CA2275386A1 - Blends of polyethylene and peo having inverse phase morphology and method of making the blends - Google Patents
Blends of polyethylene and peo having inverse phase morphology and method of making the blends Download PDFInfo
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- CA2275386A1 CA2275386A1 CA002275386A CA2275386A CA2275386A1 CA 2275386 A1 CA2275386 A1 CA 2275386A1 CA 002275386 A CA002275386 A CA 002275386A CA 2275386 A CA2275386 A CA 2275386A CA 2275386 A1 CA2275386 A1 CA 2275386A1
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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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- 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
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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
- 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
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/268—Monolayer with structurally defined element
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Abstract
A thermoplastic film comprises a polyolefin, such as polyethylene, as a major constituent, poly(ethylene oxide) as a minor constituent and has a total of from about 0.1 weight percent to about 30 weight percent of monomer grafted to the polyolefin and the poly(ethylene oxide). The film exhibits an inverse phase morphology so that the poly(ethylene oxide) forms a continuous phase and the polyolefin forms a dispersed or discontinuous phase in the film. Desirably, the film can be used in disposable personal hygiene articles.
Description
BLENDS OF POLYETHYLENE AND PEO HAVING INVERSE PHASE MORPHOLOGY
AND METHOD OF MAKING THE BLENDS
The application claims priority from the: U.S. Provisional Application 60/034,235 filed December 31,1996, the disclosure of which is incorporated herein by reference.
FIELD OF THE: INVENTION
The present invention relates to a compositional thermoplastic film comprising polyethylene and polyethylene oxide) which exhibits an inverse phase morphology.
BACKGROUND OF THE INVENTION
There are a wide variety of disposable plastic articles of manufacture in use today. Because of their low cost and convenience, they are very popular and have a high consumer demand. However, many of these articles are not degradable or easily disposed of. Consequently, they have caused and continue to cause a waste disposal problem.
Personal care products, such as diapers) sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components and materials. Such articles typically have some portion, usually the backing layer) liner, or baffle that is composed of a film constructed from a liquid repellent material. This repellent material is appropriately constructed to minimize or prevent the exuding of the absorbed liquid from the article and to obtain careater utilization of the absorbent capacity of the product. The liquid repellent film commonly used includes plastic materials such as polyethylene films and the like.
Although such products are relatively inexpensive, sanitary and easy to use, disposal of a product once soiled is not without its problems. An ideal disposal method for such products would be to use municipal sewage treatment and private residential septic systems. Products suited for disposal in sewage systems can be flushed down a convenient toilet and are termed "flushable." ~Nhile flushing such articles would be convenient, the liquid repellent material which normally does not disintegrate in water tends to plug toilets and sewer pipes. It therefore becomes necessary, although undesirable, to separate the barrier film material from the absorbent article prior to flushing.
fn an attempt to overcome the flushability problem of a water resistant film the prior art has modified the water resistant polymer. One of the more useful ways of modifying polymers involves blending them with other polymers of different stnrctures and properties. In a few cases, polymer blend combinations are thermodynamically miscible and exhibit mechanical compatibility. However) by far a greater number of blends are phase separated and generally exhibit poor mechanical compatibility. Phase separated blends can in some cases exhibit mechanical compatibility where the polymer compositions are similar, for example, polyolefin blended with other similar polyolefins, or where interfacial agents are added to improve the compatibility at the interface between the constituents of the polymer blend.
Polymer blends of polyolefins and polyethylene oxide) are melt processible but exhibit very poor mechanical compatibility. This poor mechanical compatibility is particularly manifested in blends having greater than 50 weight percent of polyolefin.
Generally the film is not affected by water since typically the majority phase, i.e.
polyolefin, will surround and encapsulate the minority phase, i.e. the polyethylene oxide).
The encapsulation of the polyethylene oxide) effectively prevents any degradability and/or flushability advantage that would be acquired by using polyethylene oxide).
In view of the problems of the prior art) it remains highly desirable to provide a blend having greater than about 50 weight percent of a polyolefin and polyethylene oxide) which would exhibit an inverse phase morphology. Films made from such a blend could be used for making barrier films for personal care products which would be flushable. The films could further be used for the manufacture of filter membranes.
SUMMARY OF THE INVENTION
Briefly, the present invention provides for a thermoplastic film comprising a polyolefin, polyethylene oxide) and an amount of monomer grafted onto the polyolefin and polyethylene oxide) so that the film exhibits an inverse phase morphology.
As used herein "inverse phase morphology" means that the volumetric majority constituent, which normally would be expected to form the continuous phase in the film, is actually the dispersed phase. Correspondingly, the volumetric minority constituent forms the continuous phase in which the volumetric majority constituent is dispersed therein.
It is an object of the invention to provide a thermoplastic film having an inverse phase morphology. More specifically, it is an object of the invention to provide a thermoplastic film having from about 55 weight percent to about 85 weight percent of a pofyolefin, from about 45 weight percent to about 15 weight percent of polyethylene oxide) and an amount of monomer grafted to the polyolefin and polyethylene oxide) such that the film exhibits an inverse phase morphology. As used herein the "weight percents" of polyolefin and polyethylene oxide) are determined using the total amount of polyolefin and polyethylene oxide) forming the thermoplastic composition without regard to the amount of monomer added.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 9 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil (0.004 inch) film having a composition of 60 weight percent polyethylene and 40 weight percent polyethylene oxide).
Fig. 2 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional .view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent poly(~sthylene oxide) with about 3 weight percent of a monomer added to the polyethylene and polyethylene oxide).
Fig. 3 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent poly(~sthylene oxide) and about 5.5 weight percent of a monomer added to the polyethylene and polyethylene oxide).
Fig. 4 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent polyethylene oxide) and about 9 weight percent of a monomer added to the polyethylene and polyethylene oxide).
DETAILED DESCRIPTIOIN OF THE INVENTION
Although the present invention is described with reference to a thermoplastic film, one skilled in the art would understand the utility of the invention toward other thermoplastic articles that can be extruded or injection molded. The film composition of the present invention comprises from about 5:i weight percent to about 85 weight percent of a polyolefin, from about 45 weight percent to about 15 weight percent of polyethylene oxide) and an amount of monomer grafted onto the polyolefin and polyethylene oxide) so that the film exhibits an inverse phase morF>hology. It has unexpectedly been discovered that this inverse phase morphology, where a hydrophilic moiety constitutes the continuous phase) can be achieved by a minority component of the film to greatly expand the water sensitivity and degradability of a film. Preferably, the blend has from about 60 weight percent to about 85 weight percent of polyethylene and from about 40 weight percent to about 15 weight percent of polyethylene oxide) with an effective amount of monomer grafted onto the polyolefin and polyethylene oxide) to render the thermoplastics phase inversion.
The saturated ethylene polymers useful in the practice of this invention are homopolymers or copolymers of ethylene and are essentially linear in structure. As used herein, the term "saturated" refers to polymers which are fully saturated, but also includes polymers containing up to about 5% unsaturation. The homopolymers of ethylene include those prepared under either low pressure, i.e., linear low density or high density polyethylene) or high pressure, i.e., branched or low density polyethylene.
The high density polyethylenes are generally characterized by a density that is about equal to or greater than 0.94 grams per cubic centimeter (g/cc). Generally, the high density polyethylenes useful as the base resin in the present invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc. The polyethylenes can have a melt index, as measured at 2.16 kg and 190°C., ranging from about 0.005 decigrams per minute (dg/min) to 100 dg/min. Desirably, the polyethylene has a melt index of 0.01 dg/min to about 50 dg/min and more desirably of 0.05 dg/min to about 25 dg/min.
Alternatively, mixtures of polyethylene can be used as the base resin in producing the graft copolymer compositions, and such mixtures can have a melt index greater than 0.005 dg/min to less than about 100 dg/min.
The low density polyethylene has a density of less than 0.94 g/cc and are usually in the range of 0.91 g/cc to about 0.93 g/cc. The low density polyethylene has a melt index ranging from about 0.05 dg/min to about 100 dg/min and desirably from 0.05 dg/min to about 20 dg/min. Ultra low density polyethylene can be used in accordance with the present invention. Generally, ultra low density polyethylene has a density of less than 0.90 g/cc.
The above polyolefins can also be manufactured by using the well known multiple-site Ziegler-Natta catalysts or the more recent single-site metalfocene catalysts.
The metallocene catalyzed polyolefins have better controlled polymer microstructures than polyolefins manufactured using Ziegler-Natta catalysts, including narrower molecular weight distribution, well controlled chemical composition distribution, co-monomer sequence length distribution, and stereoregularity. Metallocene catalysts are known to polymerize propylene into atactic, isotactic, syndiotactic, isotactic-atactic steroblock copolymer.
Copolymers of ethylene which can be useful in the present invention may include copolymers of ethylene with one or more additional polymerizable, unsaturated monomers. Examples of such copolymers in~~~ude, but are not limited to, copolymers of ethylene and alpha olefins (such as propylene, butane, hexane or octane) including linear low density polyethylene, copolymers of ethylene and vinyl esters of linear or branched carboxylic acids having 1-24 carbon atoms such as ethylene-vinyl acetate copolymers, and copolymers of ethylene and acrylic or methacrytic esters of linear, branched or cyclic alkanols having 1-28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acryllate copolymers, such as ethylene-methyl acrylate copolymers.
Polyethylene oxide) polymers suitable: for the present invention can have a molecular weight ranging from 200,000 to 8,000,000 and preferably, range from about 200,000 to about 6,000,000. Polyethylene oxide) is available from Union Carbide Corporation under the trade name of POLYO;>~. Typically, polyethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65°C, above which polyethylene oxide) resin beconnes thermoplastic and can be formed by molding, extrusion and other methods known in the art.
