7 4xby4x /10 0
C
Corn 8 2xby2x /1000 FILM THICK- a -fJESS (mil) b ~AIR VOIDS a b c 2.5 6.9 W 0. 1 sec .2sec -0.4spc 3.0 4.0 Gurl ey a POROSITY b (METHOD B) c 0.5sec 0.8sec 0.3sec 1.4sec is an ethylene-pr-opylene copolymer containing 2.7 mole percent ethylene units 0 a On 0 00 -9- P P/C 2C3a 1 39.83 0 0 Q 0 00 ;00 0 0 0 00 0 0 06 00 06 TABLE 1 B Corn 10 11
PP/C
2
C
3
PP
I:1I) 49.74 39.64
POLYM~ER
12
PP/CC
34.61 13 P P/C 2C 3 (1:1) 34.91
CALCIUM
STEARATE(%
CaCO 3 STAB ILIZER
GLASS
BEADS(%
0.32 59.75 0.10 0.40 49.74 0.12 0.40 59.46 0.50 1.04 64.27 0.09 0.17 64.83 0.09 14
PP
(1I:1I) 36.05 1.09 0.16 62.71 9 ORIENTA- Sxby5x
TION/TEMP
0 C /140*C PRODUCT PROPERTIES Corn 10 11 12 Sxby5x would 5xby5x /140’C not stretch 1401C 13 14 5exby5x 4.Sxby4.5x /140*C FILM THICK- NESS (mi AIR VOIDS Gu rl ey B5sec 10min 20sec 4. Osec.
POROSITY
(METHOD B) ‘CC. isar, ethylene-propylene copolymer cut~taining 2.7 mole percent ethylene uni ts.
14 All of the resulting products of the Examples were opaque white films.
Examples la, b, and c show that for the system LLDPE/ CaC03 films, 70% by weight of the filler gives much lower Gurley number high breathability) than 65% by weight of the filler. Examples la, b and c show that breathability is the best in the more highly oriented films. Similarly, by weight of the filler (Example 2) gives a much lower Gurley number than 60% filler, (Example Example 4 compared to Example 1 shows that the processibility of the formulation is improved by adding 1.5% of calcium stearate (Example 1) instead of 0.6% calcium stearate (Example 4); further, in comparative Example 4, die deposits and melt fractures were excessive and caused constant breakage c’ the extruded molten strands. Thus, the material could not be pelletized and extruded into castings suitable for orientation. Example 5 demonstrates the advantage of using a small amount of polypropylene additive in the LLDPE to reduce die lines. Regions of melt fracture (die lines) oa 20 thinner than the rest of the casting were greatly reduced 0 compared to the melt fracture regions commonly observed in o 0 0 compositions such as those in Examples la, b and c.
o Example 6 shows that, for polybutene/calcium carbonate °oo1 film, 70% by weight of the filler gives much lower Gurley S 25 number high breathability) than 50% by weight of the oooC filler in Example 7. Example 8, compared to Example 6, shows that 1.5% of calcium stearate allows much easier processing to a porous film than if no calcium stearate is used o (Example The film prepared in comparative Example 8 had oo 30 many visible pinholes and was extremely rough. Gurley mea- 0 °o0 surements were not possible. Castings made from this compop sition could not be oriented 4 times by 4 times at the temp- S erature of 100 0 C. Example 9 shows that, for polypropylene/ calcium carbonate films, 60% by weight of the filler gives a
C
Cc C i
C
i 15 much lower Gurley number than when only 5 0 by weight of the filler is used (Example 10). Example 11 compared to Example 9, shows that using a blend of polypropylene and ethylenepropylene copolymer gives better processing than if pure polypropylene is substituted for the blend (Example 11) because the casting of Example 11 would not stretch to form film at 140°C. Example 12 shows that high calcium stearate levels greatly improves processibility compared to a low calcium stearate level in Example 13 because the resulting film had large visible pin holes and was extremely rough.
Example 14 demonstrates a breathable composition composed of polypropylene and glass bead filler.
o O o 00 o 0000 00 0 o a 0000 o@ 0 0 000’1 0000 o 0 o 0 0000 00 0 0 0 0 0 000a 0 00 00 0 0 00 00 0 0 00 0 4400 a C 0 C 0 00 L1; I 1 r iY -L -L ii

Claims (18)

