USH582H - Blends for making skin packaging films - Google Patents

Blends for making skin packaging films Download PDF

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Publication number
USH582H
USH582H US07/026,852 US2685287A USH582H US H582 H USH582 H US H582H US 2685287 A US2685287 A US 2685287A US H582 H USH582 H US H582H
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US
United States
Prior art keywords
blend
weight
ethylene
film made
density polyethylene
Prior art date
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Abandoned
Application number
US07/026,852
Inventor
John H. Tucker
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US07/026,852 priority Critical patent/USH582H/en
Assigned to E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE., A CORP OF DE reassignment E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, DE., A CORP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: TUCKER, JOHN H.
Priority to CA000561072A priority patent/CA1321437C/en
Application granted granted Critical
Publication of USH582H publication Critical patent/USH582H/en
Abandoned 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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

Definitions

  • This invention relates to blends of ethylene/carboxylic acid copolymers with high density polyethylene and inorganic fillers, which blends are useful for making films for skin packaging applications.
  • Skin packaging is a packaging method involving placing a product on a substrate material, such as paperboard, and draping heated plastic film over the product and substrate. A vacuum is then applied to draw the film down tightly to the board and around the product to make a secure and attractive package.
  • a substrate material such as paperboard
  • a vacuum is then applied to draw the film down tightly to the board and around the product to make a secure and attractive package.
  • One common application for skin packaging is industrial skin packaging used to protect products in transit. Products as divergent as computer tapes, lamps, service repair kits and table tops may be skin packaged instead of using die-cut corrugated, foam-in-place, foam peanuts and other stabilizing or dunnage materials. Skin packaging offers high throughputs and full visibility to check for tampering or missing components and also allows for quick identification, usually at significant cost reductions.
  • Low density polyethylene films are often used for skin packaging applications, but skin packaging films of ethylene/acid copolymers have been found to possess faster cycle times, better board adhesion, improved draw and better toughness than the low density polyethylene films. Oddly enough, one drawback of the ethylene/acid copolymer films is their relatively good optical properties since they more readily show the relatively unattractive packaging board used for the skin packaging of industrial items. Additionally, the industrial items themselves are often relatively unattractive. Thus, a method for affecting the optical properties of the ethylene/acid copolymer films, while not adversely affecting the desirable properties of such films, such as adhesion, was desired.
  • the ethylene/carboxylic acid copolymers which comprise the greatest part of the blends of this invention are copolymers of ethylene with an alpha, beta-ethylenically unsaturated carboxylic acid preferably having 3 to 8 carbon atoms.
  • acid monomers include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of said dicarboxylic acids, such as methyl hydrogen fumarate, ethyl hydrogen fumarate and maleic anhydride.
  • the concentration of acidic monomer in the copolymer is generally about 1 to 20 weight %, and preferably from about 3 to 15 weight %.
  • Preferred copolymers are copolymers of ethylene with methacrylic acid or acrylic acid, or terpolymers of ethylene, maleic anhydride and esters of acrylic acid such as ethyl acrylate.
  • the most preferred copolymer is a copolymer of ethylene with methacrylic acid, having an acid content of about 9 weight % and a melt index of about 1.5.
  • the particulate inorganic fillers useful in this invention are those fillers well known in the art for incorporation into films to improve handling characteristics.
  • the preferred filler is calcium carbonate, but examples of other fillers which may be utilized include, but are not limited to, mica, aluminum silicate, magnesium silicate, and barium sulfate.
  • the filler is quite uniform in size; e.g., for the preferred calcium carbonate filler, a particle distribution would preferably range from about 0.3 to 50 microns, and more preferably from about 0.3 to 20 microns.
  • the refractive index of the filler preferably differs from that of the ethylene/acid copolymer and the high density polyethylene used in the blend.
  • the preferred high density polyethylene is a linear ethylene homopolymer of medium molecular weight distribution having a melt index of about 1.1.
  • a preferred composition comprises about 82 to 94% by weight of ethylene/acid copolymer, about 5 to 15% by weight high density polyethylene, and about 1 to 3 weight % inorganic filler.
  • blends of this invention may be made and extruded into films by methods known in the art.
  • the following examples illustrate blends and films of this invention.
  • Component A 88% by weight of ethylene/methacrylic acid copolymer having 9% methacrylic acid, a Melt Index of 1.5
  • Component B 10% by weight of high density polyethylene hav:ng a Melt Index of 1.1
  • Component C 2% by weight calcium carbonate, 3-5 micron average particle size and extruded into films 4 and 6 mil thick. Control films extruded from Component A alone and from low density polyethylene (LDPE) alone were also prepared. Properties for these films are presented in the following table. A description of the tests used follows the table.
  • the data in the table indicate that the films prepared from the blends of this invention possessed superior physical properties and better adhesion to unprimed corrugated board than the film of low density polyethylene.
  • the films according to this invention when compared to films prepared from ethylene/acid copolymer alone (Component A), also possessed a slight increase in adhesion to primed corrugated board, a reduction in film heat-up time, and no adverse reduction in film physical propeties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