The polyolefin and polyethylene oxide:) comprising the film have grafted thereto an effective amount of monomer, polyethylerne glycol ethyl ether methacrylate (available from Aldrich Chemical Company, Milwaukee, Wisconsin)) which, unexpectedly, produces in the film an inverse phase morphology. Referring to Fig. 1, one skilled in the art would expect for the polyethylene, as the major constituent, to form the continuous phase where the polyethylene oxide) is distributed therein as the discontinuous phase.
However, referring to Figs. 2-4, a film of the present invention has the polyethylene oxide) as the continuous phase with the polyethylene distributed as the discontinuous phase notwithstanding that there is a greater .amount of polyethylene. The amount of monomer grafted onto the polyolefin and poly(ethyfene oxide) is a total of from about 0.1 weight percent to about 30 weight percent) based on the weight of the polyolefin and polyethylene oxide). Desirably, the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 20 weight percent of the monomer grafted thereto.
More desirably, the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 10 weight percent of the monomer grafted thereto.
To prepare the grafted polyethylene and polyethylene oxide) constituents of the film of the invention, the polyolefin and polyethylene oxide) are reacted with the WO 98/29508 PCT/t1S97/24245 monomer in the presence of a free radical initiator. The initiator serves to initiate free radical grafting of the monomer. The method of grafting the polymer blends includes melt blending the desired weight ratios of a mixture of the polyolefin, polyethylene oxide), the monomer and a free radical initiator in an extruder and at a reaction temperature where the poiyolefin and polyethylene oxide) are converted to a molten state. Accordingly, a preferred method includes adding the polyoiefin, polyethylene oxide), monomer and free radical initiator simultaneously to the extnrder before the polymer constituents, i.e., the polyolefin and polyethylene oxide) have been melted.
Desirably, the melt extruder used for melt blending can introduce various constituents into the blend at different locations along the screw length. For example, the free radical initiator, cross-linking agents, or other reactive additives can be injected into the blend before or after one or more of the polymer constituents is melted or thoroughly mixed.
More preferably, the polyolefin and polyethylene oxide) are added at the beginning of the extruder. After melting, the monomer is added to melted polymers and further down the extruder barrel, the free radical initiator is fed to the melt blend. The method is described in greater detail in copending U.S. patent application having U.S.
serial no.
08/777,226 filed on December 31, 1996 and entitled "BLENDS OF POLYOLEFIN AND
POLYETHYLENE OXIDE) AND PROCESS FOR MAKING THE BLENDS", the entire disclosure of which is incorporated herein by reference.
The free radical initiators which can be used to graft the monomer onto the polyolefin include acyl peroxides such as benzoyl peroxide; dialkyl; diaryl;
or aralkyl peroxides such as di-t-butyl peroxide; dicumyl peroxide; cumyl butyl peroxide;
1,1-di-t-butyl peroxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene);
peroxyesters such as t-butyl peroxypivalate;
t-butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2, 5-di(perbenzoate); t-butyl di(perphthalate); dialkyl peroxymonocarbonates and peroxydicarbonates; hydroperoxides such as t-butyl hydroperoxide, p-methane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. Azo compounds such as azobisisobutyronitrile may also be used.
The amount of free radical initiator added to the extruder should be an amount sufficient to graft from about 1 percent to 100 percent of the monomer onto the polyolefin and polyethylene oxide). This ranges from about 0.1 weight percent to about 10 weight percent of initiator) and preferably, from about 0.1 weight percent to about 5 weight percent wherein all such ranges are based on the amount of monomer added to the melt blend.
Characteristic of the thermoplastic film of the invention, the film when viewed using a scanning electron microscope and using back-scattered electron detector images shows that the polyethylene oxide) forms the continuous phase wherein the pofyolefin is in a discontinuous phase, that is, dispersed thnroughout the polyethylene oxide) phase.
Back-scattered electron detector imaging produces an image wherein the higher average atomic number of the constituent produces a Ihigher intensity of back-scattered electrons, which appear brighter on the photographic image. A constituent having a lower atomic number produces a lower intensity of back-scattered electrons, which appear as a darker image on the photograph. Back-scattered electron microscope imaging is described in greater detail in Linda C. Sawyer and David T. Grubb, Polymer Microscopy, Chapman &
Hall, London) 1987, p. 25. Desirably, the poiyolefin portions of the thermoplastic film have an average cross-sectional diameter ranging from about 0.1 microns to about 50 microns, preferably from about 0.5 microns to about 30 microns and more preferably from about 0.5 microns to about 25 microns. Such "polyolefin portions" can be solidified pockets of polyolefin, fibers or combinations thereof.
The present invention is illustrated in greater detail by the specific examples presented below. It is to be understood that these examples are illustrative embodiments and are not intended to be limiting of the invention, but rather are to be construed broadly within the scope and content of the appended claims.
COMPARATIVE EXAMPLE
A 60/40 weight percent resin blend of low density polyethylene (PE) and polyethylene oxide) (PEO) was melt blended using an extruder. The PE had a melt index of 1.9 decigrams per minute (dg/min) and a density of 0.917 grams per cubic centimeter (g/cc) (Dow 5031; available from Dow Chemical Company, Midland, M!). The PEO had a molecular weight of 200,000 g/mol (POLYOX~ WSRN-80; available from Union Carbide Corp.). The extruder used for making the blend was a Wemer 8 Pfleiderer ZSK-30 extruder (available from We:mer 8 Pfleiderer Corporation, Ramsey, New Jersey). The resin blend was fed to the extruder at a rate of 34 Ib/hr.
The extruder had a pair of co-rotating screws arranged in parallel. The center distance between the two shafts was 26.2 mm. The nominal screw .diameter was 30 mm. The actual outer screw diameter was 30 mm. The inner screw diameter was 21.3 mm. The thread depth was 4.7 mm. The extruder had 14 processing barrels) with 13 heated barrels divided into 7 heating zones. The overall processing length was 1340 mm. The seven heating zones were all set at 180 degrees Centigrade (°C). The screw speed was set at 300 rpm.
All films of the melt blends in the Comparative Example and Examples 1-9 were made using a Haake counter-rotating twin screw extruder (available from Haake) 53 West Century Road, Paramus, NJ, 07652) equipped with a four inch slit die. The extruder had a length of 300 millimeters. The conical screws had 30 millimeters diameter at the feed port and a diameter of 20 millimeters at the die. The extruder had tour heating zones set at 170, 180, 180 and 190°C. The screw speed was 30 rpm. A chilled wind-up roll was used to collect the film. The chilled roll was operated at a speed sufficient to form a film having a thickness of about 4 mils (about 0.004 of an inch) and was maintained at a temperature of 15-20°C.
Referring to Fig. 1, the polyethylene formed the continuous phase and the polyethylene oxide) formed the discontinuous phase.
In accordance with the invention, a 60/40 weight percent resin blend of low density polyethylene and polyethylene oxide), as described above in the Comparative Example, was fed to the ZSK-30 extruder at a rate of 34 Ib/hr. The seven heating zones were all set at 180°C. The screw speed was 300 rpm. At barrel 4 of the extruder, a monomer, polyethylene glycol) ethyl ether methacrylate (PEG-MA; available from Aldrich Chemical Company, Milwaukee, WI), was added at the specified rate. At barrel 5 of the extruder, a free radical initiator (2,5-dimethyl-2,5-di(t-butylperoxy) hexane, supplied by Atochem, 2000 Market St., Philadelphia, PA under the tradename Lupersol 101) was added at the specified rate.
For Example 1, the PEG-MA feed rate was 1.0 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 2, the PEG-MA feed rate was 1.9 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 3, the PEG-MA feed rate was 3.1 Ib/hr and the initiator rate was 0.17 Ib/hr.
Referring to Figs. 2-4, the thermoplastic film of the invention exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
EXAMhLE 4 A 60/40 weight percent resin blend of low density polyethylene (Dow 5031) and polyethylene oxide) having a molecular weiglht of 100,000 g/mol (POLYOX~ WSRN-10) was fed to the ZSK-30 extruder at a rate of 35 Ib/hr. The seven heating zones were all set at 180°C. The screw speed was 300 rpm. A film of the melt blended resin exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
A resin blend having the specified ratio of low density polyethylene (Dow 5031) and polyethylene oxide) (POLYOX~ WSRN-80) was fed to a Haake extruder at 5.0 Ib/hr.
The Haake extruder was similar to that descrilbed above in the Comparative Example except the extruder included a two-hole strand die instead of the four inch slit die.
Simultaneously with the polymer feed to the extruder, specified amounts of the monomer, PEG-MA, and free radical initiator (Lupersol 101 ) were added at the feed throat. The extruder had four heating zones set at 170) 180, 180, and 190°C. The screw speed of the extruder was 150 rpm. The strands were cooled in air and pelletized.
For Example 5 the blend was 60/40 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 6 the blend was 65/35 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 7 the blend was 70/30 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 8 the blend was 75/25 PIJPEO, the PEG-MA feed rate was 0.50 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 9 the blend was 80/20 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
The films of Examples 5-9 exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
For Example 5, the amount of monomer grafted onto the polyethylene oxide) was determined, by proton NMR spectroscopy in deuterated water, to be 9.52 weight percent based on the amount of polyethylene oxide) in the blend. The amount of unreacted monomer was determined, by proton nuclear magnetic resonance (NMR) spectroscopy in deuterated water, to be 2.02 weight percent based on the amount of polyethylene and polyethylene oxide) in the blend. The amount of monomer grafted onto the polyethylene was determined to be 0.51 weight percent by Fourier-Transform Infrared (FT-IR) and oxygen content analysis as described in copending U. S. patent application 08/733,410 filed October 18, 1996 the entire disclosure of which is incorporated herein by reference.