1. A method for making soft, flexible, microporous films having high tensile strength and good permeance or «breathability» levels for air and water vapor and high hydrostatic resistance to penetration by liquid water, in- cluding +he steps of melt-blending a mixture of a polymer or copolymer of an alpha-olefin, a particulate filler, and cal- cium stearate as a processing aid, fabricating a film, and biaxially stretching the film, characterized in that the mixture contains 60 to 75% by weight of an inorganic filler or glass beads having particle sizes within the range of to 25 micrometers in mean diameter, the moisture level in the blended composition is maintained below 700 parts per million prior to fabricating the film, and the film is o» 9 stretched in two directions from about 1.5 to about 7 times 0000 15 in each direction at a temperature range of from about 200 oo 0 o o to about 160 0 C. 0000 0 0 o o 0000 o.oo 2. A method for making microporous films as claimed in 0 0 0 ooO claim 1, further characterized in that the particle size of O 00 00 the filler is from 10 to t5 micrometers in mean diameter. O O

3. A method for making microporous films as claimed in 000 claim 1 or 2, further characterized in that the filler is 0 0 0 00 o calcium carbonate and the particle size is about 12.5 micro- 0 00 o oo 0 meters in mean diameter. 0 0 00 00 0 I 17

4. A method for making microporous films as claimed in claim 1, 2, or 3, further characterized in that the moisture level in the blended composition is maintained below 300 parts per million prior to fabricating the film.

5. A method for making microporous films as claimed in any of the precq eding claims, further characterized in that the blended and eteded composition is cooled and its mois- ture level is simultaneously maintained by flowing air over it on a moving conveyor belt.

6. A method for making microporous films as claimed in any of the preceeding claims, further characterized in that the polymer or copolymer of an alpha-olefin is an alpha-olefin having 8 carbon atoms or a copolymer of ethylene with pro- pylene or with an alpha-olefin of 4-8 carbon atoms.

7. A method for making microporous films as claimed in claim 6, further characterized in that the polymer or copolymer of an alpha-olefin is polypropylene, polyethylene, o polybutylene, a blend of linear low density polyethylene and 0000 0 polypropylene, or a blend of polypropylene with 0 0 0 2o20 ethylene-propylene copolymer. 0 0 0 0 .oo 8. A method for making microporous films as claimed in claim 7, further characterized in that the polymer or 00 00 o° 0g copolymer of an alpha-olefin is linear low-density 0o polyethylene. o oo 0 00 os O 00 SO 0 0 00 0 0 00 00 0 0 00 0o 0 00 0 000 oso 0 oo 00 0 o 0 o o 0090 0 0 0 0 0.00 0 0 0 00 S00 0o0 0 oo o o 0 O 0 o o 0000 o o 0000 0 0 0 00 0 0 00 0 0 0 C o 0 0000″1 o E 1 i aP sc 18

9. A method for making microporous films as claimed in any one of claims 1 to 7 further characterized in that the mixture contains about to 37% by weight of polypropylene, and the filler is calcium carbonate. A method for making microporous films as claimed in claim 9, further characterized in that the mixture contains about 33% by weight of polypropylene, about 65% by weight of calcium carbonate, about 0.5 to 2% by weight of calcium stearate, and the film is stretched in two directions to 7 times at a temperature of about 150 to 130″C.

11. A method for making microporous films as claimed in claim 9, further characterized in that the mixture contains about 2% by weight of calcium stearate, the moisture level is maintained below 300 ppm, and the film is stretched in two directions 5 times in each direction at a temperature of about 130 0 C.

12. A method for making microporous films as claimed in any one of claims 1 to 7 or 9 to 11 further characterized in that the mixture contains about 20 to 37% by weight of polypropylene, and the filler is glass beads.

13. A method for making microporous films as claimed in claim 12, further characterized in that the mixture contains about 33.5% by weight of polypropylene, about 65% by weight of glass beads, about 0.5 to 2% by weight of calcium stearate, and the film is stretched in two directions to 7 times at a temperature of about 130 to 150 0 C.

14. A method for making microporous films as claimed in claim 13, further characterized in that the mixture contains about 2% by weight of calcium stearate, the moisture level is maintained below 300 ppm, and the film is stretched in two directions 5 times in each direction at a temperature of about 130°C. A method for making microporous films as claimed in any one of claims 1 to 7, 11 or 14, characterized in that the mixture contains about 35 to 25% by weight of polybutylene, and the filler is calcium carbonate.