New blends of ethylene/carboxylic acid copolymers with high density polyethylene and inorganic fillers such as calcium carbonate are disclosed and are useful for making films for skin packaging applications.

Description

BACKGROUND OF THE INVENTION
This invention relates to blends of ethylene/carboxylic acid copolymers with high density polyethylene and inorganic fillers, which blends are useful for making films for skin packaging applications.
Skin packaging is a packaging method involving placing a product on a substrate material, such as paperboard, and draping heated plastic film over the product and substrate. A vacuum is then applied to draw the film down tightly to the board and around the product to make a secure and attractive package. One common application for skin packaging is industrial skin packaging used to protect products in transit. Products as divergent as computer tapes, lamps, service repair kits and table tops may be skin packaged instead of using die-cut corrugated, foam-in-place, foam peanuts and other stabilizing or dunnage materials. Skin packaging offers high throughputs and full visibility to check for tampering or missing components and also allows for quick identification, usually at significant cost reductions.
Low density polyethylene films are often used for skin packaging applications, but skin packaging films of ethylene/acid copolymers have been found to possess faster cycle times, better board adhesion, improved draw and better toughness than the low density polyethylene films. Oddly enough, one drawback of the ethylene/acid copolymer films is their relatively good optical properties since they more readily show the relatively unattractive packaging board used for the skin packaging of industrial items. Additionally, the industrial items themselves are often relatively unattractive. Thus, a method for affecting the optical properties of the ethylene/acid copolymer films, while not adversely affecting the desirable properties of such films, such as adhesion, was desired.
SUMMARY OF THE INVENTION
A method of modifying ethylene/acid copolymers by blending them with high density polyethylene and inorganic fillers has now been found which serves to degrade the optical properties of films made therefrom without degrading the adhesive and other desirable properties of such films. Surprisingly, this modification of the ethylene/acid copolymers leads to films which not only retain the adhesive properties of the unmodified copolymers, but in some cases leads to films with adhesive properties superior to that of the unmodified copolymers. Specifically, this invention relates to novel blends comprising:
(a) about 75 to 95.5% by weight of one or more ethylene/carboxylic acid copolymers;
(b) about 5 to 20% by weight of high density polyethylene; and
(c) about 0.5 to 5% by weight of a particulate inorganic filler, and to films made therefrom.
DETAILED DESCRIPTION OF THE INVENTION
The ethylene/carboxylic acid copolymers which comprise the greatest part of the blends of this invention are copolymers of ethylene with an alpha, beta-ethylenically unsaturated carboxylic acid preferably having 3 to 8 carbon atoms. Examples of acid monomers include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of said dicarboxylic acids, such as methyl hydrogen fumarate, ethyl hydrogen fumarate and maleic anhydride. The concentration of acidic monomer in the copolymer is generally about 1 to 20 weight %, and preferably from about 3 to 15 weight %. Preferred copolymers are copolymers of ethylene with methacrylic acid or acrylic acid, or terpolymers of ethylene, maleic anhydride and esters of acrylic acid such as ethyl acrylate. The most preferred copolymer is a copolymer of ethylene with methacrylic acid, having an acid content of about 9 weight % and a melt index of about 1.5.
The particulate inorganic fillers useful in this invention are those fillers well known in the art for incorporation into films to improve handling characteristics. The preferred filler is calcium carbonate, but examples of other fillers which may be utilized include, but are not limited to, mica, aluminum silicate, magnesium silicate, and barium sulfate. Preferably, so as not to adversely affect the quality of the film, the filler is quite uniform in size; e.g., for the preferred calcium carbonate filler, a particle distribution would preferably range from about 0.3 to 50 microns, and more preferably from about 0.3 to 20 microns. Also, when it is desired to degrade the optical properties of the film (e.g., increase haze or reduce transparency), the refractive index of the filler preferably differs from that of the ethylene/acid copolymer and the high density polyethylene used in the blend.
The preferred high density polyethylene is a linear ethylene homopolymer of medium molecular weight distribution having a melt index of about 1.1.