While the invention has been described with reference to a preferred embodiment those skilled in the art will appreciate that various substitutions) omissions, changes and modifications may be made without departing from the spirit hereof.
Accordingly, it is intended that the foregoing examples be deemed merely exemplary of the present invention an not be deemed a limitation thereof.
AND METHOD OF MAKING THE BLENDS
The application claims priority from the: U.S. Provisional Application 60/034,235 filed December 31,1996, the disclosure of which is incorporated herein by reference.
FIELD OF THE: INVENTION
The present invention relates to a compositional thermoplastic film comprising polyethylene and polyethylene oxide) which exhibits an inverse phase morphology.
BACKGROUND OF THE INVENTION
There are a wide variety of disposable plastic articles of manufacture in use today. Because of their low cost and convenience, they are very popular and have a high consumer demand. However, many of these articles are not degradable or easily disposed of. Consequently, they have caused and continue to cause a waste disposal problem.
Personal care products, such as diapers) sanitary napkins, adult incontinence garments, and the like are generally constructed from a number of different components and materials. Such articles typically have some portion, usually the backing layer) liner, or baffle that is composed of a film constructed from a liquid repellent material. This repellent material is appropriately constructed to minimize or prevent the exuding of the absorbed liquid from the article and to obtain careater utilization of the absorbent capacity of the product. The liquid repellent film commonly used includes plastic materials such as polyethylene films and the like.
Although such products are relatively inexpensive, sanitary and easy to use, disposal of a product once soiled is not without its problems. An ideal disposal method for such products would be to use municipal sewage treatment and private residential septic systems. Products suited for disposal in sewage systems can be flushed down a convenient toilet and are termed "flushable." ~Nhile flushing such articles would be convenient, the liquid repellent material which normally does not disintegrate in water tends to plug toilets and sewer pipes. It therefore becomes necessary, although undesirable, to separate the barrier film material from the absorbent article prior to flushing.
fn an attempt to overcome the flushability problem of a water resistant film the prior art has modified the water resistant polymer. One of the more useful ways of modifying polymers involves blending them with other polymers of different stnrctures and properties. In a few cases, polymer blend combinations are thermodynamically miscible and exhibit mechanical compatibility. However) by far a greater number of blends are phase separated and generally exhibit poor mechanical compatibility. Phase separated blends can in some cases exhibit mechanical compatibility where the polymer compositions are similar, for example, polyolefin blended with other similar polyolefins, or where interfacial agents are added to improve the compatibility at the interface between the constituents of the polymer blend.
Polymer blends of polyolefins and polyethylene oxide) are melt processible but exhibit very poor mechanical compatibility. This poor mechanical compatibility is particularly manifested in blends having greater than 50 weight percent of polyolefin.
Generally the film is not affected by water since typically the majority phase, i.e.
polyolefin, will surround and encapsulate the minority phase, i.e. the polyethylene oxide).
The encapsulation of the polyethylene oxide) effectively prevents any degradability and/or flushability advantage that would be acquired by using polyethylene oxide).
In view of the problems of the prior art) it remains highly desirable to provide a blend having greater than about 50 weight percent of a polyolefin and polyethylene oxide) which would exhibit an inverse phase morphology. Films made from such a blend could be used for making barrier films for personal care products which would be flushable. The films could further be used for the manufacture of filter membranes.
SUMMARY OF THE INVENTION
Briefly, the present invention provides for a thermoplastic film comprising a polyolefin, polyethylene oxide) and an amount of monomer grafted onto the polyolefin and polyethylene oxide) so that the film exhibits an inverse phase morphology.
As used herein "inverse phase morphology" means that the volumetric majority constituent, which normally would be expected to form the continuous phase in the film, is actually the dispersed phase. Correspondingly, the volumetric minority constituent forms the continuous phase in which the volumetric majority constituent is dispersed therein.
It is an object of the invention to provide a thermoplastic film having an inverse phase morphology. More specifically, it is an object of the invention to provide a thermoplastic film having from about 55 weight percent to about 85 weight percent of a pofyolefin, from about 45 weight percent to about 15 weight percent of polyethylene oxide) and an amount of monomer grafted to the polyolefin and polyethylene oxide) such that the film exhibits an inverse phase morphology. As used herein the "weight percents" of polyolefin and polyethylene oxide) are determined using the total amount of polyolefin and polyethylene oxide) forming the thermoplastic composition without regard to the amount of monomer added.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 9 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil (0.004 inch) film having a composition of 60 weight percent polyethylene and 40 weight percent polyethylene oxide).
Fig. 2 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional .view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent poly(~sthylene oxide) with about 3 weight percent of a monomer added to the polyethylene and polyethylene oxide).
Fig. 3 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent poly(~sthylene oxide) and about 5.5 weight percent of a monomer added to the polyethylene and polyethylene oxide).
Fig. 4 is a scanning electron microscopic photomicrograph of a back-scattered electron image of a cross-sectional view of a 4 mil film having a composition of 60 weight percent polyethylene, 40 weight percent polyethylene oxide) and about 9 weight percent of a monomer added to the polyethylene and polyethylene oxide).
DETAILED DESCRIPTIOIN OF THE INVENTION
Although the present invention is described with reference to a thermoplastic film, one skilled in the art would understand the utility of the invention toward other thermoplastic articles that can be extruded or injection molded. The film composition of the present invention comprises from about 5:i weight percent to about 85 weight percent of a polyolefin, from about 45 weight percent to about 15 weight percent of polyethylene oxide) and an amount of monomer grafted onto the polyolefin and polyethylene oxide) so that the film exhibits an inverse phase morF>hology. It has unexpectedly been discovered that this inverse phase morphology, where a hydrophilic moiety constitutes the continuous phase) can be achieved by a minority component of the film to greatly expand the water sensitivity and degradability of a film. Preferably, the blend has from about 60 weight percent to about 85 weight percent of polyethylene and from about 40 weight percent to about 15 weight percent of polyethylene oxide) with an effective amount of monomer grafted onto the polyolefin and polyethylene oxide) to render the thermoplastics phase inversion.
The saturated ethylene polymers useful in the practice of this invention are homopolymers or copolymers of ethylene and are essentially linear in structure. As used herein, the term "saturated" refers to polymers which are fully saturated, but also includes polymers containing up to about 5% unsaturation. The homopolymers of ethylene include those prepared under either low pressure, i.e., linear low density or high density polyethylene) or high pressure, i.e., branched or low density polyethylene.
The high density polyethylenes are generally characterized by a density that is about equal to or greater than 0.94 grams per cubic centimeter (g/cc). Generally, the high density polyethylenes useful as the base resin in the present invention have a density ranging from about 0.94 g/cc to about 0.97 g/cc. The polyethylenes can have a melt index, as measured at 2.16 kg and 190°C., ranging from about 0.005 decigrams per minute (dg/min) to 100 dg/min. Desirably, the polyethylene has a melt index of 0.01 dg/min to about 50 dg/min and more desirably of 0.05 dg/min to about 25 dg/min.
Alternatively, mixtures of polyethylene can be used as the base resin in producing the graft copolymer compositions, and such mixtures can have a melt index greater than 0.005 dg/min to less than about 100 dg/min.
The low density polyethylene has a density of less than 0.94 g/cc and are usually in the range of 0.91 g/cc to about 0.93 g/cc. The low density polyethylene has a melt index ranging from about 0.05 dg/min to about 100 dg/min and desirably from 0.05 dg/min to about 20 dg/min. Ultra low density polyethylene can be used in accordance with the present invention. Generally, ultra low density polyethylene has a density of less than 0.90 g/cc.
The above polyolefins can also be manufactured by using the well known multiple-site Ziegler-Natta catalysts or the more recent single-site metalfocene catalysts.
The metallocene catalyzed polyolefins have better controlled polymer microstructures than polyolefins manufactured using Ziegler-Natta catalysts, including narrower molecular weight distribution, well controlled chemical composition distribution, co-monomer sequence length distribution, and stereoregularity. Metallocene catalysts are known to polymerize propylene into atactic, isotactic, syndiotactic, isotactic-atactic steroblock copolymer.
Copolymers of ethylene which can be useful in the present invention may include copolymers of ethylene with one or more additional polymerizable, unsaturated monomers. Examples of such copolymers in~~~ude, but are not limited to, copolymers of ethylene and alpha olefins (such as propylene, butane, hexane or octane) including linear low density polyethylene, copolymers of ethylene and vinyl esters of linear or branched carboxylic acids having 1-24 carbon atoms such as ethylene-vinyl acetate copolymers, and copolymers of ethylene and acrylic or methacrytic esters of linear, branched or cyclic alkanols having 1-28 carbon atoms. Examples of these latter copolymers include ethylene-alkyl (meth)acryllate copolymers, such as ethylene-methyl acrylate copolymers.
Polyethylene oxide) polymers suitable: for the present invention can have a molecular weight ranging from 200,000 to 8,000,000 and preferably, range from about 200,000 to about 6,000,000. Polyethylene oxide) is available from Union Carbide Corporation under the trade name of POLYO;>~. Typically, polyethylene oxide) is a dry free flowing white powder having a crystalline melting point in the order of about 65°C, above which polyethylene oxide) resin beconnes thermoplastic and can be formed by molding, extrusion and other methods known in the art.
The polyolefin and polyethylene oxide:) comprising the film have grafted thereto an effective amount of monomer, polyethylerne glycol ethyl ether methacrylate (available from Aldrich Chemical Company, Milwaukee, Wisconsin)) which, unexpectedly, produces in the film an inverse phase morphology. Referring to Fig. 1, one skilled in the art would expect for the polyethylene, as the major constituent, to form the continuous phase where the polyethylene oxide) is distributed therein as the discontinuous phase.