16. A method for making microporous films as claimed in claim further characterized in that the mixture contains about 28% by weight of polybutylene, about 70% by weight of calcium carbonate, about 0.2 to 4% by weight of calcium stearate, and the film is stretched in two directions to 5 times at a temperature of about 20 to 105°C.

17. A method for making microporous films as claimed in claim 16, further characterized in that the mixture contains about 2% by weight of calcium stearate, the moisture level is maintained below 300 ppm, and the temperature of about 100*C. C’00 t t co 00 0 0 00 j s, 19 film is stretched in two directions 4 times in each direction at a ao oo 00 0 0o 00 0000 0 0 0000 0 0 o a 0 0 000o o o o 0 00 00 00 o 0 0o 00 00 0 0 0 0 00 0 00 t C :U L 4 20

19. A method for making microporous films as claimed in claim 18, further characterized in that the mixture contains about 28% by weight of polyethylene, about 70% by weight of calcium carbonate, about 0.1 to 3.5% by weight of calcium stearate, and the e4.t4kg\is stretched in two directions 1.5 to 5 times at a temperature of about to 20 to 105″C. A method for making microporous films as claimed in claim 19, further characterized in that the mixture con- tains about 0.5 to 2% by weight of calcium stearate, the moisture level is maintained below 300 ppm, and theea-teig is stretched in two directions 4 times in each direction at a temperature of about 1000C.

21. A method for making microporous films as claimed in any of the preceeding claims, further characterized in that the mixture contains from about 0.1 to about 2% by weight of a stabilizer against degradation by exposure to UV light, oxygen, and heat. 0 0 0 o0 0 0000 00 0 0 0 0 0 0000 0 0 0o o 00 0 0 0 0 0 0 0 0 00 0 0 00 0° 0 a 0 0 0 0 a it s0 t l4 J 1~ i 21

22. A method for making soft, flexible, microporous films having high tensile strength and good permeance of «breathability» levels for air and water vapour and high hydrostatic resistance to penetration by liquid water substantially as hereinbefore described with reference to any one of the Examples.

23. A biaxially oriented microporous film comprising a polymer or copolymer of an alpha-olefin, a particulate filler, and calcium stearate, characterized in that it is made by the method as claimed in any one of the preceeding claims and further characterized in that it has a Gurley porosity, based on method B, ASTM D-726, of 0.1 second to 20 seconds so that the film has good air and water vapor transmission rates but is oCoo substantially impenetrable by liquid water. 0090 o o0 24. A cover sheet for panty liners or a diaper containing a 0 0 0 0 0 0° microporous film according to claim 23. 0oo» 25. A bed sheet or a hospital gown manufactured from a microporous O 0 ooo film according to claim 23. 0ooO0 26. An ion-permeable separator in a liquid-containing battery o 0o manufactured from a microporous film in which the particulate filler is inert to the liquid contained in the battery.

27. A soft, flexible, microporous film having high tensile strength o and good permeance of «breathability» levels for air and water vapour and 0 0 °0oo o high hydrostatic resistance to penetration by liquid water whenever 0000 0°00 prepared by the method according to claim 22. 0 00 0 o o0 DATED this FOURTEENTH day of DECEMBER 1990 °go 0 0 Hercules Incorporated 0 0000 0o s! Patent Attorneys for the Applicant SPRUSON FERGUSON

AU39034/89A
1988-07-27
1989-07-27
Breathable microporous film and methods for making it

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Breathable microporous film and methods for making it

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Also Published As

Publication number
Publication date

MX166789B
(en)

1993-02-04

US4923650A
(en)

1990-05-08

IL91130A
(en)

1993-05-13

BR8903742A
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1990-03-20

CN1041167A
(en)

1990-04-11

DK370689D0
(en)

1989-07-27

EP0352802A2
(en)

1990-01-31

DK370689A
(en)

1990-01-28

AU3903489A
(en)

1990-02-01

EP0352802A3
(en)

1990-08-16

IL91130A0
(en)

1990-03-19

CA1327259C
(en)

1994-03-01

NZ230093A
(en)

1991-11-26

JPH02127445A
(en)

1990-05-16

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