A preferred composition comprises about 82 to 94% by weight of ethylene/acid copolymer, about 5 to 15% by weight high density polyethylene, and about 1 to 3 weight % inorganic filler.
The blends of this invention may be made and extruded into films by methods known in the art. The following examples illustrate blends and films of this invention.
EXAMPLES
A blend was made incorporating the following:
Component A: 88% by weight of ethylene/methacrylic acid copolymer having 9% methacrylic acid, a Melt Index of 1.5
Component B: 10% by weight of high density polyethylene hav:ng a Melt Index of 1.1
Component C: 2% by weight calcium carbonate, 3-5 micron average particle size and extruded into films 4 and 6 mil thick. Control films extruded from Component A alone and from low density polyethylene (LDPE) alone were also prepared. Properties for these films are presented in the following table. A description of the tests used follows the table.
              TABLE                                                       
______________________________________                                    
Film Properties                                                           
             BLEND A BLEND A   A LDPE                                     
Film           4 mil  4 mil  6 mil                                        
                                  6 mil                                   
                                       5 mil                              
                                            5 mil                         
______________________________________                                    
ADH,PP COR (g/in.)                                                        
MD             729    681    873  736  771  811                           
TD             629    581    718  651  703  694                           
ADH,UPUP COR (g/in.)                                                      
MD             314    308    356  363  395  201                           
TD             333    296    364  349  411  218                           
TEMPERATURE, F.                                                           
               190    230    195  198  190  230                           
HEAT UP, sec.  17     18     16.5 17.5 17.3 30                            
HAZE           --     --     71   1.5  --   12.8                          
GLOSS          --     --     4    90   --   18                            
TRANSPARENCY   --     --     0.2  43        0.8                           
ELMENDORF (g/mil)                                                         
MD             --     --     209  224  --   84                            
TD             --     --     229  240  --   101                           
SPENCER IMPACT                                                            
(in-lbs/mil)   --     --     3.1  4.3  --   2                             
TENSILE (psi)                                                             
MD             --     --     3959 4331 --   2814                          
TD             --     --     3999 4266 --   2947                          
ELONGATION (%)                                                            
MD             --     --     512  536  --   540                           
TD             --     --     502  574  --   530                           
______________________________________                                    
 ADH,PP COR  Adhesion to primed printed corrugated board                  
 ADH,UPUP COR  Adhesion to unprimed unprinted corrugated board            
 TEMPERATURE  Amount of heat retained in the film as it contacts the board
 to activate the primer or adhesive on the board for good adhesion        
 HEAT UP  The optimum amount of time required to soften the film for skin 
 packaging, i.e., the amount of time required to "double drape" the film. 
 HAZE  ASTM D100361                                                       
 GLOSS  ASTM D245770                                                      
 TRANSPARENCY  ASTM D174670                                               
 ELMENDORF  ASTM D192267                                                  
 SPENCER IMPACT  ASTM D342085                                             
 TENSILE  ASTM D82283                                                     
 ELONGATION  ASTM D82283                                                  
 MELT INDEX  (Referred to elsewhere in this specification)  D1238
The data in the table indicate that the films prepared from the blends of this invention possessed superior physical properties and better adhesion to unprimed corrugated board than the film of low density polyethylene. The films according to this invention, when compared to films prepared from ethylene/acid copolymer alone (Component A), also possessed a slight increase in adhesion to primed corrugated board, a reduction in film heat-up time, and no adverse reduction in film physical propeties.