However, referring to Figs. 2-4, a film of the present invention has the polyethylene oxide) as the continuous phase with the polyethylene distributed as the discontinuous phase notwithstanding that there is a greater .amount of polyethylene. The amount of monomer grafted onto the polyolefin and poly(ethyfene oxide) is a total of from about 0.1 weight percent to about 30 weight percent) based on the weight of the polyolefin and polyethylene oxide). Desirably, the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 20 weight percent of the monomer grafted thereto.
More desirably, the polyolefin and polyethylene oxide) have a total of from about 1 weight percent to about 10 weight percent of the monomer grafted thereto.
To prepare the grafted polyethylene and polyethylene oxide) constituents of the film of the invention, the polyolefin and polyethylene oxide) are reacted with the WO 98/29508 PCT/t1S97/24245 monomer in the presence of a free radical initiator. The initiator serves to initiate free radical grafting of the monomer. The method of grafting the polymer blends includes melt blending the desired weight ratios of a mixture of the polyolefin, polyethylene oxide), the monomer and a free radical initiator in an extruder and at a reaction temperature where the poiyolefin and polyethylene oxide) are converted to a molten state. Accordingly, a preferred method includes adding the polyoiefin, polyethylene oxide), monomer and free radical initiator simultaneously to the extnrder before the polymer constituents, i.e., the polyolefin and polyethylene oxide) have been melted.
Desirably, the melt extruder used for melt blending can introduce various constituents into the blend at different locations along the screw length. For example, the free radical initiator, cross-linking agents, or other reactive additives can be injected into the blend before or after one or more of the polymer constituents is melted or thoroughly mixed.
More preferably, the polyolefin and polyethylene oxide) are added at the beginning of the extruder. After melting, the monomer is added to melted polymers and further down the extruder barrel, the free radical initiator is fed to the melt blend. The method is described in greater detail in copending U.S. patent application having U.S.
serial no.
08/777,226 filed on December 31, 1996 and entitled "BLENDS OF POLYOLEFIN AND
POLYETHYLENE OXIDE) AND PROCESS FOR MAKING THE BLENDS", the entire disclosure of which is incorporated herein by reference.
The free radical initiators which can be used to graft the monomer onto the polyolefin include acyl peroxides such as benzoyl peroxide; dialkyl; diaryl;
or aralkyl peroxides such as di-t-butyl peroxide; dicumyl peroxide; cumyl butyl peroxide;
1,1-di-t-butyl peroxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3 and bis(a-t-butyl peroxyisopropylbenzene);
peroxyesters such as t-butyl peroxypivalate;
t-butyl peroctoate; t-butyl perbenzoate; 2,5-dimethylhexyl-2, 5-di(perbenzoate); t-butyl di(perphthalate); dialkyl peroxymonocarbonates and peroxydicarbonates; hydroperoxides such as t-butyl hydroperoxide, p-methane hydroperoxide, pinane hydroperoxide and cumene hydroperoxide and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. Azo compounds such as azobisisobutyronitrile may also be used.
The amount of free radical initiator added to the extruder should be an amount sufficient to graft from about 1 percent to 100 percent of the monomer onto the polyolefin and polyethylene oxide). This ranges from about 0.1 weight percent to about 10 weight percent of initiator) and preferably, from about 0.1 weight percent to about 5 weight percent wherein all such ranges are based on the amount of monomer added to the melt blend.
Characteristic of the thermoplastic film of the invention, the film when viewed using a scanning electron microscope and using back-scattered electron detector images shows that the polyethylene oxide) forms the continuous phase wherein the pofyolefin is in a discontinuous phase, that is, dispersed thnroughout the polyethylene oxide) phase.
Back-scattered electron detector imaging produces an image wherein the higher average atomic number of the constituent produces a Ihigher intensity of back-scattered electrons, which appear brighter on the photographic image. A constituent having a lower atomic number produces a lower intensity of back-scattered electrons, which appear as a darker image on the photograph. Back-scattered electron microscope imaging is described in greater detail in Linda C. Sawyer and David T. Grubb, Polymer Microscopy, Chapman &
Hall, London) 1987, p. 25. Desirably, the poiyolefin portions of the thermoplastic film have an average cross-sectional diameter ranging from about 0.1 microns to about 50 microns, preferably from about 0.5 microns to about 30 microns and more preferably from about 0.5 microns to about 25 microns. Such "polyolefin portions" can be solidified pockets of polyolefin, fibers or combinations thereof.
The present invention is illustrated in greater detail by the specific examples presented below. It is to be understood that these examples are illustrative embodiments and are not intended to be limiting of the invention, but rather are to be construed broadly within the scope and content of the appended claims.
COMPARATIVE EXAMPLE
A 60/40 weight percent resin blend of low density polyethylene (PE) and polyethylene oxide) (PEO) was melt blended using an extruder. The PE had a melt index of 1.9 decigrams per minute (dg/min) and a density of 0.917 grams per cubic centimeter (g/cc) (Dow 5031; available from Dow Chemical Company, Midland, M!). The PEO had a molecular weight of 200,000 g/mol (POLYOX~ WSRN-80; available from Union Carbide Corp.). The extruder used for making the blend was a Wemer 8 Pfleiderer ZSK-30 extruder (available from We:mer 8 Pfleiderer Corporation, Ramsey, New Jersey). The resin blend was fed to the extruder at a rate of 34 Ib/hr.
The extruder had a pair of co-rotating screws arranged in parallel. The center distance between the two shafts was 26.2 mm. The nominal screw .diameter was 30 mm. The actual outer screw diameter was 30 mm. The inner screw diameter was 21.3 mm. The thread depth was 4.7 mm. The extruder had 14 processing barrels) with 13 heated barrels divided into 7 heating zones. The overall processing length was 1340 mm. The seven heating zones were all set at 180 degrees Centigrade (°C). The screw speed was set at 300 rpm.
All films of the melt blends in the Comparative Example and Examples 1-9 were made using a Haake counter-rotating twin screw extruder (available from Haake) 53 West Century Road, Paramus, NJ, 07652) equipped with a four inch slit die. The extruder had a length of 300 millimeters. The conical screws had 30 millimeters diameter at the feed port and a diameter of 20 millimeters at the die. The extruder had tour heating zones set at 170, 180, 180 and 190°C. The screw speed was 30 rpm. A chilled wind-up roll was used to collect the film. The chilled roll was operated at a speed sufficient to form a film having a thickness of about 4 mils (about 0.004 of an inch) and was maintained at a temperature of 15-20°C.
Referring to Fig. 1, the polyethylene formed the continuous phase and the polyethylene oxide) formed the discontinuous phase.
In accordance with the invention, a 60/40 weight percent resin blend of low density polyethylene and polyethylene oxide), as described above in the Comparative Example, was fed to the ZSK-30 extruder at a rate of 34 Ib/hr. The seven heating zones were all set at 180°C. The screw speed was 300 rpm. At barrel 4 of the extruder, a monomer, polyethylene glycol) ethyl ether methacrylate (PEG-MA; available from Aldrich Chemical Company, Milwaukee, WI), was added at the specified rate. At barrel 5 of the extruder, a free radical initiator (2,5-dimethyl-2,5-di(t-butylperoxy) hexane, supplied by Atochem, 2000 Market St., Philadelphia, PA under the tradename Lupersol 101) was added at the specified rate.
For Example 1, the PEG-MA feed rate was 1.0 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 2, the PEG-MA feed rate was 1.9 Ib/hr and the initiator rate was 0.068 Ib/hr.
For Example 3, the PEG-MA feed rate was 3.1 Ib/hr and the initiator rate was 0.17 Ib/hr.
Referring to Figs. 2-4, the thermoplastic film of the invention exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
EXAMhLE 4 A 60/40 weight percent resin blend of low density polyethylene (Dow 5031) and polyethylene oxide) having a molecular weiglht of 100,000 g/mol (POLYOX~ WSRN-10) was fed to the ZSK-30 extruder at a rate of 35 Ib/hr. The seven heating zones were all set at 180°C. The screw speed was 300 rpm. A film of the melt blended resin exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
A resin blend having the specified ratio of low density polyethylene (Dow 5031) and polyethylene oxide) (POLYOX~ WSRN-80) was fed to a Haake extruder at 5.0 Ib/hr.
The Haake extruder was similar to that descrilbed above in the Comparative Example except the extruder included a two-hole strand die instead of the four inch slit die.
Simultaneously with the polymer feed to the extruder, specified amounts of the monomer, PEG-MA, and free radical initiator (Lupersol 101 ) were added at the feed throat. The extruder had four heating zones set at 170) 180, 180, and 190°C. The screw speed of the extruder was 150 rpm. The strands were cooled in air and pelletized.
For Example 5 the blend was 60/40 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 6 the blend was 65/35 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 7 the blend was 70/30 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
For Example 8 the blend was 75/25 PIJPEO, the PEG-MA feed rate was 0.50 Iblhr and the initiator rate was 0.025 Ib/hr.
For Example 9 the blend was 80/20 PIJPEO, the PEG-MA feed rate was 0.50 Ib/hr and the initiator rate was 0.025 Ib/hr.
The films of Examples 5-9 exhibited an inverse phase morphology having the polyethylene oxide) as the continuous phase and the polyethylene as the discontinuous phase.
For Example 5, the amount of monomer grafted onto the polyethylene oxide) was determined, by proton NMR spectroscopy in deuterated water, to be 9.52 weight percent based on the amount of polyethylene oxide) in the blend. The amount of unreacted monomer was determined, by proton nuclear magnetic resonance (NMR) spectroscopy in deuterated water, to be 2.02 weight percent based on the amount of polyethylene and polyethylene oxide) in the blend. The amount of monomer grafted onto the polyethylene was determined to be 0.51 weight percent by Fourier-Transform Infrared (FT-IR) and oxygen content analysis as described in copending U. S. patent application 08/733,410 filed October 18, 1996 the entire disclosure of which is incorporated herein by reference.