Claims (20)

What is claimed is:
1. A blend useful for extruding into skin packaging films comprising:
(a) about 75 to about 95.5% by weight of one or more ethylene/carboxylic acid copolymers;
(b) about 5 to about 20% by weight of high density polyethylene; and
(c) about 0.5 to 5% by weight of one or more particulate inorganic fillers.
2. A blend according to claim 1 where said ethylene/carboxylic acid copolymer is a copolymer of ethylene with methacrylic acid or acrylic acid having an acid content of about 3 to 15 weight %.
3. A blend according to claim 1 where said ethylene/carboxylic acid copolymer is a copolymer of ethylene with about 9 weight % methacrylic acid.
4. A blend according to claim 1 where said inorganic filler is calcium carbonate.
5. A blend according to claim 4 where said inorganic calcium carbonate has an average particle size of about 3 to 5 microns.
6. A blend according to claim 1 where said high density polyethylene has a melt index of about 1.1.
7. A blend according to claim 1 which comprises about 82 to 94% by weight of ethylene/acid copolymer, about 5 to 15% by weight high density polyethylene, and about 1 to 3% by weight inorganic filler.
8. A blend according to claim 1 where said ethylene/carboxylic acid copolymer is a copolymer of ethylene with methacrylic acid or acrylic acid having an acid content of about 3 to 15 weight %, said inorganic filler is calcium carbonate, and said high density polyethylene has a melt index of about 1.1.
9. A blend according to claim 8 which comprises about 82 to 94% by weight of said high density polyethylene, and about 1 to 3% by weight of said calcium carbonate.
10. A blend according to claim 9 which comprises about 88% by weight of ethylene/acid copolymer, about 10% by weight of high density polyethylene, and about 2% by weight of calcium carbonate.
11. A film made from the blend of claim 1.
12. A film made from the blend of claim 2.
13. A film made from the blend of claim 3.
14. A film made from the blend of claim 4.
15. A film made from the blend of claim 5.
16. A film made from the blend of claim 6.
17. A film made from the blend of claim 7.
18. A film made from the blend of claim 8.
19. A film made from the blend of claim 9.
20. A film made from the blend of claim 10.
US07/026,852 1987-03-17 1987-03-17 Blends for making skin packaging films Abandoned USH582H (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US07/026,852 USH582H (en) 1987-03-17 1987-03-17 Blends for making skin packaging films
CA000561072A CA1321437C (en) 1987-03-17 1988-03-10 Blends for making skin packaging films

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/026,852 USH582H (en) 1987-03-17 1987-03-17 Blends for making skin packaging films

Publications (1)

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USH582H true USH582H (en) 1989-02-07

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CA (1) CA1321437C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013329A1 (en) * 1993-11-10 1995-05-18 E.I. Du Pont De Nemours And Company Multi-phase film and methods relating thereto
US6162852A (en) * 1996-12-13 2000-12-19 Isolyser Company, Inc. Degradable polymers