While the invention has been described with reference to a preferred embodiment those skilled in the art will appreciate that various substitutions) omissions, changes and modifications may be made without departing from the spirit hereof.
Accordingly, it is intended that the foregoing examples be deemed merely exemplary of the present invention an not be deemed a limitation thereof.
Claims (21)
1. A thermoplastic article comprising:
a) a polyolefin as a major constituent;
b) poly(ethylene oxide) as a minor constituent; and c) an amount of monomer grafted to said polyolefin and said poly(ethylene oxide) whereby said article exhibits an inverse phase morphology so that said minor constituent forms a continuous phase and said major constituent forms a dispersed phase in said thermoplastic article.
a) a polyolefin as a major constituent;
b) poly(ethylene oxide) as a minor constituent; and c) an amount of monomer grafted to said polyolefin and said poly(ethylene oxide) whereby said article exhibits an inverse phase morphology so that said minor constituent forms a continuous phase and said major constituent forms a dispersed phase in said thermoplastic article.
2. The thermoplastic article of claim 1 comprising from 55 weight percent to about 85 weight percent of said polyolefin and from about 45 weight percent to about 15 weight percent of said polyethylene oxide).
3. The thermoplastic article of claim 1 comprising from 60 weight percent to about 85 weight percent of said polyolefin and from about 40 weight percent to about 15 weight percent of said poly(ethylene oxide).
4. The thermoplastic article of claim 1 wherein said polyolefin is polyethylene.
5. The thermoplastic article of claim 1 wherein said polyolefin is polypropylene.
6. The thermoplastic article of claim 1 wherein said monomer is polyethylene glycol ethyl ether methacrylate.
7. The thermoplastic article of claim 1 wherein a total of about 0.1 weight percent to about 30 weight percent, based on the total amount of polyolefin and poly{ethylene oxide), of said monomer is grafted onto said polyolefin and said poly(ethylene oxide).
8. The thermoplastic article of claim 1 wherein a total of about 1 weight percent to about 20 weight percent, based on the total amount of polyolefin and polyethylene oxide), of said monomer is grafted onto said polyolefin and said poly(ethylene oxide).
9. The thermoplastic article of claim 1 wherein a total of about 1 weight percent to about 10 weight percent, based on the total amount of polyolefin and poly(ethylene oxide), of said monomer is grafted onto said polyolefin and said poly(ethylene oxide).
10. The thermoplastic article of claim 1 wherein said article is a film.
11. The thermoplastic film of claim 10 wherein the polyolefin in the dispersed phase has an average cross-sectional diameter of from about 0.1 microns to about 50 microns.
12. The thermoplastic film of claim 10 wherein the polyolefin in the dispersed phase has an average cross-sectional diameter of from about 0.5 microns to about 30 microns.
13. The thermoplastic film of claim 10 wherein the polyolefin in the dispersed phase has an average cross-sectional diameter of from about 0.5 microns to about 25 microns.
14. A thermoplastic film comprising:
a) polyethylene as a major constituent;
b) poly(ethylene oxide) as a minor constituent; and c) an amount of polyethylene glycol ethyl ether methacrylate grafted to said polyethylene and said poly(ethylene oxide) whereby said film exhibits an inverse phase morphology so that said poly(ethylene oxide) forms a continuous phase and said polyethylene forms a dispersed or discontinuous phase in said thermoplastic film.
a) polyethylene as a major constituent;
b) poly(ethylene oxide) as a minor constituent; and c) an amount of polyethylene glycol ethyl ether methacrylate grafted to said polyethylene and said poly(ethylene oxide) whereby said film exhibits an inverse phase morphology so that said poly(ethylene oxide) forms a continuous phase and said polyethylene forms a dispersed or discontinuous phase in said thermoplastic film.
15. The thermoplastic film of claim 14 comprising from 55 weight percent to about 85 weight percent of said polyolefin and from about 45 weight percent to about 15 weight percent of said poly(ethylene oxide).
16. The thermoplastic film of claim 14 comprising from 60 weight percent to about 85 weight percent of said polyolefin and from about 40 weight percent to about 15 weight percent of said poly(ethylene oxide).
17. The thermoplastic film of claim 14 wherein a total of about 0.1 weight percent to about 30 weight percent, based on the total amount of polyolefin and polyethylene oxide), of said monomer is grafted onto said polyolefin and said polyethylene oxide).
18. The thermoplastic film of claim 14 wherein a total of about 1 weight percent to about 20 weight percent, based on the total amount of polyolefin and polyethylene oxide), of said monomer is grafted onto said polyolefin and said poly(ethylene oxide).
19. The thermoplastic film of claim 14 wherein a total of about 1 weight percent to about 10 weight percent, based on the total amount of polyolefin and poly(ethylene oxide), of said monomer is grafted onto said polyolefin and said poly(ethylene oxide).
20. A thermoplastic film comprising:
a) from 55 weight percent to about 85 weight percent of polyethylene;
b) from about 45 weight percent to about 15 weight percent poly(ethylene oxide); and c) from about 0.1 weight percent to about 30 weight percent, based on the total amount of polyolefin and poly(ethylene oxide), of polyethylene glycol ethyl ether methacrylate grafted to said polyethylene and said poly(ethylene oxide) whereby said film exhibits an inverse phase morphology so that said poly(ethylene oxide) forms a continuous phase and said polyethylene forms a dispersed or discontinuous phase in said thermoplastic film.
a) from 55 weight percent to about 85 weight percent of polyethylene;
b) from about 45 weight percent to about 15 weight percent poly(ethylene oxide); and c) from about 0.1 weight percent to about 30 weight percent, based on the total amount of polyolefin and poly(ethylene oxide), of polyethylene glycol ethyl ether methacrylate grafted to said polyethylene and said poly(ethylene oxide) whereby said film exhibits an inverse phase morphology so that said poly(ethylene oxide) forms a continuous phase and said polyethylene forms a dispersed or discontinuous phase in said thermoplastic film.
21. The thermoplastic film of claim 20 wherein the polyethylene in the dispersed phase has an average cross-sectional diameter of from about 0.1 microns to about 50 microns.
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US08/855,324 US5912076A (en) | 1996-12-31 | 1997-05-13 | Blends of polyethylene and peo having inverse phase morphology and method of making the blends |
US08/855,324 | 1997-05-13 | ||
PCT/US1997/024245 WO1998029508A1 (en) | 1996-12-31 | 1997-12-19 | Blends of polyethylene and peo having inverse phase morphology and method of making the blends |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6100330A (en) | 1996-12-31 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Water-degradable film of monomer grafted to polyolefin and poly(ethylene oxide) |
US6111014A (en) | 1996-12-31 | 2000-08-29 | Kimberly-Clark Worldwide, Inc. | Film of monomer-grafted polyolefin and poly(ethylene oxide) |
US5912076A (en) * | 1996-12-31 | 1999-06-15 | Kimberly-Clark Worldwide, Inc. | Blends of polyethylene and peo having inverse phase morphology and method of making the blends |
AU2016899A (en) * | 1997-12-31 | 1999-07-19 | Kimberley-Clark Worldwide, Inc. | Flushable fiber compositions comprising modified polypropylene and modified poly(ethylene oxide) and process for making the same |
US6071451A (en) * | 1997-12-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Process for making a nonwoven, porous fabric from polymer composite materials |
US6372850B2 (en) | 1997-12-31 | 2002-04-16 | Kimberly-Clark Worldwide, Inc. | Melt processable poly (ethylene oxide) fibers |
US6090472A (en) * | 1997-12-31 | 2000-07-18 | Kimberly-Clark Worldwide, Inc. | Nonwoven, porous fabric produced from polymer composite materials |
US6160200A (en) | 1998-06-29 | 2000-12-12 | The Procter & Gamble Company | Directionally preferential waste passage member for use with disposable absorbent article |