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3365520A (en) 1965-05-27 1968-01-23 Union Carbide Corp Novel ethylene polymer compositions containing 1-olefin/carboxylic acid salt interpolymers
US3410928A (en) 1962-06-19 1968-11-12 Union Carbide Corp Blends of an olefin high polymer with an ethylene/acrylic acid copolymer
US3682767A (en) 1970-10-02 1972-08-08 Du Pont Ethylene copolymer blend for liquid packaging film
US3709957A (en) 1964-09-02 1973-01-09 Du Pont Polyethylene blends of ethylenemethacrylic acid copolymer and polyethylene
US3900635A (en) 1972-02-22 1975-08-19 Union Carbide Corp Multilayer shrinkable film for poultry bags
US4199491A (en) 1977-12-23 1980-04-22 Idemitsu Kosan Company Limited Polyolefin resin composition
US4331779A (en) 1979-02-22 1982-05-25 The Dow Chemical Co. Ethylenic polymer foams having improved dimensional stability
US4387188A (en) 1981-02-23 1983-06-07 E. I. Du Pont De Nemours And Company Molding resins based on blends of acid copolymer/linear polyolefin/reinforcing fiber
US4420580A (en) 1982-02-08 1983-12-13 The Dow Chemical Company Method for preparing filled polyolefin resins and the resin made therefrom
US4423164A (en) 1981-02-04 1983-12-27 Rami Bar Polymeric films for use in agriculture
DE3324830A1 (en) 1982-08-28 1984-03-01 Alkor GmbH Kunststoffe, 8000 München Cardboard provided with a polyolefin coating, preferably for files, ring binders and other organisational and office requisites

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410928A (en) 1962-06-19 1968-11-12 Union Carbide Corp Blends of an olefin high polymer with an ethylene/acrylic acid copolymer
US3709957A (en) 1964-09-02 1973-01-09 Du Pont Polyethylene blends of ethylenemethacrylic acid copolymer and polyethylene
US3365520A (en) 1965-05-27 1968-01-23 Union Carbide Corp Novel ethylene polymer compositions containing 1-olefin/carboxylic acid salt interpolymers
US3682767A (en) 1970-10-02 1972-08-08 Du Pont Ethylene copolymer blend for liquid packaging film
US3900635A (en) 1972-02-22 1975-08-19 Union Carbide Corp Multilayer shrinkable film for poultry bags
US4199491A (en) 1977-12-23 1980-04-22 Idemitsu Kosan Company Limited Polyolefin resin composition
US4331779A (en) 1979-02-22 1982-05-25 The Dow Chemical Co. Ethylenic polymer foams having improved dimensional stability
US4423164A (en) 1981-02-04 1983-12-27 Rami Bar Polymeric films for use in agriculture
US4387188A (en) 1981-02-23 1983-06-07 E. I. Du Pont De Nemours And Company Molding resins based on blends of acid copolymer/linear polyolefin/reinforcing fiber
US4420580A (en) 1982-02-08 1983-12-13 The Dow Chemical Company Method for preparing filled polyolefin resins and the resin made therefrom
DE3324830A1 (en) 1982-08-28 1984-03-01 Alkor GmbH Kunststoffe, 8000 München Cardboard provided with a polyolefin coating, preferably for files, ring binders and other organisational and office requisites

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Copy of Contract between Du Pont and Stone Container Corp. (and related papers).
Misc. Shipment or Return Order dated 3-11-86.
Notebook page by Tucker dated 3/3/86 titled "Melt Blend for Industrial Skin Pkg."

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013329A1 (en) * 1993-11-10 1995-05-18 E.I. Du Pont De Nemours And Company Multi-phase film and methods relating thereto
US6162852A (en) * 1996-12-13 2000-12-19 Isolyser Company, Inc. Degradable polymers
US20030144422A1 (en) * 1996-12-13 2003-07-31 Isolyser Company, Inc. Novel degradable polymers

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Publication number Publication date
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Owner name: E.I. DU PONT DE NEMOURS AND COMPANY, WILMINGTON, D

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TUCKER, JOHN H.;REEL/FRAME:004721/0254

Effective date: 19870312

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