AU1198000A (en) * | 1998-09-22 | 2000-04-10 | Zms, Llc | Near-net-shape polymerization process and materials suitable for use therewith |
EP1166156A1 (en) | 1999-03-16 | 2002-01-02 | Zms, Llc | Precision integral articles |
WO2000075228A1 (en) * | 1999-06-07 | 2000-12-14 | Kimberly-Clark Worldwide, Inc. | Inverse phase blends of poly(ethylene oxide) and polyolefin and reactive extrusion method of making inverse phase blends |
AU5897000A (en) * | 1999-06-29 | 2001-01-31 | Kimberly-Clark Worldwide, Inc. | Compositions comprising a blend of poly(ethylene oxide) and grafted polyolefin and method of making the same |
US6416690B1 (en) | 2000-02-16 | 2002-07-09 | Zms, Llc | Precision composite lens |
US6607819B2 (en) | 2000-12-28 | 2003-08-19 | Kimberly-Clark Worldwide, Inc. | Polymer/dispersed modifier compositions |
US6403706B1 (en) | 2000-12-28 | 2002-06-11 | Kimberly-Clark Worldwide, Inc. | Methods of making polymer/dispersed modifier compositions |
US6509419B1 (en) | 2001-07-12 | 2003-01-21 | Kimberly-Clark Worldwide, Inc. | Chemically modified polyethylene oxide compositions with improved environmental stability |
US6515075B1 (en) | 2001-07-12 | 2003-02-04 | Kimberly-Clark Worldwide, Inc. | Films, fibers and articles of chemically modified polyethylene oxide compositions with improved environmental stability and method of making same |
AU2002357177A1 (en) * | 2001-12-12 | 2003-06-23 | North Carolina State University | Methods of co2-assisted reactive extrusion |
US20050154128A1 (en) * | 2003-11-26 | 2005-07-14 | Kopchik Richard M. | Polyolefin composition having dispersed nanophase and method of preparation |
US20070197730A1 (en) * | 2003-11-26 | 2007-08-23 | Fina Technology, Inc. | Hydrophilic polypropylene compositions and methods of forming the same |
US8153730B2 (en) * | 2003-11-26 | 2012-04-10 | Fina Technology, Inc. | Polyolefin blends used as masterbatch concentrates |
JP2008090133A (en) | 2006-10-04 | 2008-04-17 | Konica Minolta Medical & Graphic Inc | Copolymer and heat developable photosensitive material containing the same |
JP5764561B2 (en) | 2009-09-14 | 2015-08-19 | ダウ グローバル テクノロジーズ エルエルシー | Polymers containing units derived from ethylene and siloxane |
JP5766702B2 (en) * | 2009-09-14 | 2015-08-19 | ダウ グローバル テクノロジーズ エルエルシー | Polymers containing units derived from ethylene and poly (alkoxide) |
WO2011032176A1 (en) | 2009-09-14 | 2011-03-17 | Dow Global Technologies Inc. | Polymers comprising units derived from ethylene and polyalkene |
CA2855876C (en) * | 2011-11-16 | 2020-03-31 | Chevron Phillips Chemical Company Lp | Low density polyethylene and metallocene-catalyzed linear low density polyethylene blend |
US8975305B2 (en) | 2012-02-10 | 2015-03-10 | Kimberly-Clark Worldwide, Inc. | Rigid renewable polyester compositions having a high impact strength and tensile elongation |
US11965083B2 (en) | 2013-06-12 | 2024-04-23 | Kimberly-Clark Worldwide, Inc. | Polyolefin material having a low density |
US11286362B2 (en) | 2013-06-12 | 2022-03-29 | Kimberly-Clark Worldwide, Inc. | Polymeric material for use in thermal insulation |
US10752745B2 (en) * | 2013-06-12 | 2020-08-25 | Kimberly-Clark Worldwide, Inc. | Polyolefin film for use in packaging |
CN105358107B (en) | 2013-06-12 | 2019-12-27 | 金伯利-克拉克环球有限公司 | Absorbent article comprising nonwoven web formed from porous polyolefin fibers |
WO2015187198A1 (en) | 2014-06-06 | 2015-12-10 | Kimberly-Clark Worldwide, Inc. | Hollow porous fibers |
BR112015029119B1 (en) | 2013-06-12 | 2021-06-22 | Kimberly-Clark Worldwide, Inc | POLYMERIC MATERIAL WITH MULTIMODAL PORE SIZE DISTRIBUTION |
SG11201510050QA (en) | 2013-06-12 | 2016-01-28 | Kimberly Clark Co | Pore initiation technique |
RU2016107779A (en) | 2013-08-09 | 2017-09-12 | Кимберли-Кларк Ворлдвайд, Инк. | POLYMER MATERIAL FOR THREE-DIMENSIONAL PRINTING |
BR112016028045A8 (en) | 2014-06-02 | 2021-05-04 | Anavo Tech Llc | modified biopolymers, and their production methods |
KR102330971B1 (en) | 2014-06-06 | 2021-11-25 | 킴벌리-클라크 월드와이드, 인크. | Thermoformed article formed from a porous polymeric sheet |
CN104130484B (en) * | 2014-06-27 | 2016-08-24 | 佛山市顺德区众锐塑料机械制造有限公司 | A kind of PE film packing material and preparation method thereof |
BR112017009619B1 (en) | 2014-11-26 | 2021-10-05 | Kimberly-Clark Worldwide, Inc. | POLYOLEFIN MATERIAL, FIBER, NON-WOVEN WEFT, ABSORBENT ARTICLE, AND METHOD FOR FORMATION OF A POLYOLEFIN MATERIAL |
BR112017015225B1 (en) | 2015-01-30 | 2022-07-12 | Kimberly-Clark Worldwide, Inc. | PACKAGING FOR ABSORBENT ARTICLE WITH NOISE REDUCTION |
GB2549059B (en) | 2015-01-30 | 2021-06-16 | Kimberly Clark Co | Film with reduced noise for use in an absorbent article |
MX2018006309A (en) | 2015-11-23 | 2019-09-04 | Tethis Inc | Coated particles and methods of making and using the same. |
JP7326814B2 (en) * | 2019-03-28 | 2023-08-16 | 凸版印刷株式会社 | Liquid-repellent film, liquid-repellent laminate and packaging material |
Family Cites Families (140)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE25880E (en) | 1958-03-26 | 1965-10-12 | Ethoxyline besin emulsions | |
FR1317598A (en) | 1961-03-13 | 1963-05-08 | ||
US3323978A (en) * | 1963-05-09 | 1967-06-06 | Phillips Petroleum Co | Artificial textile fibres and their production |
US3670731A (en) | 1966-05-20 | 1972-06-20 | Johnson & Johnson | Absorbent product containing a hydrocolloidal composition |
US3539666A (en) * | 1968-06-18 | 1970-11-10 | Grace W R & Co | Method for preparing a nonwoven fabriclike member |
BE754115A (en) | 1968-07-08 | 1971-01-29 | Dow Chemical Co | ALKYLENE OXIDE COPOLYMERS THAT MAY BE USED IN THE MANUFACTURE OF ELASTOMERIC ARTICLES |
GB1324781A (en) * | 1969-06-09 | 1973-07-25 | Union Carbide Corp | Polymer blends and their uses in the production of ultra fine fibres |
US3717541A (en) * | 1970-06-30 | 1973-02-20 | Grace W R & Co | Non-woven fabric-like member |
US3676529A (en) | 1970-07-24 | 1972-07-11 | Goodyear Tire & Rubber | Curable graft polymers of polyalkylene oxides |
US3954928A (en) * | 1970-07-28 | 1976-05-04 | Teijin Ltd. | Process for making sheet-formed reticulated fibrous structures |
US3666737A (en) | 1970-08-06 | 1972-05-30 | Goodyear Tire & Rubber | Method and process of preparing improved polyethers |
US3763277A (en) | 1971-07-01 | 1973-10-02 | Union Carbide Corp | Process for the preparation of inter-polymers of poly(ethylene oxide) |
US3734876A (en) | 1971-07-06 | 1973-05-22 | Union Carbide Corp | Cross-linked polyalkylene oxide |
BE789277A (en) * | 1971-09-27 | 1973-03-26 | Union Carbide Corp | COMPOSITION OF ETHYLENE POLYMER DEGRADABLE UNDER THE ACTION OF WEATHER |
US5480928A (en) | 1971-12-01 | 1996-01-02 | Union Carbide Chemicals & Plastics Technology Corporation | Preparation of stable dispersions of ethylene oxide polymers |
US3830888A (en) | 1972-04-03 | 1974-08-20 | Exxon Research Engineering Co | Compositions comprising a blend of a vinyl resin and grafted olefin polymer |
US3953655A (en) | 1972-04-03 | 1976-04-27 | Exxon Research And Engineering Company | Polymers with improved properties and process therefor |
US3867324A (en) | 1972-07-28 | 1975-02-18 | Union Carbide Corp | Environmentally degradable-biodegradable blend of an oxyalkanoyl polymer and an environmentally degradable ethylene polymer |
US4029720A (en) | 1972-08-10 | 1977-06-14 | Badische Anilin- & Soda-Fabrik Aktiengesellschaft | Block or graft copolymers of polyalkylene oxides and vinylaromatic or diene polymers |
DE2252508A1 (en) | 1972-10-26 | 1974-05-09 | Basf Ag | GROP COPOLYMERISATE BASED ON METHYL METHACRYLATE POLYMERISATE |
US3843589A (en) | 1973-02-05 | 1974-10-22 | Union Carbide Corp | Stable pumpable slurries of ethylene oxide polymers |
JPS521740B2 (en) * | 1973-04-06 | 1977-01-18 | ||
US3993551A (en) | 1973-09-10 | 1976-11-23 | Union Carbide Corporation | Process for cocrosslinking water soluble polymers and products thereof |
US3957605A (en) | 1973-09-10 | 1976-05-18 | Union Carbide Corporation | Process for radiation cocrosslinking water soluble polymers and products thereof |
US3891584A (en) | 1974-02-22 | 1975-06-24 | Nat Starch Chem Corp | Water-dispersible hot melt adhesives and products using same |
NL156425B (en) * | 1974-04-18 | 1978-04-17 | Kureha Chemical Ind Co Ltd | PROCESS FOR THE PREPARATION OF ENTCOPOLYMERS AND FORMED PRODUCTS, WHOLE OR PARTLY CONSISTING OF AN ENTCOPOLYMER, PREPARED IN ACCORDANCE WITH THIS PROCESS. |
FR2278348A2 (en) | 1974-06-28 | 1976-02-13 | Rhone Poulenc Ind | BIORESORBABLE SURGICAL ARTICLES |
US4018729A (en) * | 1974-10-01 | 1977-04-19 | Union Carbide Corporation | Shaped article for conditioning hair a blend of water-soluble and water-insoluble polymers with interpenetrating networks |
US3963805A (en) | 1974-10-30 | 1976-06-15 | Union Carbide Corporation | Water swellable poly(alkylene oxide) |
US3972961A (en) | 1974-11-13 | 1976-08-03 | E. I. Du Pont De Nemours And Company | Process for the preparation of graft copolymers |
DE2513251C3 (en) | 1975-03-26 | 1978-09-07 | Bayer Ag, 5090 Leverkusen | Process for the production of bifilar acrylic fibers |
US4225650A (en) | 1975-10-22 | 1980-09-30 | Exxon Research & Engineering Co. | Crosslinkable polymer powder and laminate |
FR2336422A1 (en) * | 1975-12-23 | 1977-07-22 | Ato Chimie | PROCESS FOR CHEMICAL MODIFICATION OF POLYOLEFINS WITH A VIEW TO IMPROVING THEIR WETABILITY |
CS194571B1 (en) | 1977-12-22 | 1979-12-31 | Bedrich Klabacka | Pencil-lead modificated by thermoplastic material |
US4186233A (en) * | 1978-03-27 | 1980-01-29 | The Dow Chemical Company | Disposable composite insensitive to surface moisture but disintegratable in aqueous liquid |
US4528334A (en) | 1978-11-24 | 1985-07-09 | Union Carbide Corporation | Carboxylated poly(oxyalkylenes) |
JPS592462B2 (en) | 1980-02-22 | 1984-01-18 | 呉羽化学工業株式会社 | Antistatic resin composition |
US4496619A (en) | 1981-04-01 | 1985-01-29 | Toray Industries, Inc. | Fabric composed of bundles of superfine filaments |
DE3220324C2 (en) | 1981-06-03 | 1994-02-03 | Daicel Chem | Mass containing polycaprolactone |
DE3277458D1 (en) | 1981-11-05 | 1987-11-19 | Takeo Saegusa | Polymer compositions |
DE3271192D1 (en) | 1981-11-23 | 1986-06-19 | Ici Plc | Process of melt spinning of a blend of a fibre-forming polymer and an immiscible polymer and melt spun fibres produced by such process |
US4594389A (en) | 1982-09-13 | 1986-06-10 | The Goodyear Tire & Rubber Company | Blends of higher α- olefin polymers and 1,2-epoxide polymers |
US4617235A (en) | 1983-05-23 | 1986-10-14 | Unitika Ltd. | Antistatic synthetic fibers |
JPS6021966A (en) | 1983-07-12 | 1985-02-04 | カネボウ株式会社 | Production of polishing fiber |
US4795668A (en) | 1983-10-11 | 1989-01-03 | Minnesota Mining And Manufacturing Company | Bicomponent fibers and webs made therefrom |
US4883699A (en) | 1984-09-21 | 1989-11-28 | Menlo Care, Inc. | Polymeric article having high tensile energy to break when hydrated |
SE444950B (en) | 1984-09-28 | 1986-05-20 | Ytkemiska Inst | COVERED ARTICLE, PROCEDURES AND METHODS OF PRODUCING THEREOF AND USING THEREOF |
US4725492A (en) | 1984-11-19 | 1988-02-16 | Mitsubishi Petrochemical Co., Ltd. | Composite heat-insulating material |
EP0183566B1 (en) | 1984-11-30 | 1992-04-01 | Mitsui Petrochemical Industries, Ltd. | Heat-fixable electrophotographic toner |
US4624051A (en) * | 1984-12-07 | 1986-11-25 | The Gillette Company | Shaving unit |
JPS61272217A (en) * | 1985-05-29 | 1986-12-02 | Ube Ind Ltd | Polyolefin resin composition |
US4868222A (en) * | 1985-06-10 | 1989-09-19 | The Dow Chemical Company | Preparation of asymmetric membranes by the solvent extraction of polymer components from polymer blends |
US4619988A (en) | 1985-06-26 | 1986-10-28 | Allied Corporation | High strength and high tensile modulus fibers or poly(ethylene oxide) |
US4705525A (en) | 1985-06-28 | 1987-11-10 | Ciba-Geigy Corporation | Water-soluble or water-dispersible graft polymers, process for their preparation and the use thereof |
US4743244A (en) | 1985-06-28 | 1988-05-10 | Arco Chemical Company | Water absorbing polymer compositions and articles prepared therefrom |
US4705526A (en) | 1985-07-18 | 1987-11-10 | Ciba-Geigy Corporation | Water-soluble or water-dispersible graft polymers and the preparation and use thereof |
US4874540A (en) | 1986-07-18 | 1989-10-17 | Ecolab Inc. | Graft copolymers of a polyether moiety on a polycarboxylate backbone |
US4857602A (en) | 1986-09-05 | 1989-08-15 | American Cyanamid Company | Bioabsorbable surgical suture coating |
JPS6399943A (en) | 1986-10-16 | 1988-05-02 | 三菱油化株式会社 | Thermoplastic resin laminate |
US5162074A (en) | 1987-10-02 | 1992-11-10 | Basf Corporation | Method of making plural component fibers |
JPH01246411A (en) * | 1988-03-25 | 1989-10-02 | Akio Sawashita | Alga-proof monofilament |
US5216050A (en) | 1988-08-08 | 1993-06-01 | Biopak Technology, Ltd. | Blends of polyactic acid |
JP2703971B2 (en) | 1989-01-27 | 1998-01-26 | チッソ株式会社 | Ultrafine composite fiber and its woven or nonwoven fabric |
DE3910563A1 (en) | 1989-04-01 | 1990-10-04 | Cassella Ag | HYDROPHILIC, SWELLABLE Graft Copolymers, THE PRODUCTION AND USE THEREOF |
DE3911433A1 (en) | 1989-04-07 | 1990-10-11 | Cassella Ag | HYDROPHILIC SWELLABLE GRAFT POLYMERISATES, THEIR PRODUCTION AND USE |
US5217495A (en) | 1989-05-10 | 1993-06-08 | United States Surgical Corporation | Synthetic semiabsorbable composite yarn |
GB8913743D0 (en) | 1989-06-15 | 1989-08-02 | Bicc Plc | Manufacture of extruded products |
WO1991000935A1 (en) | 1989-07-13 | 1991-01-24 | Mitsubishi Rayon Co., Ltd. | Porous fiber and production thereof |
US5360419A (en) | 1989-12-08 | 1994-11-01 | Kimberly-Clark Corporation | Absorbent structure possessing improved integrity |
EP0436966B1 (en) | 1990-01-09 | 2000-03-22 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Methods for manufacture of porous resin mouldings, ultrafine fibres and ultrafine fibre nonwoven fabrics |
US5407442A (en) | 1990-02-12 | 1995-04-18 | Karapasha; Nancy | Carbon-containing odor controlling compositions |
US5264491A (en) | 1990-03-22 | 1993-11-23 | Edison Polymer Innovation Corporation | Compatibilization of polymer blends |
US5097005A (en) | 1990-05-11 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Novel copolyesters and their use in compostable products such as disposable diapers |
US5219646A (en) | 1990-05-11 | 1993-06-15 | E. I. Du Pont De Nemours And Company | Polyester blends and their use in compostable products such as disposable diapers |
US5097004A (en) | 1990-05-11 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Novel polyesters and their use in compostable products such as disposable diapers |
DE4026719A1 (en) | 1990-08-24 | 1992-02-27 | Huels Chemische Werke Ag | MELT FLUFFICALLY APPLICABLE PROTECTION MEASURES |
CA2049271C (en) * | 1990-08-28 | 1998-05-05 | Roger L. Juhl | Transferable modifier containing film |
US5095619A (en) * | 1990-09-28 | 1992-03-17 | The Gillette Company | Shaving system |
EP0480643B1 (en) | 1990-10-10 | 1996-05-22 | Minnesota Mining And Manufacturing Company | Graft copolymers and graft copolymer/protein compositions |
CA2050021C (en) * | 1990-10-16 | 2002-07-02 | Kimberly-Clark Worldwide, Inc. | Environmentally friendly polymeric web compositions |
MX9101416A (en) | 1990-10-16 | 1994-05-31 | Kimberly Clark Co | ENVIRONMENTALLY FRIENDLY POLYMERIC FABRIC COMPOSITIONS. |
JPH04198275A (en) * | 1990-11-26 | 1992-07-17 | Nippon Petrochem Co Ltd | Thermoplastic resin composition having good moldability |
EP0503909A1 (en) * | 1991-03-14 | 1992-09-16 | Chevron Research And Technology Company | Substantially non-crosslinked maleic anhydride-modified ethylene polymers and process for preparing same |
EP0503608A1 (en) | 1991-03-14 | 1992-09-16 | National Starch and Chemical Investment Holding Corporation | Hot melt adhesive with wetness indicator |
DE69211745T2 (en) * | 1991-04-04 | 1997-02-20 | Nof Corp | Thermoplastic resin composition |
CA2065966A1 (en) * | 1991-04-23 | 1992-10-24 | Robert J. Petcavich | Disposable recyclable plastic articles and moldable synthetic resin blends for making the same |
AU666592B2 (en) * | 1991-04-23 | 1996-02-15 | Robert J. Petcavich | Disposable degradable recyclable plastic articles and synthetic resin blends for making the same |
US5217798A (en) | 1991-05-07 | 1993-06-08 | National Starch And Chemical Investment Holding Corporation | Water sensitive hot melt adhesives for nonwoven applications |
NZ242597A (en) * | 1991-05-14 | 1995-07-26 | Grace W R & Co | Co-extruded water soluble laminated polymeric film and methods of extruding it |
PL169131B1 (en) * | 1991-06-26 | 1996-06-28 | Procter & Gamble | Biodegradable moisture absorbing product |
US5260371A (en) | 1991-07-23 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for making melt stable ethylene vinyl alcohol polymer compositions |
JP2911657B2 (en) | 1991-08-22 | 1999-06-23 | 株式会社クラレ | High moisture-absorbing and water-absorbing ethylene-vinyl alcohol copolymer fiber and method for producing the same |
US5571878A (en) * | 1991-09-24 | 1996-11-05 | Chevron Chemical Company | Ethylene-alkyl acrylate copolymers and derivatives having improved melt-point temperatures and adhesive strength and processes for preparing same |
US5424380A (en) | 1991-10-31 | 1995-06-13 | Tosoh Corporation | Resin composition |
DE4139613A1 (en) | 1991-11-30 | 1993-06-03 | Cassella Ag | HYDROPHILIC SWELLABLE Graft Polymers |
EP0555197A3 (en) | 1992-01-29 | 1993-11-18 | Monsanto Co | Antistatic agent for thermoplastic polymers |
DE69325401T2 (en) | 1992-02-20 | 1999-11-25 | Du Pont | Water dispersions containing three-block polymer dispersants |
US5352515A (en) | 1992-03-02 | 1994-10-04 | American Cyanamid Company | Coating for tissue drag reduction |
DE69304576T2 (en) | 1992-03-25 | 1997-04-17 | Showa Denko Kk | Thermoplastic resin composition and color-coated molded article made therefrom |
US5209849A (en) | 1992-04-24 | 1993-05-11 | Gelman Sciences Inc. | Hydrophilic microporous polyolefin membrane |
DK0647142T3 (en) * | 1992-06-26 | 1999-06-14 | Procter & Gamble | Biodegradable liquid-impermeable monolayer film compositions |
AU681589B2 (en) * | 1992-06-26 | 1997-09-04 | Procter & Gamble Company, The | Biodegradable, liquid impervious multilayer film compositions |
CA2100419C (en) | 1992-07-21 | 1997-02-04 | Tadayuki Ohmae | Graft copolymer, process for production thereof, and plasticizer comprising said copolymer as active component |
US5369168A (en) * | 1992-08-03 | 1994-11-29 | Air Products And Chemicals, Inc. | Reactive melt extrusion grafting of thermoplastic polyvinyl alcohol/polyolefin blends |
US5382703A (en) | 1992-11-06 | 1995-01-17 | Kimberly-Clark Corporation | Electron beam-graftable compound and product from its use |
US5468259A (en) * | 1992-12-07 | 1995-11-21 | Sheth; Paresh J. | Dyeable polyolefin compositions and dyeing polyolefin compositions |
KR0120326B1 (en) | 1992-12-24 | 1997-10-22 | 김준웅 | Thermoplastic biodegrable, and aliphatic polyester and method of making the same |
EP0612773B1 (en) | 1993-02-26 | 1996-12-27 | Mitsubishi Chemical Corporation | Thermoplastic resin composition and process for preparing modified polyolefin type resin |
KR960015447B1 (en) | 1993-03-16 | 1996-11-14 | 주식회사 삼양사 | Biodegradable polymer |
US5366804A (en) | 1993-03-31 | 1994-11-22 | Basf Corporation | Composite fiber and microfibers made therefrom |
DE4312753A1 (en) * | 1993-04-20 | 1994-10-27 | Basf Ag | Use of polyacetals for the production of compostable moldings, as a coating agent and as an adhesive |
US5522841A (en) | 1993-05-27 | 1996-06-04 | United States Surgical Corporation | Absorbable block copolymers and surgical articles fabricated therefrom |
AT403695B (en) * | 1993-07-26 | 1998-04-27 | Danubia Petrochem Polymere | Blends made from elastomeric polypropylenes and from nonolefinic thermoplastics |
US5618911A (en) | 1993-08-19 | 1997-04-08 | Toyo Boseki Kabushiki Kaisha | Polymer containing lactic acid as its constituting unit and method for producing the same |
US5395308A (en) * | 1993-09-24 | 1995-03-07 | Kimberly-Clark Corporation | Thermoplastic applicator exhibiting accelerated breakup when immersed in water |
US5415905A (en) * | 1993-09-29 | 1995-05-16 | Exxon Chemical Patents Inc. | Dispersible film |
ATE174389T1 (en) | 1993-10-15 | 1998-12-15 | Kuraray Co | WATER-SOLUBLE, HOT-FELTED BINDING FIBERS MADE OF POLYVINYL ALCOHOL, NON-WOVEN MATERIALS CONTAINING THESE FIBERS AND METHOD FOR PRODUCING SUCH FIBER AND THIS NON-WOVEN MATERIAL |
WO1995011929A1 (en) * | 1993-10-27 | 1995-05-04 | Chevron Chemical Company | Low-haze ionomers of copolymers of alpha-olefins, carboxylic acid esters, and optional comonomers, and processes for making and acidifying these ionomers |
CA2128483C (en) * | 1993-12-16 | 2006-12-12 | Richard Swee-Chye Yeo | Flushable compositions |
US5498785A (en) * | 1994-01-14 | 1996-03-12 | Chevron Chemical Company | Continuous process for the aminolysis of ethylene copolymers |
AU703156B2 (en) * | 1994-01-28 | 1999-03-18 | Procter & Gamble Company, The | Biodegradable copolymers and plastic articles comprising biodegradable copolymers of 3-hydroxyhexanoate |
ID23491A (en) * | 1994-01-28 | 1995-09-07 | Procter & Gamble | COOPOLYMERS WHICH CAN BE DIODODEGRADED AND PLASTIC MATERIALS CONTAINED FROM CO-COLLIMERS WHICH CAN BE DIBIODEGRADED |
SG49096A1 (en) * | 1994-01-28 | 1998-05-18 | Procter & Gamble | Biodegradable 3-polyhydtoxybuyrate/3- polyhydroxyhexanoate copolymer films |
ZA95627B (en) * | 1994-01-28 | 1995-10-05 | Procter & Gamble | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
SG44660A1 (en) * | 1994-02-28 | 1997-12-19 | Procter & Gamble | Spray processes using a gaseous flow for preparing biodegradable fibrils nonwoven fabrics comprising biodegradable fibrils and articles comprising such nonwoven fabrics |
CA2186590C (en) * | 1994-02-28 | 2001-07-03 | Isao Noda | Stirring processes for preparing biodegradable fibrils |
KR0141431B1 (en) | 1994-05-17 | 1998-07-01 | 김상웅 | Biodegradable hydrogel copolymer |
US5549791A (en) * | 1994-06-15 | 1996-08-27 | The Procter & Gamble Company | Individualized cellulosic fibers crosslinked with polyacrylic acid polymers |
US5589545A (en) | 1994-07-18 | 1996-12-31 | Union Carbide Chemicals & Plastics Technology Corporation | Lubricious polymer blends comprising polyethylene oxide, polyethylene and a polylactone |
US5674578A (en) | 1994-12-27 | 1997-10-07 | Hollister Incorporated | Water soluble/dispersible multilayered film of high interlayer adhesive strength and collection pouches formed therefrom |
US5472518A (en) * | 1994-12-30 | 1995-12-05 | Minnesota Mining And Manufacturing Company | Method of disposal for dispersible compositions and articles |
DE19500426C1 (en) | 1995-01-10 | 1996-03-21 | Leuna Werke Gmbh | High-viscosity polypropylene (PP) graft copolymer prodn. |
US5759569A (en) * | 1995-01-10 | 1998-06-02 | The Procter & Gamble Company | Biodegradable articles made from certain trans-polymers and blends thereof with other biodegradable components |
GB2295553B (en) * | 1995-02-09 | 1997-05-21 | Ecoprogress Ltd | A water dispersible bodily liquid absorbent composite |
DE69612901T2 (en) | 1995-03-27 | 2001-09-20 | Mitsubishi Chem Corp | Process for the treatment of modified polymers |
US5750605A (en) | 1995-08-31 | 1998-05-12 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesives based on sulfonated polyesters |
US6087550A (en) | 1995-11-09 | 2000-07-11 | H. B. Fuller Licensing & Financing, Inc. | Non-woven application for water dispersable copolyester |
US5698322A (en) | 1996-12-02 | 1997-12-16 | Kimberly-Clark Worldwide, Inc. | Multicomponent fiber |
US5912076A (en) * | 1996-12-31 | 1999-06-15 | Kimberly-Clark Worldwide, Inc. | Blends of polyethylene and peo having inverse phase morphology and method of making the blends |
US5700872A (en) | 1996-12-31 | 1997-12-23 | Kimberly Clark Worlwide, Inc. | Process for making blends of polyolefin and poly(ethylene oxide) |
-
1997
- 1997-05-13 US US08/855,324 patent/US5912076A/en not_active Expired - Fee Related
- 1997-12-19 JP JP53034298A patent/JP2001507744A/en active Pending
- 1997-12-19 AU AU56245/98A patent/AU728926B2/en not_active Ceased
- 1997-12-19 KR KR10-1999-7005914A patent/KR100468345B1/en not_active IP Right Cessation
- 1997-12-19 IL IL13051497A patent/IL130514A0/en unknown
- 1997-12-19 WO PCT/US1997/024245 patent/WO1998029508A1/en active IP Right Grant
- 1997-12-19 EP EP97952694A patent/EP0951508B1/en not_active Expired - Lifetime
- 1997-12-19 CN CNB971818053A patent/CN1137207C/en not_active Expired - Fee Related
- 1997-12-19 DE DE69726011T patent/DE69726011T2/en not_active Expired - Fee Related
- 1997-12-19 CA CA002275386A patent/CA2275386A1/en not_active Abandoned
-
1999
- 1999-06-07 US US09/327,142 patent/US6214933B1/en not_active Expired - Fee Related
- 1999-06-11 US US09/330,583 patent/US6225406B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE69726011D1 (en) | 2003-12-11 |
AU728926B2 (en) | 2001-01-18 |
JP2001507744A (en) | 2001-06-12 |
AU5624598A (en) | 1998-07-31 |
US6225406B1 (en) | 2001-05-01 |
EP0951508B1 (en) | 2003-11-05 |
CN1137207C (en) | 2004-02-04 |
DE69726011T2 (en) | 2004-04-22 |
WO1998029508A1 (en) | 1998-07-09 |
KR100468345B1 (en) | 2005-01-27 |
US5912076A (en) | 1999-06-15 |
EP0951508A1 (en) | 1999-10-27 |
IL130514A0 (en) | 2001-04-30 |
KR20000069775A (en) | 2000-11-25 |
CN1246136A (en) | 2000-03-01 |
US6214933B1 (en) | 2001-04-10 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |