U.S. patent number RE40,941 [Application Number 10/714,474] was granted by the patent office on 2009-10-20 for monolithic polymer composition having a releasing material.
This patent grant is currently assigned to CSP Technologies, Inc.. Invention is credited to Ihab Hekal.
United States Patent |
RE40,941 |
Hekal |
October 20, 2009 |
Monolithic polymer composition having a releasing material
Abstract
The present invention includes processes and resulting
structures for producing a modified polymer having interconnecting
channels. The interconnecting channels act as controlled
transmission passages through the polymer. A hydrophilic agent is
blended into the polymer so that it is distributed within the
polymer. In one embodiment, a releasing material is blended into
the polymer so that the releasing material is distributed within
the product. The product is solidified so that the hydrophilic
agent forms passages in the product through which a desired
composition is communicable to the releasing material that is
entrained within the product. The solidified product may be used to
form a desired shaped article such as plug type inserts and liners
for closed containers, or it may be formed into a film, sheet, bead
or pellet.
Inventors: |
Hekal; Ihab (Orange Park,
FL) |
Assignee: |
CSP Technologies, Inc.
(Amsterdam, NY)
|
Family
ID: |
27492166 |
Appl.
No.: |
10/714,474 |
Filed: |
November 13, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
09087830 |
May 29, 1998 |
6124006 |
|
|
|
08812315 |
Mar 5, 1997 |
6130263 |
|
|
|
08611298 |
Mar 5, 1996 |
5911937 |
|
|
|
08424996 |
Apr 19, 1995 |
|
|
|
Reissue of: |
09157032 |
Sep 18, 1998 |
06316520 |
Nov 13, 2001 |
|
|
Current U.S.
Class: |
523/102; 523/122;
523/132; 524/387; 524/503 |
Current CPC
Class: |
B01J
20/28014 (20130101); F26B 21/083 (20130101); B01J
20/28042 (20130101); B29C 45/16 (20130101); B65D
81/264 (20130101); B65D 81/266 (20130101); C08J
9/26 (20130101); C08L 23/02 (20130101); C08L
23/10 (20130101); C08L 69/00 (20130101); C08L
77/00 (20130101); B01J 20/28033 (20130101); C08L
23/02 (20130101); C08L 23/02 (20130101); C08L
23/02 (20130101); C08L 23/10 (20130101); C08L
69/00 (20130101); C08L 29/00 (20130101); C08L
77/00 (20130101); C08L 77/00 (20130101); C08L
77/00 (20130101); C08L 69/00 (20130101); C08L
71/00 (20130101); C08L 23/0861 (20130101); C08L
29/04 (20130101); C08L 71/02 (20130101); C08L
101/00 (20130101); C08L 2666/04 (20130101); C08L
2666/14 (20130101); C08L 2666/02 (20130101); C08L
2666/22 (20130101); C08L 2666/04 (20130101); C08L
2666/02 (20130101); C08L 2666/14 (20130101) |
Current International
Class: |
A61L
9/01 (20060101); A01N 25/00 (20060101) |
Field of
Search: |
;523/102,122,132
;524/387,503 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
4013799 |
|
Oct 1999 |
|
DE |
|
0172774 |
|
Feb 1986 |
|
EP |
|
0225593 |
|
Jun 1987 |
|
EP |
|
931087639 |
|
Sep 1993 |
|
EP |
|
0 824 480 |
|
Feb 1998 |
|
EP |
|
96/29603 |
|
Sep 1996 |
|
WO |
|
PCT/US97/03610 |
|
May 1997 |
|
WO |
|
PCT/WO97/27483 |
|
Jul 1997 |
|
WO |
|
PCT/WO97/32663 |
|
Sep 1997 |
|
WO |
|
WO 97/32663 |
|
Sep 1997 |
|
WO |
|
PCT/WO 98/39231 |
|
Sep 1998 |
|
WO |
|
WO 96/333108 |
|
Oct 1999 |
|
WO |
|
Other References
"SCI's Memorandum of Law in Support of it Motion for Summary
Judgment of Patent Invalidity", Sud-Chemie Inc.v. CSP Technologies,
Inc., dated Oct. 24, 2004, 42pgs. cited by other .
13p--Sep. 29, 2004--CSP Technologies Inc. 's Corrected First
Supplemental Response To Interrogatory No. 5. cited by other .
Consent Judgment And Dismissal With Prejudice Feb. 9, 2007--4pgs.
cited by other .
Counterclaims Of Defendant CSP Technologies, Inc. dated Apr. 20,
2005--10 Pgs. cited by other .
Cover Sheet For The Deposition and Deposition Of Ihab Hekal Sep.
24, 2004--90pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Klaus
Langer Apr. 26, 2006--78 pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Barry
Schindler Jul. 7, 2004--121pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of David
Holbrook Dec. 3, 2004 85pgs. cited by other .
Cover Sheet For The Deposition Designation Of Didier Lancesseur
Apr. 25, 2006 84pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition of Didier
Lancesseur Oct. 28, 2004--85pgs. cited by other .
Cover Sheet For The Deposition and Deposition Of Edith Mathiowitz
Oct. 29, 2004--152pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Eric
Judek Dec. 21, 2004--122pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Ihab
Hekal Sep. 23, 2004--147pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of
Jonathan Freedman Jul. 13, 2004--77pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of
Jonathan Freedman Jul. 13, 2004--71pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Klaus
Langer--Oct. 27, 2004--93pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Klaus
Langer--Oct. 28, 2004--57pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Peter
Sagona--Sep. 23, 2004--79pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Pierre
Rousseau--Dec. 1, 2004--51pgs. cited by other .
Cover Sheet For The Deposition Of Robert Garren--Jul. 8,
2004--135pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of Sumeet
Kumar--Sep. 8, 2004--35pgs. cited by other .
Cover Sheet For The Deposition Designation and Deposition Of
William Spano Oct. 11, 2005--123 pgs. cited by other .
CSP Technologies Inc.'s Reply In Support Of Its Motion For Partial
Summary Judgment Of Infringement And Ex. A, B, D, E, F, G dated
Dec. 2, 2005 19 pgs. cited by other .
CSP Technologies Memorandum In Support Of Its Motion For Partial
Summary Judgment Of Infringement dated Oct. 21, 2005 22 pgs. cited
by other .
CSP Technologies, Inc.'s Memorandum in Support of Its Motion for
Partial Summary Judgment of Infringement, dated Oct. 21, 2005,
22pgs. and Exhibits 2, 3, 4, 5, 8, 12, 13. cited by other .
CSP Technologies, Inc.'s Opposition to Sud-Chemie, Inc.'s Second
Motion for Summary Judgment of Patent Invalidity and SCI's New
Untimely Defenses and Declaration and Exhibits 1-4, 6, 7, 9, 10,
12-15, dated Nov. 17, 2005--30 pgs. and Exhibits 1, 6, 7, 8, 11,
12, 13, 15. cited by other .
CSP Technologies, Inc. 's Proposed Findings Of Fact And Conclusions
Of Law, dated Jun. 21, 2006 52pgs. cited by other .
CSP Technologies, Inc.'s Reply in Support of Its Motion for Partial
Summary Judgement of Infringement and Exhibit A, B, D, E, F, G
dated Dec. 2, 2005--19pgs and Exhibit C. cited by other .
CSP Technologies' Answer, Affirmative Defenses And Counterclaims To
Sud-Chemie Inc.'s Second Amended Complaint dated May 2,
2005--83pgs. cited by other .
CSP's Opposition To SCI's Motion For Reconsideration dated Sep. 18,
2006 6pgs. cited by other .
CSP's Response To SCI's Post-Trial Reply Brief dated Aug. 8, 2006,
4pgs. cited by other .
CSP's Response To SCI's Trial Brief And Proposed Findngs Of Fact
And Conclusions Of Law, dated Jul. 17, 2006 29 pgs. cited by other
.
CSP's Second Supplemental Objections And Responses To SCI's Second
Set Of Interrogatory (No. 6) dated Dec. 3, 2004 6pgs. cited by
other .
CSP's Sur-Reply to SCI's Second Motion for Summary Judgment of
Invalidity, dated Dec. 16, 2005 11pgs. cited by other .
CSP's Trial Brief, dated Jun. 21, 2006, 60pgs. cited by other .
CV Of Donald R. Paul 37pgs May 17, 2005. cited by other .
Declaration of Donald R. Paul, PhD, In Support of SCI's Second
Motion for Summary Judgment of Non-Infringement, 4pgs Oct. 25,
2004. cited by other .
Declaration Of Jean Pierre Giraud 4pgs Jul. 6, 2005. cited by other
.
Deposition Of Glenn H. Fredrickson dated Aug. 24, 2005 10pgs. cited
by other .
Deposition Transcript of Donald Paul, PhD Sep. 8, 2005--7pgs. cited
by other .
Deposition Transcript of Robert Abrams, Nov. 17, 2004. cited by
other .
Deposition Transcript Of Sherman David Winters dated Sep. 7, 2005.
cited by other .
Entry On Claim Construction dated Mar. 14, 2005. cited by other
.
Expert Report Of Christopher W. Macosko Dated May 20, 2005 155 Pgs.
cited by other .
Expert Report of Donald R. Paul, PhD, on behalf of Plaintiff
Sud-Chemie Inc. Pursuant to Fed.R.Civ.Pro.26(a)(2)(B), 4pgs dated
May 20, 2005. cited by other .
First Supplemental Expert Report Of Christopher W. Macosko 51pgs
Aug. 22, 2005. cited by other .
Frederickson et al., "Project on Morphology Control in
Polymer-Polymer-Particle Alloys" undated, 2 pgs Mar. 2000. cited by
other .
Fredrickson, "A New Method For Stabilizing Co-Continuous Polymer
Blend Morphologies", For Capitol Specialty Plastics, 21 Pgs Mar.
2000. cited by other .
Galloway, Et Al., "Comparison Of Method For The Detection Of
Co-continuity In Poly (Ethylene Oxide)/ Polystyrene Blends",
Polymer Engineering And Science, Apr. 2004, vol. 44, No. 4, Pgs 15
pgs. cited by other .
Giles, David, "Differential Scanning Calorimetry (DSC) tests done
at the University of Minnesota" results for CSP Technologies, Inc.
May 20, 2005, 8pgs. cited by other .
Karger Et Al., "Intracrystalline Self-Diffusion Of Water And
Short-Chain-Length Paraffins In A-Type Zeolites", Zeolites, vol. 9,
May 1989, 3pgs. cited by other .
Letters To The Editor, Journal Of Colloid And Interface Sciences,
vol. 44, No. 1, Jul. 1973 "Self-Diffusion Measurement Of Water
Adsorbed In Any Zeolite By Means OF NMR Pulsed Field Gradient
Techniques", 2pgs. cited by other .
Massey, "Permeability Properties Of Plastics And Elastomers, A
Guide To Packaging And Barrier Materials", 2nd Ed., 2003, Plastics
Design Library, 6pgs. cited by other .
Mathiowitz Et Al., "Novel Desiccants Based On Designed Polymeric
Blends", Journal Of Applied Polymer Science, vol. 80, 317-327 2001.
cited by other .
MVTR Analysis of SCI Samples, Mocon Testing Services, Mar. 23,
2005, including "Standard Test Method for Water Vapor Transmission
Rate Through Plastic Film and Sheeting Using a Modulated Infrared
Sensor" ASTM International, 8pgs. cited by other .
Nago et al., "Microporous Polypropylene Sheets Containing Caco3
Filter : Effects Of Stretching Ratio And Removing Caco3 Filler",
Tokuyama Corp. Dec. 3, 1996. cited by other .
Official Reporters Transcript Of Markman Hearing--105pgs Mar. 4,
2004. cited by other .
Order Declaring The Defendant's Patents Valid And Infringed By Aug.
4, 2006. cited by other .
Plaintiff Sud-Chemie Inc.'s Reply To The Second Amended May 2,
2005. cited by other .
Plaintiff Sud-Chemie Inc.'s Reply To The Third Amended
Counterclaims Of Defendant CSP Technologies, Inc. dated May 2,
2005--16pg. cited by other .
Plaintiff, Aug. 4, 2006--108 pgs. cited by other .
Potschke Et Al., "Formation Of Co-Continuous Structures In
Melt-Mixed Immiscible Polymer Blends", Journal Of Molecular
Science, Part C--Polymer Reviews, vol. 43, No. 1, pp. 87-141, 2003.
cited by other .
Provisional Application for "Absorbent Polymeric Composition",
Certificate of Express Mail, Provisional Application Transmittal
Sheet, 20 pgs. Specification, 7 sheets drawings, 2 postcards Apr.
22, 2002. cited by other .
Rebuttal Of Expert Report Of Christopher W. Macosko, Jul. 7, 2005,
147 Pgs. cited by other .
SCI's Brief in Opposition to CSP's Motion for Partial Summary
Judgement of Infringement, dated Nov. 17, 2005--26pgs and Exhibits
2, 4, 5, 6, 9. cited by other .
SCI's Fourth Supplemental Objections and Responses to CSP's First
Set of Interrogatories Nos. 1-11, 85pgs, Oct. 21, 2004. cited by
other .
SCI's Objections And Responses To CSP's First Set Of Requests For
Admissions Nos. 1-26--Oct. 21, 2004--11pgs. cited by other .
SCI's Objections And Responses To CSP's Second Set Of
Interogatories Nos. 12-23 dated Dec. 3, 2004 24pgs. cited by other
.
SCI's Opposition To CSP's Motion For Leave To File A Response To
SCI's Post-Trial Reply Brief dated Aug. 15, 2006--6pgs, Ex. C Parts
1-8, Attachment A, Attachment B, Attachment D. cited by other .
SCI's Opposition To CSP's Motion For Leave To File A Response To
SCI's Post-Trial Reply Brief, 6pgs, Exhibits A, B, C (Parts 1-9)
and D dated **, ***pgs. cited by other .
SCI's Post-Trial Brief, dated Jun. 26, 2006 60pgs. cited by other
.
CSP Technologies, Inc. Drug Master File No. 14789 Feb. 3, 2003
66pgs. cited by other .
CSP's Responses to SCI's Third Set of Interrogatories (Nos. 7-11)
Mar. 31, 2004. cited by other .
CV of Edith Mathiowitz Jun. 19, 1998. cited by other .
USPTO File Wrapper of US Publication No. 2005/0089687--211 pgs.
Dec. 24, 2002. cited by other .
SCI's Opposition to CSP's Motion in Limine to Exclude SCI's
Allegedly Untimely Expert Reports Apr. 6, 2006 12 pgs. cited by
other .
SCI's Post-Trial Reply, dated Jul. 17, 2006 27pgs. cited by other
.
SCI's Proposed Findings Of Fact And Conclusions Of Law, dated Jun.
21, 2006 80 pgs. cited by other .
SCI's Reply Brief in Support of its Motion for Summary Judgment of
Patent Invalidity, dated Dec. 2, 2005--30 pgs. cited by other .
SCI's Second Memorandum of Law in Support of its Motion for Summary
Judgment of Patent Invalidity, dated Oct. 21, 2005--42pgs with
Exhibits 3, 4, 5, 6, 7, 8, 9, 10, 21, 22, 25, 36, 38, 40, 41, 52,
53, 54, 55, 56. cited by other .
SCI's Sixth Supplemental Objections And Responses To CSP's First
Set Of Interrogatories Nos. 1-11 dated May 3, 2005 95pgs. cited by
other .
Sud-Chemie Inc.'s Motion For Reconsideration Of Portions Of The
Order Declaring The Defendant's Patents Valid And Infringed By
Plaintiff dated Sep. 6, 2006 17pgs--Exhibits A, B, C. cited by
other .
Sud-Chemie Inc.'s Second Amended Complaint, 25 Pgs With Exhibit
A--U.S. Pat. No. 5,911,937--Hekal--16pgs, Exhibit AA, Exhibit B,
Exhibit C, Exhibit D, Exhibit D, Exhibit G, Exhibit H, Exhibit I
and Exhibit M. cited by other .
Trial Transcript May 15, 2006 48pgs. cited by other .
Trial Transcripts May 16, 2006 48pgs. cited by other .
Trial Transcript May 17, 2006 47pgs. cited by other .
Trial Transcripts May 18, 2006 53pgs. cited by other .
Trial Transcripts May 19, 2006 42pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Pat. 6,124,006 Issued Sep.
26, 2000, 146Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Pat. 6,177,183 Issued Jan.
23, 2000, 246 Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Pat. 6,194,079 Issued Feb.
27, 2001, 254 Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Pat. 6,214,255 Issued Apr.
10, 2001, 160 Pgs. cited by other .
U.S. Patent Office Wrapper, U.S. Pat. 6,488,231 Issued Nov. 26,
2002, 121 Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Appl. No. 08/161,298 Filed
Mar. 5, 1996--193 Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S.Appl. No. 08/424,996 Filed
Apr. 19, 1995--317 Pgs. cited by other .
U.S. Patent Office File Wrapper, U.S. Appl. 09/086,880, Filed May
29, 1990, 143 Pgs. cited by other .
U.S. Patent Office Technology Fair, Jul. 27, 2000, Patent Center
1700, Presentation Abstracts and Presenter Biographies, 28pgs.
cited by other .
US Patent Application Specification For "Desiccant Blended In A
Thermoplastic", Inventor Ihab Hekal, Filed Jun. 4, 1998, U.S. Appl.
No. 09/090,635, 22 Pgs. cited by other .
US Patent Office File Wrapper, US Pat. 6,130,263 Issued Oct. 26,
2000 200Pgs. cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Fifth
Supplemental Objections And Responses To CSP's First Set Of
Interrogatories Nos. 1-11", (Pp. 1-70). cited by other .
(Attachment: "The Prior Art Invalidates The Asserted Claims") (Pp.
1-15). cited by other .
Sud-Chemie, Inc.vs. CSP Technologies, Inc.: "CSP's Supplemental
Responses To SCI'S First Set Of Interrogatories Nos. 1-4", (Pp.
1-8). cited by other .
(Attachment: "Exhibit A"--Chart Comparing U.S. Patent No.
5,911,937, 6,124,006 and 6,214,255 to "SCI Infringing Product").
cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Second
Supplemental Responses To SCI's First Set Of Interrogatories Nos.
1-4", (Pp. 1-14). cited by other .
(Attachment: "Exhibit A" --A Letter From Kevin W. McCabe to
Margaret M. Duncan, Esq., "Exhibit B"-Dictionary (P. 847), "Exhibit
C"-Dictionary (Pp. 756). cited by other .
"Exhibit D"Dictionary (P. 1305), "Exhibit E" (P. 1250), "Exhibit
G"-Chart Comparing U.S. Patent No. 5,911,937, 6,124,006 and
6,214,255 to "SCI Infringing Product"). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Third
Supplemental Responses To SCI's First Set Of Interrogatories Nos.
1-4", (Pp. 1-18). cited by other .
(Attachment: "Exhibit A"-Letter From Kevin W. McCabe to Margaret M.
Duncan, Esq., "Exhibit B"-Dictionary (P. 22), "Exhibit
C"-Dictionary (P. 847). cited by other .
"Exhibit D"--Dictionary (P. 756), "Exhibit S"-Dictionary (P. 921),
"Exhibit F"-Dictionary (P. 1305), "Exhibit G"-Dictionary (P. 1250),
"Exhibit H"-Dictionary (P. 1251). cited by other .
"Exhibit I"-Chart Comparing U.S. Patent No. 5,911,937, 6,124,006
and 6,214,255 to "SCI Infringing Product" ). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP'S Fourth
Supplemental Responses To SCI's First Set of Interrogatories Nos.
1-4", (Pp. 1-15). cited by other .
Sud-Chemie, Inc .vs. CSP Technologies, Inc.: "CSP's Objections and
Responses to SCI's Second Set of Interrogatories Nos. 5-6", (Pp.
1-6). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Supplemental
Responses To SCI's Second Set Of Interrogatories Nos. 5 and 6",
(Pp. 1-5). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Responses To
SCI's Third Set of Interrogatories Nos. 7-11", (Pp. 1-9). cited by
other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP'S Objections And
Responses To SCI's Fourth Set of Interrogatories" (Pp. 1-8). cited
by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: CSP Technologies'
First Supplemental Response to Interrogatory No. 5 (Pp. 1-11).
cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP
Technologies'Corrected First Supplemental Response to Interrogatory
No. 5", (pp. 1-11). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Answers To
Plaintiff SCi'S First Set Of Requests for Admission", (Pp. 1-3).
cited by other .
(Attachment: "CSP's Objections and Responses to SCI's Second Set of
Requests for Admission" (Pp. 1-4) With Attachment.) cited by other
.
Sud-Chemie, Inc. vs.CSP Technologies, Inc.: "SCI's Third
Supplemental Objections and Responses to CSP'S First Set of
Interrogatories Nos. 1-11", (Pp. 1-63). cited by other .
(Attachment: "The Prior Art Invalidates The Asserted Claims") (Pp.
1-13). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Complaint For
Declaratory Judgment". (Pp. 1-5). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: Declaration Of Robert
S. Abrams In Support Of CSP Technologies, Inc.'s Motion To Dismiss
Or Transfer Sud-Chemie's. cited by other .
Declaratory Judgment Action, (Pp. 1-5). cited by other .
(Attachment: "Exhibit 1"--Letter From Klaus Langer to Robert S.
Abrams, "2"--Letter From Robert S. Abrams Klaus Langer). cited by
other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: CSP Technologies,
Inc.'s Memorandum of Points and Authorities in Support of Its
Motion to Dismiss or Transfer. cited by other .
Sud-Chemie's Declaratory Judgment Action , (pp. 1-23). cited by
other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Sud-Chemie, Inc.'s
First Amended Complaint", (pp. 1-7). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Consented to Motion
for Leave to Withdraw the Defendants Motion to Dismiss
or-Transfer", (pp. 1-3). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Answer and Counter
Claims of Defendant and Counterclaim Plaintiff CSP Technologies,
Inc.", (pp. 1-13). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Joint Proposed Case
Management Plan", (pp. 1-21). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc., Plaintiff Sud-Chemie,
Inc.'s Reply to the Counterclaims of Defendant CSP Technologies,
Inc. , (pp. 1-6). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Motion for
Leave to Amend its Answer and Counterclaims", (pp. 1-8). cited by
other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: CSP Technologies'
Motion to Dismiss Sud-Chemie's Declaratory Judgement Action for
Lack of a Justiciable Controversy as to certain patents and
Products, (pp. 1-3). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP
Technologies'Motion For Judgement On The Pleading Dismissing
Sud-Chemie's Amended Third Count For Inequitable Conbuct". (Pp.
1-6). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP Technologies
Memorandum In Support of its Motion to Dismiss Sud-Chemies
Declaratory Judgment Action for Lack of a Justiciable Controversy
as to Certain Patents and Products", (pp. 1-15). cited by other
.
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Opposition To
CSP's Motion for Leave to Amend its Answer And Counterclaims", (pp.
1-4). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Opposition To
CSP's Motion for Judgement on the Pleadings" (pp. 1-12). cited by
other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Opening Brief
on Claim Construction", (pp. 1-30). cited by other .
Sud-Chemine, Inc. vs. CSP Technologies, Inc.: "Plaintiff SCI's
Brief on The Construction of the '937, '006, and '255 Patents",
(pp. 1-29). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: CSP Technologies'Reply
in Support of its Motion for Leave to Amend its Answer and
Counterclaims , (pp. 1-4). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc."CSP Technologies' Reply
in Support of its Motion for Judgement on the Pleadings Dismissing
Sud-Chemie's Amended Third-Count for Inequitable Conduct", (pp.
1-9). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.L CSP Technologies'Reply
in Support of Its Motion to Dismiss Sud-Chemie's Declaratory
Judgment Action as to Certain Patents and Products , (pp. 1-15).
cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Opposition to
CSP's Reply in Support of Its Motion for Leave to Amend Its Answer
and Counterclaims", (pp. 1-8). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Plaintiff SCI's Reply
Breif on the Construction of the '937, '006, And '255 Patents",
(pp. 1-22). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Response To
SCI's Breif on Claim Construction", (pp. 1-36). cited by other
.
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Plaintiff's Motion
for Summary Judgment of No Literal Infringement", (pp. 1-12). cited
by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Plaintiff SCI's Breif
in Support of Its Motion for Summary Judgment of No Literal
Infrigement", (pp. 1-12). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Official Reporter's
Transcript Of Markman Hearing", (pp. 1-106). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP Technologies'
Breif In Opposition to SCI's Motion for Summary Judgement of No
Literal Infringement", (pp. 1-18). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Declaration of
Christopher W. Macosko", (pp. 1-8). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "Second Declaration of
Christopher W. Macosko", (pp. 1-6). cited by other .
Sud-Chemie, Inc . vs. CSP Technologies, Inc.: SCI's Sur-Reply Brief
Regarding SCI's Motion for Summary Judgment of No Literal
Infringement , (pp. 1-5). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Motion to
Dismiss All Claims Relating to U.S. Patent No. 6,124,006 for Lack
of a Justiciable Controversy", (pp. 1-3). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: CSP's Memorandum in
Support of Its Motion to Dismiss All Claims Relating to U.S. Patent
No. 6,124,006 for Lack of a Justicable-Controversy (pp. 1-4). cited
by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Opposition to
CSP's Motion to Dismiss All Claims Relating To U.S. Pat. No.
6,124,006 for Lack of a Justiciable-Controversy and SCI's
Cross-Motion in Limine Regarding the Presumtion of Validity", (pp.
1-11). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Reply in
Support of Its Motion to Dismiss All Claims Relating To U.S. Patent
No. 6,124,006 for Lack of a Justiciable-Controversy and CSP's
Opposition To SCI's Cross-Motion in Limine Regarding the Presumtion
Of Validity", (pp. 1-13). cited by other .
Sud-Chemie, Inc .vs. CSP Technologies, Inc.: "SCI's Reply Brief in
Support of Its Motion for Summary Judgement of No Literal
Infringement", (pp. 1-21). cited by other .
Sud-Chemie, Inc .vs. CSP Technologies, Inc.: "CSP Technologies'
Surreply in Opposition to SCI's Motion for Summary Judgment of No
Literal Infringement", (pp. 1-17). cited by other .
Sud-Chemie,Inc. vs. SCP Technologies, Inc.: "SCI's Memorandum of
Law in Support of Its Motion for Summary Judgment of Patent
Invalidty", (pp. 1-35) (With Attachment Cited Below). cited by
other .
(Attachment No. 1:Sud-Chemie, Inc. vs. CSP Technologies, Inc.:
"CSP's Fourth Supplemental Responses to SCI's First Set-of
Interrogatories Nos. 1-4") (pp. 1-15) With Attachment). cited by
other .
( Attachment No. 2: Hekal, "United States Patent No. 5,911,937").
cited by other .
(Attachment No. 3: Hekal, "United States Patent No. 6,124,006").
cited by other .
(Attachment No. 4: Sud-Chemie, Inc. Vs. CSP Technologies, Inc.:
"CSP's Answers To Plaintiff First Set Of Requests For Admission",
(pp. 1-4). cited by other .
(Attachment No. 5: Sud-Chemie, Inc. Vs. CSp Technologies, Inc.:
"CSP's Responses to SCI's Third Set Of Interrogatories Nos. 7-11",
(Pp. 1-9). cited by other .
(Attachment No. 6: Sud-Chemie, Inc. Vs. CSP Technologies, Inc.:
"Declaration Of Professor Donald R. Paul In Support Of SCI's Motion
For Summary Judment Of-Patent Invalidity", (pp. 1-6). cited by
other .
(Attachment No. 7: Sud-Chemie, Inc. Vs. CSP Technologies, Inc.:
"Deposition Transcript Of Ihab Hekal"(Sep. 24, 2004) (7 Pages).
cited by other .
(Attachment No. 8: "Hekal, United States Patent No. 6,130,263").
cited by other .
(Attachment No. 9: "Hekal,United States Patent No. 6,214,255 B1").
cited by other .
(Attachment No. 10: Sud-Chemie, Inc. Vs. CSP Technologies, Inc.:
"Deposition Of Glenn Frederickson Taken On Tuesday, Oct. 12, 2004",
(19 Pages). cited by other .
(Attachment No. 11: Sud-Chemie, Inc.Vs. CSP Technologies, Inc.:
"Videotaped Deposition Of Defendant By Ihab Hekal", (Sep. 23, 2004)
(7 Pages). cited by other .
(Attachment No. 12: Lancessenr, "United S.tates Patent No.
5,432,214"). cited by other .
(Attachment No. 13: Chart Comparing U.S. Patent No. 5,911,937,
6,124,006 and 6,214,255 to "SCI Infringing Product", (pp. 1-5).
cited by other .
(Attachment No. 14: "Project On Morphology Control In
Polymer-Polymer-Particle Alloys", (pp. 1-2). cited by other .
(Attachment No. 15: "European Patent Application No. 0,401,666
A2"). cited by other .
(Attachment No. 16: "Shigeta et al., U.S. Patent No. 5,078,909").
cited by other .
(Attachment No. 17: "International Application No.
PCT/US96/05261"). cited by other .
(Attachment No. 18: "Hekal, United States Patent No. 6,174,952
B1"). cited by other .
(Attachment No. 19: "Hekal, United States Patent No. 6,194,079
B1"). cited by other .
(Attachment No. 20: "Hekal, United States Patent No. 6,465,532
B1"). cited by other .
(Attachment No. 21: "Hekal, United States Patent No. 6,486,231
B1"). cited by other .
(Attachment No. 22: "Memo To Dr. Hekal From Rob Garren"). cited by
other .
(Attachment No. 23: Sud-Chemie, Inc. Vs. CSP Technologies, Inc.:
"Deposition Of Robert Garren, on Jul. 8, 2004", (4 Pages). cited by
other .
(Attachment No. 24: "Letter To Calvin L. Loop From Robert S.
Abrams") (With Attachment). cited by other .
(Attachment No. 25: "Letter To Calvin L. Loop From Robert S.
Abrams"). cited by other .
(Attachment No. 26: "Memo To Calvin Loop From Rob Garren"). cited
by other .
(Attachment No. 27: "Memo To Calvin Loop From Beki Urioste"). cited
by other .
(Attachment No. 28: "Memo To Dr. Hekal, Clavin Loop, Robert Abrams
From Rob Garren"). cited by other .
(Attachment No. 29: "Summary On New Polymer Technology"). cited by
other .
(Attachment No. 30: "Diagrams"). cited by other .
(Attachment No. 31: "Diagrams"). cited by other .
(Attachment No. 32: "Diagrams"). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP Technologies
Inc.'s Opposition to Sud-Chemie, Inc.'s Summary Judgment Motion and
Exhibits 7, 9A,9B,9C, (D, (E,12,14,15 & 17", (pp. 1-34). cited
by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Reply Brief in
Support of Its Motion for Summary Judgment of Patent Invalidity",
(pp. 1-21). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "CSP's Local Rule
56.1(d) Surreply in Opposition to SCI's Motion for Summary of
Patent Invalidity", (pp. 1-10). cited by other .
Sud-Chemie, Inc. vs. CSP Technologies, Inc.: "SCI's Motion for
Summary Judgment of Patent Invalidity", (pp. 1-2). cited by
other.
|
Primary Examiner: McDowell; Suzanne E.
Attorney, Agent or Firm: Greenberg Traurig, LLP
Parent Case Text
RELATED APPLICATION
This application is a continuation-in-part of U.S. Ser. No.
09/087,830, filed May 29, 1998, now U.S. Pat. No. 6,124,006, which
in turns is a continuation-in-part of U.S. Ser. No. 08/812,315,
filed Mar. 5, 1997, now U.S. Pat. No. 6,130,263, which in turn is a
continuation-in-part of U.S. Ser. No. 08/611,298, filed on Mar. 5,
1996, now U.S. Pat. No. 5,911,937, which in turn is a
continuation-in-part of U.S. Ser. No. 08/424,996, filed Apr. 19,
1995, now abandoned.
Claims
What is claimed is:
1. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol, PVOH, polyvinvlpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds, glucose, fructose and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and a
releasing agent selected from the group consisting of pesticides,
nematocides, fungicides and rodenticides; wherein the composition
comprises at least three phases and has interconnecting channels
with the releasing agent in or adjacent to these channels.
2. The article of manufacture of claim 1 wherein the polymer is a
thermoplastic.
3. The article of manufacture of claim 1, wherein the hydrophilic
agent is a polyglycol.
4. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols, poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol PVOH, polyvinylpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds, glucose, fructose, and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and a
releasing agent selected from the group consisting of fragrance
flavor and perfume sources; wherein the composition comprises at
least three phases and has interconnecting channels with the
releasing agent in or adjacent to these channels.
5. The article of manufacture of claim 4 wherein the polymer is a
thermoplastic.
6. The article of manufacture of claim 4 wherein the hydrophilic
agent is a polyglycol.
7. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols, poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol, PVOH, polyvinylpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds, glucose, fructose, and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and a
releasing agent selected from the group consisting of
antimicrobial, corrosion inhibitors, ripening and antiripening
agents; wherein the composition comprises at least three phases and
has interconnecting channels with the releasing agent in or
adjacent to these channels.
8. The article of manufacture of claim 7 wherein the polymer is a
thermoplastic.
9. The article of manufacture of claim 7 wherein the hydrophilic
agent is a polyglycol.
10. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent having a solubility in
water above about 1% at 25.degree. C. and atmospheric pressure and
is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and a releasing agent
selected from the group consisting of pesticides, nematocides,
fungicides and rodenticides; wherein the composition comprises at
least three phases and having interconnecting channels with the
releasing agent in or adjacent to these channels.
11. The article of manufacture of claim 10 wherein the polymer is a
thermoplastic.
12. The article of manufacture of claim 10 wherein the hydrophilic
agent is a polyglycol.
13. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent having a solubility in
water above about 1% at 25.degree. C. and atmospheric pressures and
is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and a releasing agent
selected from the group consisting of fragrance, flavor and perfume
sources; wherein the composition comprises at least three phases
and having interconnecting channels with the releasing agent in or
adjacent to these channels.
14. The article of manufacture of claim 13 wherein the polymer is a
thermoplastic.
15. The article of manufacture of claim 13 wherein the hydrophilic
agent is a polyglycol.
16. An article of manufacture comprising a monolithic composition
formed by combining at least the following components: a polymer
having a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; a hydrophilic agent having a solubility in
water above about 1% at 25.degree. C. and atmospheric pressure and
is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and a releasing agent
selected from the group consisting of antimicrobial, corrosion
inhibitors ripening and antiripening agents; wherein the
composition comprises at least three phases and having
interconnecting channels with the releasing agent in or adjacent to
these channels.
17. The article of manufacture of claim 16 wherein the polymer is a
thermoplastic.
18. The article of manufacture of claim 16 wherein the hydrophilic
agent is a polyglycol.
19. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols, poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol, PVOH, polyvinylpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds, glucose, fructose, and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and (c) a
releasing agent selected from the group consisting of pesticides,
nematocides, fungicides and rodenticides; wherein the composition
comprises at least three phases and has interconnecting channels
with the releasing agent in or adjacent to these channels.
20. The article of manufacture of claim 19 wherein the polymer is a
thermoplastic.
21. The article of manufacture of claim 19 wherein the hydrophilic
agent is a polyglycol.
22. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols, poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol, PVOH, polyvinylpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds glucose, fructose, and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and (c) a
releasing agent selected from the group consisting of fragrance,
flavor and perfume sources; wherein the composition comprises at
least three phases and has interconnecting channels with the
releasing agent in or adjacent to these channels.
23. The article of manufacture of claim 22 wherein the polymer is a
thermoplastic.
24. The article of manufacture of claim 22 wherein the hydrophilic
agent is a polyglycol.
25. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent is at least about
.[.10%.]. .Iadd.5% .Iaddend.by weight of the .[.polymer.].
.Iadd.composition .Iaddend.and is selected from the group
consisting of polyglycols, poly(ethylene glycol), poly(propylene
glycol), EVOH, pentaerithritol, PVOH, polyvinylpyrollidine,
vinylpyrollidone or poly(N-methyl pyrollidone), and saccharide
based compounds, glucose, fructose, and their alcohols, mannitol,
dextrin, and hydrolized starch and mixtures thereof; and (c) a
releasing agent selected from the group consisting of
antimicrobial, corrosion inhibitors, ripening and anti-ripening
agents; wherein the composition comprises at least three phases and
has interconnecting channels with the releasing agent in or
adjacent to these channels.
26. The article of manufacture of claim 25 wherein the polymer is a
thermoplastic.
27. The article of manufacture of claim 25 wherein the hydrophilic
agent is a polyglycol.
28. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent having a solubility
in water above about 1% at 25.degree. c. and atmospheric pressure
and is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and (c) a releasing agent
selected from the group consisting of pesticides, nematocides,
fungicides and rodenticides; wherein the composition comprises at
least three phases and has interconnecting channels with the
releasing agent in or adjacent to these channels.
29. The article of manufacture of claim 28 wherein the polymer is a
thermoplastic.
30. The article of manufacture of claim 28 wherein the hydrophilic
agent is a polyglycol.
31. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent having a solubility
in water above about 1% at 25.degree. C. and atmospheric pressure
and is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and (c) a releasing agent
selected from the group consisting of fragrance, flavor and perfume
sources; wherein the composition comprises at least three phases
and has interconnecting channels with the releasing agent in or
adjacent to these channels.
32. The article of manufacture of claim 31 wherein the polymer is a
thermoplastic.
33. The article of manufacture of claim 31 wherein the hydrophilic
agent is a polyglycol.
34. An article of manufacture comprising a monolithic composition
comprising at least the following components: (a) a polymer having
a solubility in water below about 0.1% at 25.degree. C. and
atmospheric pressure; (b) a hydrophilic agent having a solubility
in water above about 1% at 25.degree. C. and atmospheric pressure
and is at least about .[.10%.]. .Iadd.5% .Iaddend.by weight of the
.[.polymer.]. .Iadd.composition.Iaddend.; and (c) a releasing agent
selected from the group consisting of antimicrobial, corrosion
inhibitors ripening and anti-ripening agents; wherein the
composition comprises at least three phases and has interconnecting
channels with the releasing agent in or adjacent to these
channels.
35. The article of manufacture of claim 34 wherein the polymer is a
thermoplastic.
36. The article of manufacture of claim 34 wherein the hydrophilic
agent is a polyglycol.
.Iadd.37. An article of manufacture comprising a monolithic
composition formed by combining at least the following components:
a water-insoluble polymer; a releasing material selected from the
group consisting of antimicrobials, wherein the releasing material
is composed of a particle and the particle is at least about 5% by
weight of the composition; an agent that controls the transmission
between an exterior of the polymer and the interiorly located
releasing material and wherein the agent is hydrophilic, wherein an
affinity between the agent and the releasing material is greater
than between the polymer and the releasing material; and wherein
the composition comprises an interconnecting channel composed of
the agent..Iaddend.
.Iadd.38. An article of manufacture comprising a monolithic
composition formed by combining at least the following components:
a water-insoluble polymer; a releasing material selected from the
group consisting of aromatic medicines, wherein the releasing
material is composed of a particle and the particle is at least
about 5% by weight of the composition; an agent that controls the
transmission between an exterior of the polymer and the interiorly
located releasing material, wherein an affinity between the agent
and the releasing material is greater than between the polymer and
the releasing material; and wherein the composition comprises an
interconnecting channel composed of the agent and wherein the agent
is hydrophilic..Iaddend.
.Iadd.39. The article of manufacture of claim 1, wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.40. The article of manufacture of claim 1 wherein the polymer
is about 35% by weight of the polymer composition..Iaddend.
.Iadd.41. The article of manufacture of claim 1 wherein the polymer
is about 68% by weight of the polymer composition..Iaddend.
.Iadd.42. The article of manufacture of claim 1 wherein the polymer
is about 35% to about 68% by weight of the polymer
mixture..Iaddend.
.Iadd.43. The article of manufacture of claim 1 wherein the
hydrophilic agent is about 12% of the polymer
composition..Iaddend.
.Iadd.44. The article of manufacture of claim 1 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.45. The article of manufacture of claim 1 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.46. The article of manufacture of claim 1 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.47. The article of manufacture of claim 1 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
.Iadd.48. The article of manufacture of claim 10 wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.49. The article of manufacture of claim 10 wherein the
polymer is about 35% by weight of the polymer
composition..Iaddend.
.Iadd.50. The article of manufacture of claim 10 wherein the
polymer is about 68% by weight of the polymer
composition..Iaddend.
.Iadd.51. The article of manufacture of claim 10 wherein the
polymer is about 35% to about 68% by weight of the polymer
composition..Iaddend.
.Iadd.52. The article of manufacture of claim 10 wherein the
hydrophilic agent is about 12% of the polymer
composition..Iaddend.
.Iadd.53. The article of manufacture of claim 10 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.54. The article of manufacture of claim 10 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.55. The article of manufacture of claim 10 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.56. The article of manufacture of claim 10 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
.Iadd.57. The article of manufacture of claim 19 wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.58. The article of manufacture of claim 19 wherein the
polymer is about 35% by weight of the polymer
composition..Iaddend.
.Iadd.59. The article of manufacture of claim 19 wherein the
polymer is about 68% by weight of the polymer
composition..Iaddend.
.Iadd.60. The article of manufacture of claim 19 wherein the
polymer is about 35% to about 68% by weight of the polymer
composition..Iaddend.
.Iadd.61. The article of manufacture of claim 19 wherein the
hydrophilie agent is about 12% of the polymer
composition..Iaddend.
.Iadd.62. The article of manufacture of claim 19 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.63. The article of manufacture of claim 19 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.64. The article of manufacture of claim 19 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.65. The article of manufacture of claim 19 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
.Iadd.66. The article of manufacture of claim 28 wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.67. The article of manufacture of claim 28 wherein the
polymer is about 35% by weight of the polymer
composition..Iaddend.
.Iadd.68. The article of manufacture of claim 28 wherein the
polymer is about 68% by weight of the polymer
composition..Iaddend.
.Iadd.69. The article of manufacture of claim 28 wherein the
polymer is about 35% to about 68% by weight of the polymer
composition..Iaddend.
.Iadd.70. The article of manufacture of claim 28 wherein the
hydrophilic agent is about 12% of the polymer
composition..Iaddend.
.Iadd.71. The article of manufacture of claim 28 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.72. The article of manufacture of claim 28 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.73. The article of manufacture of claim 28 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.74. The article of manufacture of claim 28 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
.Iadd.75. An article of manufacture comprising a monolithic
composition comprising at least the following components: a
water-insoluble polymer; a releasing material selected from the
group consisting of biologically active ingredients, wherein the
releasing material is composed of a particle and the particle is at
least about 5% by weight of the composition; an agent that acts as
a transmission bridge between an exterior of the polymer and the
interiorly located releasing material and wherein the agent is
hydrophilic, wherein the affinity between the agent and the
releasing material is greater than between the polymer and the
releasing material; and wherein the composition comprises an
interconnecting channel composed of the agent..Iaddend.
.Iadd.76. The article of manufacture of claim 75, wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.77. The article of manufacture of claim 75 wherein the
polymer is about 35% by weight of the polymer
composition..Iaddend.
.Iadd.78. The article of manufacture of claim 75 wherein the
polymer is about 68% by weight of the polymer
composition..Iaddend.
.Iadd.79. The article of manufacture of claim 75 wherein the
polymer is about 35% to about 68% by weight of the polymer
composition..Iaddend.
.Iadd.80. The article of manufacture of claim 75 wherein the
hydrophilic agent is about 12% of the polymer
composition..Iaddend.
.Iadd.81. The article of manufacture of claim 75 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.82. The article of manufacture of claim 75 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.83. The article of manufacture of claim 75 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.84. The article of manufacture of claim 75 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
.Iadd.85. An article of manufacture comprising a monolithic
composition comprising at least the following components: a
water-insoluble polymer; a releasing material selected from the
group consisting of antimicrobials, wherein the releasing material
is composed of a particle and the particle is at least about 5% by
weight of the composition; an agent that acts as a transmission
bridge between an exterior of the polymer and the interiorly
located releasing material and wherein the agent is hydrophilic,
wherein the affinity between the agent and the releasing material
is greater than between the polymer and the releasing material; and
wherein the composition comprises an interconnecting channel
composed of the agent..Iaddend.
.Iadd.86. An article of manufacture comprising a monolithic
composition comprising at least the following components: a
water-insoluble polymer; a releasing material selected from the
group consisting of aromatic medicines, wherein the releasing
material is composed of a particle and the particle is at least
about 5% by weight of the composition; an agent that acts as a
transmission bridge between an exterior of the polymer and the
interiorly located releasing material and wherein the agent is
hydrophilic, wherein an affinity between the agent and the
releasing material is greater than between the polymer and the
releasing material; and wherein the composition comprises an
interconnecting channel composed of the agent..Iaddend.
.Iadd.87. An article of manufacture comprising a monolithic
composition formed by combining at least the following components:
a water-insoluble polymer; a releasing material selected from the
group consisting of biologically active ingredients, wherein the
releasing material is composed of a particle and the particle is at
least about 5% by weight of the composition; an agent that controls
the transmission between an exterior of the polymer and the
interiorly located releasing material and wherein the agent is
hydrophilic, wherein an affinity between the agent and the
releasing material is greater than between the polymer and the
releasing material; and wherein the composition comprises an
interconnecting channel composed of the agent..Iaddend.
.Iadd.88. The article of manufacture of claim 87 wherein the
releasing agent is least about 40% by weight of the polymer
composition..Iaddend.
.Iadd.89. The article of manufacture of claim 87 wherein the
polymer is about 35% by weight of the polymer
composition..Iaddend.
.Iadd.90. The article of manufacture of claim 87 wherein the
polymer is about 68% by weight of the polymer
composition..Iaddend.
.Iadd.91. The article of manufacture of claim 87 wherein the
polymer is about 35% to about 68% by weight of the polymer
composition..Iaddend.
.Iadd.92. The article of manufacture of claim 87 wherein the
hydrophilic agent is about 12% of the polymer
composition..Iaddend.
.Iadd.93. The article of manufacture of claim 87 wherein the
releasing agent is about 40% by weight of the polymer
composition..Iaddend.
.Iadd.94. The article of manufacture of claim 87 wherein the
releasing agent is about 60% by weight of the polymer
composition..Iaddend.
.Iadd.95. The article of manufacture of claim 87 wherein the
releasing agent is about 40% to about 60% by weight of the polymer
composition..Iaddend.
.Iadd.96. The article of manufacture of claim 87 wherein the
releasing agent is about 53% by weight of the polymer
composition..Iaddend.
Description
FIELD OF THE INVENTION
This invention generally relates to monolithic compositions
comprising a water-insoluble polymer, a hydrophilic agent and a
releasing material. In one embodiment, the present invention
relates to modified polymers blended with one or more releasing
materials to form a releasing material entrained polymer. The
invention further relates to an entrained polymer that includes
means by which the releasing material located within interior
portions of the polymer structure are exposed to conditions that
are exterior to the polymer body. In one embodiment, the entrained
polymer of the present invention is useful in the manufacture of
containers and packaging for items requiring controlled
environments.
BACKGROUND OF THE INVENTION
There are many items that are preferably stored, shipped and/or
utilized in an environment that must be controlled and/or
regulated. For example, in the moisture control area, containers
and/or packages having the ability to absorb excess moisture
trapped therein have been recognized as desirable. One application
in which moisture absorbing containers are desired is for the
shipment and storage of medications whose efficacy is compromised
by moisture. The initial placement of medicines into a sealed
moisture free container is usually controllable. Furthermore, the
container for the medicine is selected so that is has a low
permeability to moisture. Therefore, the medication will normally
be protected from moisture until it reaches the end user. Once the
medicine is received by the customer, however, the container must
be repeatedly opened and closed to access the medication. Each time
the container is opened and unsealed, moisture bearing air will
most likely be introduced into the container and sealed therein
upon closure. Unless this moisture is otherwise removed from the
atmosphere or head space of the container, it may be detrimentally
absorbed by the medication. For this reason, it is a well known
practice to include a desiccating unit together with the medication
in the container.
Other items, electronic components may require reduced moisture
conditions for optimal performance. These components may be sealed
in containers, but excess moisture that is initially trapped
therein must be removed. Furthermore, the housings may not be
completely moisture tight, and moisture may be allowed to seep into
the container. This moisture must also be retained away from the
working components. For these reasons, it is important to include a
desiccating agent within the housing for absorbing and retaining
excess moisture. Because of the delicacy of many of the components
that are to be protected from the moisture, it is important that
the desiccant used not be of a "dusting" nature that may
contaminate and compromise the performance of the components.
Therefore, it has been recognized as advantageous to expose a
desiccating agent to the interior space of such containers, while
at the same time shielding the working components from actual
contact with the desiccating material, including desiccant dust
that may be produced therefrom.
In other instances, moisture may be released from items that have
been placed in containers or sealed in packaging wrap for shipping
and/or storage. Prime examples of such items are food stuffs-that
release moisture during shipping and storage. In the instance of
containers that are sealed and substantially impermeable to
moisture, the released moisture will remain within the container.
If not removed, this released moisture may have ill effects on the
very item that released the moisture. It has been found that a
substantial amount of moisture is released from certain food
products within the first forty-eight (48) hours after manufacture
and packaging. This released moisture will remain until removed. If
the moisture is not removed shortly after its release, it may cause
the food to degrade into a condition that is not saleable. In these
cases, desiccants may be included together with the contained items
to continually absorb the released moisture until the product is
unpacked. In this way, a relatively dry environment is maintained
about the stored item.
SUMMARY OF THE INVENTION
The present invention discloses both a structure and a method by
which interconnecting channels are established throughout the
composition. These interconnecting channels communicate the
entrained releasing material to the appropriate areas of the
exterior of the composition in a manner that permits the desired
property to migrate from outside the plastic structure to interior
locations where the releasing material is positioned. Furthermore,
these interconnecting channels through which the desired property
is permitted to travel are occupied by hydrophilic agents (e.g.,
channeling agents) that control the transmission rate into the
composition. The hydrophilic agents are used to act as bridges from
the surface of the composition inwardly to the releasing material
positioned within the composition.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a perspective view of a plug, insert, or tablet
constructed from the composition of the present invention showing,
in an exaggerated scale, the openings of the interconnecting
channels at the exterior surface of the plug.
FIG. 2 is an exaggerated, cross-sectional view of a solidified plug
formed from a water-insoluble polymer having a hydrophilic agent
and a releasing material blended therewith.
FIG. 3 is an exaggerated cross-sectional view of a portion of a
container having the composition of the present invention formed
into a plug insert located in the bottom of a container constructed
from a polymer that acts as a transmission rate barrier.
FIG. 4 is an exaggerated cross-sectional view of a portion of a
container the composition of the present invention formed into a
plug that has been comolded into the bottom of a container that is
constructed from a polymer that acts as a transmission rate
barrier.
FIG. 5 is an exaggerated cross-sectional view of a portion of a
container the composition of the present invention formed into a
liner insert located within the interior of a container constructed
from a polymer that acts as a transmission rate barrier.
FIG. 6 is an exaggerated cross-sectional view of a portion of a
container having the composition of the present invention formed
into a liner that has been comolded at the interior of a container
that is constructed from a polymer that acts as a transmission rate
barrier.
FIG. 7 is an exaggerated cross-sectional view of the composition of
the present invention formed into a sheet located adjacent to a
barrier sheet constructed from a polymer that acts as a
transmission rate barrier.
FIG. 8 is an exaggerated cross-sectional view the composition of
the present invention formed into a sheet that has been comolded at
an interior of a barrier sheet so that the products are integrally
molded together and comprise one unified laminate.
FIG. 9 is a graphical view of a swelling and weight loss analysis
of three film samples: Film #2, Film #3 and Film #4.
FIG. 10 is a graphical view of a DSC curve of a sample of 100%
polyglycol.
FIG. 11 is a graphical view of a DSC curve of a sample of Film
#4.
FIG. 12 is a graphical view of a DSC curve of a sample of Film
#5.
FIG. 13 is a graphical view of an DSC curve of a sample of Film
#6.
FIG. 14 is a graphical view of a DSC curve of a sample of Film
#7.
FIG. 15 is a graphical view of a DSC curve of a sample of Film #2
in a pre-incubation state.
FIG. 16 is a graphical view of a DSC curve of a sample of Film #2
in a post-incubation state.
FIG. 17 is a graphical view of a DSC curve of a sample of Film #3
in a pre-incubation state.
FIG. 18 is a graphical view of a DSC curve of a sample of Film #3
in a post-incubation state.
FIGS. 19a-c are scanning electron photomicrographs of a film sample
of Film #4.
FIGS. 20a-c are scanning electron photomicrographs of a film sample
of Film #5.
FIGS. 21a-c are scanning electron photomicrographs of a film sample
of Film #6.
FIGS. 22a-d are scanning electron photomicrographs of a film sample
of Film #3.
FIGS. 23a and 23b is a graphical view of showing the precent
moisture gain per weight of molecular sieve at 10% Rh and
72.degree. F. and 20% RH and 72.degree. F., respectively.
Among those benefits and improvements that have been disclosed,
other objects and advantages of this invention will become apparent
from the following description taken in conjunction with the
accompanying drawings. The drawings constitute a part of this
specification and include exemplary embodiments of the present
invention and illustrate various objects and features thereof.
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are
disclosed herein; however, it is to be understood that the
disclosed embodiments are merely exemplary of the invention that
may be embodied in various forms. The figures are not necessarily
to scale, some features may be exaggerated to show details of
particular components. Therefore, specific structural and
functional details disclosed herein are not to be interpreted as
limiting, but merely as a basis for the claims and as a
representative basis for teaching one skilled in the art to
variously employ the present invention.
It has been discovered that certain compounds, which are referred
to herein as hydrophilic agents (e.g., channeling agents), may be
combined with a water-insoluble polymer that is used in the
formation of shaped articles. In practice, in one embodiment the
water-insoluble polymer base into which the hydrophilic agent is
blended includes, as examples, any polyethylene and
polypropylene.
In one embodiment, a releasing material and hydrophilic agent are
added to the water-insoluble polymer when the polymer is in a
molten state or before the polymer is in the molten state, so that
the material and hydrophilic agent may be blended and thoroughly
mixed throughout the polymer to insure that the blend is uniformly
mixed before reaching the melt phase. For example, such a technique
is useful when the releasing material, hydrophilic agent and
polymer are all powders.
In another embodiment, the hydrophilic agent and polymer are mixed
prior to adding the releasing material. The hydrophilic agent is
added either before the polymer is in the molten state or after the
polymer is in the molten state. For example, the releasing material
may be added to the polymer during the thermal process of forming
sheets.
After thorough blending and processing, following by cooling, the
hydrophilic agent forms, interconnecting channels that act as
transmission communicating passages throughout the polymer. In
addition, the composition of the present invention is monolithic
and the water-insoluble polymer hydrophilic agent and releasing
material form a three phase system.
For purposes of the present invention, the term "phase" means a
portion of a physical system that is uniform throughout, has
defined boundaries and, in principle, be separated physically from
other phases. The term "interconnecting channels" means channels
that penetrate through the water-insoluble polymer and that may be
interconnected to each other. The term "water-insoluble polymer"
means a polymer having a solubility in water below about 0.1% at
25.degree. C. and atmospheric pressure. The term "hydrophilic
agent" is defined as a material that is not substantially
cross-linked and that has a solubility in water of at least about
1% at 25.degree. C. and atmospheric pressure. Suitable hydrophilic
agents include "channeling" agents. The term "monolithic
composition" means a composition that does not consist of two or
more discrete macroscopic layers. Accordingly, a "monolithic
composition" does not include a multi-layer composite. Moreover,
for purposes of the present invention, the term "melting point" is
defined as the first order transition point of the material
determined by DSC. The term "not mutually soluble" means immiscible
with each other.
In one embodiment, suitable hydrophilic agents of the present
invention include polyglycols such as poly(ethylene glycol) and
poly(propylene glycol) and mixtures thereof. Other suitable
materials include EVOH, glycerin, pentaerithritol, PVOH,
polyvinylpyrollidine, vinylpyrollidone or poly(N-methyl
pyrollidone) and saccharide based compounds such as glucose,
fructose, and their alcohols, mannitol, dextrin and hydrolyzed
starch being suitable for the purposes of the present invention
since they are hydrophilic compounds.
In another embodiment, suitable hydrophilie agents of the present
invention may also include any hydrophilic material wherein, during
processing, the hydrophilic agent is heated above its melt point
upon melt mixing, and subsequently upon cooling separates from the
polymer to form the interconnecting channeled structure of the
present invention and a three phase system of a water-insoluble
polymer, hydrophilic agent and a releasing material.
The present invention may be employed with a variety of releasing
material. Such material may comprise any suitable form which will
release dispersant to surrounding atmosphere, including solid, gel,
liquid, and in some cases a gas. These substances can perform a
variety of functions including: serving as a fragrance, flavor, or
perfume source; supplying a biologically active ingredient such as
pesticide, pest repellent, antimicrobials, bait, aromatic
medicines, etc.; providing humidifying or desiccating substances;
delivering air-borne active chemicals, such as corrosion
inhibitors; ripening agents and odor-making agents, etc.
The biocides of the present invention may include, but are not
limited to, pesticides, herbicides, nematacides, fungicides,
rodenticides and/or mixtures thereof. In addition to the biocides,
the covering of the present invention can also release nutrients,
plant growth regulators, pheromones, defoliants and/or mixture
thereof.
The incorporation of a quaternary ammonium compound, not only
functions as a surfactant but also imparts to the surface of the
manufactured product aseptic properties or establishes conditions
for reducing the number of microbial organisms, some of which can
be pathogenic. Numerous other antimicrobial agents, such as
benzalkonium chloride and related types of compounds as
hexachlorophene, may also be used.
Other releasing materials include fragrances, including natural,
essential oils and synthetic perfumes, and blends thereof. Typical
perfumery materials which may form part of, or possible the whole
of, the active ingredient include: natural essential oils such as
lemon oil, mandarin oil, clove leaf oil, petitgrain oil, cedar wood
oil, patchouli oil, lavandin oil, neroli oil, ylang oil, rose
absolute or jasmin absolute; natural resins such as labdanum resin
or olibanum resin; single perfumery chemicals which may be isolated
from natural sources of manufactured synthetically, as for example
alcohols such as geraniol, nerol, citronellol, linalol,
tetrahydrogeraniol, betaphenylethyl alcohol, methyl phenyl
carbinol, dimethyl benzyl carbinol, menthol or cedrol; acetates and
other esters derived form such alcohols-aldehydes such as citral,
citronellal, hydroxycitronellal, lauric aldehyde, undecylenic
aldehyde, cinnamaldehyde, amyl cinnamic aldehyde, vanillin or
heliotropin; acetals derived from such aldehydes; ketones such as
methyl hexyl ketone, the ionones and methylionones; phenolic
compounds such as eugenol and isoeugenol; synthetic musks such as
musk xylene, musk ketone and ethylene brassylate.
In one embodiment relating to releasing material having a
relatively fine particle size, many small interconnecting channels
throughout the polymer should be produced, as opposed to a few
large interconnecting channels that will expose less surface area
within the polymer. In one embodiment, dimer agents such as
polypropylene maleic anhydride, or any plasticizer, may be
optionally added to the mixture reducing viscosities and increasing
the mixing compatibility of the polymer and hydrophilic agent.
In yet another embodiment, releasing materials are selected having
a polarity that causes an affinity between the releasing agent and
the hydrophilic agent. For this reason, during the separating
process when the interconnecting channels are formed throughout the
polymer, it is believed that the releasing material will migrate
toward the hydrophilic agent domains to which it is attracted. In
this manner, it is theorized that the hydrophilic agent is
permitted to act as a bridge between moisture located exteriorly to
the polymer structure and the releasing material that is located
within the polymer. This is particularly true with respect to a
releasing material that is bound within the hydrophilic agent
filled passages. In a further embodiment, polar plasticizers such
as glycerin may be further added to the mixture which enhance the
dispersion or mixing of the releasing material into the hydrophilic
agent.
It is believed that the higher the releasing material concentration
in the mixture, the greater the absorption capacity will be of the
final composition. However, the higher releasing material
concentration should cause the body to be more brittle and the
mixture to be more difficult to either thermally form, extrude or
injection mold. In one embodiment, the releasing material loading
level can range from 10% to 20%, 20% to 40% and 40% to 60% by
weight with respect to the polymer.
In one embodiment, the water-insoluble polymer of the present
invention may be any thermoplastic material. Examples of suitable
thermoplastic materials include polyolefins such as polypropylene
and polyethylene, polyisophrene, polybutadiene, polybutene,
polysiloyane, polycarbonates, polyamides, ethylene-vinyl acetate
copolymers, ethylene-methacrylate copolymer, poly(vinyl chloride),
polystyrene, polyesters, polyanhydrides, polyacrylonitrile,
polysulfones, polyacrylic ester, acrylic, polyurethane and
polyacetal, copolymers or mixtures thereof.
In yet another embodiment, the components are first dry mixed in a
mixer such as a Henschel, and then fed to a compounder. A Leistritz
twin screw extruder, for example, or a Werner Pfleider mixer can be
used to achieve a good melt mix at about 140.degree. C. to about
170.degree. F. The melt can then be either extruded to form, for
example, a film or converted into pellets using dry air cooling on
a vibrating conveyer. The formed pellets, containing channels, can,
for example, then be either injection molded into beads, sieves, or
co-injected with polypropylene as the inside layer of a
container.
In yet a further another embodiment, because the composition of the
present invention may typically be more brittle than the polymer
without the releasing material, the package may be molded so that
an interior portion of the package is the composition of the
present invention while the exterior portions are formed from pure
polymer or the composition of the present invention with a lower
releasing material loading level. For example, a package having an
interior portion composed of the composition of the present
invention and an exterior portion composed of pure polymer
typically will not only be more durable and less brittle, but it
will also act as a barrier that resists the transmission of
moisture from the exterior into the interior of the package. In
this manner, the capacity of the releasing material is potentiated
by exposing it exclusively to the interior of the package from
which it is desired that the material will be released.
The composition of the present invention has numerous applications.
One application is the construction of rigid containers that are
suitable for containing relatively small volumes of product such as
food stuffs and medicines. In many cases, these types of products
must be shipped and stored in controlled environments (e.g. reduced
moisture and/or oxygen). In another embodiment, the composition of
the present invention may be formed into an insert for inclusion
within the interior of the container. An example of one form of an
insert is a plug of any suitable shape. While the plug would serve
its purpose by being merely deposited within the container, it may
also be fixed to an interior location so that it does move about
within the interior space. In a further embodiment, it is
anticipated that a plug formed into a disc may be shaped and sized
to be pressed fit into the bottom of a polymer formed
container.
In another embodiment, a liner may be formed from the composition
of the present invention that has an exterior surface substantially
conforming to an interior surface of the container body. Like the
disc, the liner may be sized so that it may be press-fit into
position within the polymer body where it is held sufficiently
snugly to prevent its unintended disengagement therefrom.
Alternatively, in a further embodiment, either the plug or liner
may be initially constructed and allowed to harden, and then the
container body subsequently constructed thereabout so that the
greater shrinkage characteristics of the polymer body not
containing the releasing material tightly shrink-fits the container
body about the plug or liner so that neither becomes easily
disengaged from the other. In still a further embodiment, the
insert taking the form of either a plug or a liner may be
substantially simultaneously comolded with the polymer container
body so that each is integrally joined with the other. In the event
of a co-molding process, the viscosities of the desiccant laden
insert and the polymer container body should typically be
approximately equal to facilitate the proper and desired location
of the two phases of liquid or molten material that are molded
together.
In yet another embodiment, composition of the present invention may
be used to form sheeting that is joined with another sheet. In at
least one embodiment, the sheets are effectively laminated one to
the other so that an exterior layer may be established adjacent to
the composition of the present invention which is substantially air
and moisture impermeable. The laminate sheet may then be used to
wrap an item which is to be stored in a controlled environment. One
means by which the joinder process may be accomplished is through a
thermal extrusion procedure.
In each of the embodiments of the present invention described
herein, advantages and enhancements over the prior art methods and
structures stem from the discovery of the ability to create
interconnecting channels throughout the composition of the present
invention so that a rigid body may be constructed from the
composition of the present invention while also exposing the
releasing material to the environment. Furthermore, the discovery
of employing a hydrophilic agent that also acts as a transmission
rate bridge between the exterior of the polymer body and the
interiorly located releasing material greatly enhances the
structures' ability to quickly remove the desired property located
exteriorly to the entrained structure, while at the same time
taking advantage of a greater portion of the material's
capacities.
One embodiment of the present invention includes a process for
producing the composition of the present invention. In one
embodiment, the process comprises blending a water-insoluble
polymer and a hydrophilic agent. Either prior to blending the
hydrophilic agent or after blending the hydrophilic agent, the
releasing material is blended into the polymer so that the additive
is uniformly distributed within the polymer and the hydrophilic
agent is distributed within the polymer. Subsequently, after the
composition is solidified, the result is that the hydrophilic agent
forms interconnecting channels in the composition through which the
desired property is transmitted through the polymer to the
releasing material within the composition. In another embodiment,
the hydrophilic agent and releasing material are all thoroughly
mixed in dry powder form, and then the polymer blend is melted and
formed into a desired shape by molding. Interconnecting channels
are formed in the composition through which the desired property is
transmitted through the polymer to the releasing material within
the composition.
In an alternative embodiment of the present invention, the
monolithic composition comprising a water-insoluble polymer, a
hydrophilic agent and a releasing material may be made by first
producing a two phase system comprising the water-insoluble polymer
and the hydrophilic agent, then immersing the two phase system in a
solution containing the releasing material. As a result, the
releasing material is taken up by the composition and results in a
monolithic composition consisting of at least three phases
comprising the water-soluble polymer, the hydrophilic agent and the
releasing material. It is to be understood that, for purposes of
the present invention, immersing includes soaking, coating or other
methods that result in an uptake of the releasing material by the
composition.
One specific example consists of (1) mixing the water-insoluble
polymer and the hydrophilic agent to produce a uniform blend; (2)
heating the blend of step (1) to a temperature above the melting
point of the hydrophilic agent; (3) cooling the blend of step (2)
to form the desired shaped article; (4) immersing the shaped
article of step (3) in a solution containing the releasing
material; (5) drying under suitable conditions that would not
detrimentally affect the materials; and (6) forming a shaped
article comprising a monolithic composition comprising the
water-insoluble polymer; the hydrophilic agent and the releasing
material.
This alternative embodiment may be well-suited for materials that
are heat-sensitive and thus, that may not be capable of
withstanding the temperatures required to melt the hydrophilic
agent during processing. An example of such high temperatures are
the temperatures incurred during the extrusion step. Consequently,
the releasing material may be added downstream from the extrusion
and thus, are not subject to higher temperatures, which may
detrimentally effect the material. A further example of this
alternative embodiment relates to producing the solution for the
releasing material. In one embodiment, an aqueous solution of the
releasing material is produced.
In one embodiment, the composition of the present invention is used
to form a plug for inclusion within a package constructed of a
barrier substance. In another, the composition of the present
invention is used to form a liner of inclusion within a container
constructed from a barrier substance. In still another embodiment,
the composition of the present invention is used to form an
absorption sheet. The absorption sheet may optionally be combined
with a barrier sheet constructed of a barrier substance for use as
a packaging wrap. In another embodiment, the composition of the
present invention is used to form an absorbing insert for a
container.
Referring to FIG. 1 of the accompanying drawings of an embodiment
of the present invention, an insert constructed from the
composition of the present invention 20 is illustrated. For
purposes of this disclosure of the present invention, the words
"entrain" and "contain" have been used interchangeably when
referring to the inclusion of a desiccating agent 30 in a polymer
25 matrix. The insert is in the form of a plug 55 that may be
deposited into a container body 60 (FIG. 5) thereby establishing a
container 61 (FIG. 5). Referring to FIG. 2, a cross-sectional view
is shown of the plug 55 that has been constructed from a polymer
mixture comprising the water-insoluble polymer 25 that has been
uniformly blended with the releasing material 30 and the
hydrophilic agent 35. In the illustration of FIG. 2, the
composition of the present invention has been solidified so that
interconnecting channels 45 have formed throughout the composition
to establish passages throughout the solidified plug 55. As may be
appreciated in both FIGS. 1 and 2, the passages terminate in
channel openings 48 at an exterior surface of the plug 55.
FIG. 3 illustrates the embodiment of a plug 55 similar in
construction and makeup to the plug 55 of FIG. 2, where
interconnecting channels are very fine. This can result from the
use of polyglycols as the hydrophilic agent, or the use of a dimer
agent (i.e., a plasticizer) together with a hydrophilic agent. The
dimer agent 50 may enhance the compatibility between the polymer 25
and the hydrophilic agent 35. This enhanced compatibility is
facilitated by a lowered viscosity of the blend which should
promote a more thorough blending of the two compounds 25,35 which
resists combination into a uniform solution. Upon solidification of
the composition of the present invention that has had a dimer agent
added thereto, the interconnecting channels which are formed
therethrough have a greater dispersion and a smaller porosity
thereby establishing a greater density of interconnecting channels
throughout the plug 55. In one embodiment, this same effect occurs
readily when a polyglycol is used as the hydrophilic agent due to
the general comparability of polyglycols with hydrophobic
thermoplastics such as polyolefins. The interconnecting channels
are created to provide pathways for controlled transmission of the
desired property from the exterior of the solidified plug 55 to
interior locations where the entrained releasing material 30 is
bound.
It is believed that these interconnecting channels are required
because of the hydrophobic characteristics of the polymer 25 that
resist permeability therethrough and therefore acts as a barrier.
For this reason, the polymer 25 itself is referred to as a barrier
substance within which a releasing material 30 may be entrained. To
expose the releasing material 30 entrained within the interior of
the polymer 25, however, the interconnecting channels 45 are
provided. Without these interconnecting channels 45, it is believed
that relatively small quantities of the releasing material would be
released by the entrained releasing material 30. It is further
believed that these small amounts derive from the limited number of
releasing material particles 30 that would be exposed at the
exterior surface of the formed body and the very small amounts of
the releasing agent that would be able to pass through the
substantially impermeable polymer 25. Because of these
characteristics, the water-insoluble polymer 25 is referred to as a
barrier even though it may not be completely impermeable.
FIG. 3 illustrates an embodiment of the present invention of a plug
55 which has been deposited into a container body 60 thereby
establishing a releasing container 61. The container body 60 has an
interior surface 65 and is constructed substantially from the
composition of the present invention. In this manner, the
transmission property is resisted from being transmitted across a
wall of the container 60 when the container 60 is closed. As may be
seen in FIG. 3, the plug 55 has been press fit into a bottom
location of the container 60. It is contemplated that the plug 55
may be merely deposited in the container 60 for loose containment
therein, but it is preferable coupled to the body of the container
60 in a manner that fixes the plug 55 to the container 60. The
couple between the plug 55 and the container body 60 is intended to
prevent the dislocation and relative movement of the plug 55
thereabout. This connection may be accomplished by a snug press fit
between the plug 55 and the interior surface 65 of the body 60, or
it may be mechanically connected in such manners as adhesives,
prongs, lips or ridges that extend about the plug 55 to hold the
plug 55 in place. In yet another embodiment, it is contemplated
that the container body 60 may be molded about the plug 55 so that
during the curing process of the container body 60 the body 60
shrinks about the plug 55 thereby causing a shrink-fit to be
established between the two components. This type of couplement may
also be accomplished in a comolding process or sequential molding
process with the same results achieved because the plug 55 will
have less shrinkage than the polymer 25 comprised container body
60.
FIG. 4 illustrates a releasing container 61 having the composition
of the present invention formed of a plug 55 located at a bottom
location of the container 60 similar to the configuration
illustrated in FIG. 3, but the plug 55 and container body 60 are
comolded so that a unified body 61 is formed with a less distinct
interface between the plug 55 and body 60 components.
FIGS. 5 and 6 illustrate concepts similar to those of FIGS. 3 and
4, however the proportions of the plug 55 have been extended so
that a liner 70 is formed which covers a greater portion of the
interior surface 65 of the container 61. The liner 70 is not
localized in the bottom portion of the container body 60, but has
walls which extend upwardly and cover portions of the walls of the
container 61. Like the plug 55, the liner 70 may be separately
molded and subsequently combined with the container body 60 or it
may be comolded therewith into the unified body illustrated in FIG.
6.
FIGS. 7 and 8 illustrate an embodiment of the invention in which a
releasing material formed of a sheet of the present invention 75 is
created for combination with a barrier sheet 80. The
characteristics of the sheets are similar to those described with
respect to the plug 55 and liner 70 and container body 60. That is,
FIG. 7 illustrates an embodiment in which the two sheets 75, 80 are
separately molded, and later combined to form a packaging wrap
having releasing material characteristics at an interior surface
and resistant characteristics at an exterior surface. FIG. 8
illustrates a comolded process wherein an interface between the
sheet 75 and the barrier sheet 80 is less distinct than in the
embodiment of FIG. 7. This product can be produced by a thermal,
forming process. In such a process, the polymer layer is melted and
partially formed into a sheet with the releasing material 30 being
deposited on top of that layer just prior to being pressed or
extruded through a slit like opening in the thermal forming
machine. It is contemplated that the separate sheets 75, 80 of FIG.
7 may be joined together with an adhesive or other suitable means
to form a laminate from the plurality of sheets 75, 80.
Alternatively, the sheeting 75, 80 may be manufactured from a
thermal extrusion process whereby both sheets 75, 80 are
manufactured at the same time and effectively comolded together to
form the embodiment illustrated in FIG. 8.
In a further embodiment of the present invention, a plug 55 is
formed from the mixture for inclusion within a container 60 that is
constructed from a barrier substance. In one embodiment, the plug
55 is deposited into a container 60 that is constructed from a
barrier substance. In this manner, a container 61 is created. The
plug 55 may be coupled to an interior surface of the container body
60 so that the plug 55 is fixed relative to the container 60.
Alternatively, a container 60 constructed from a barrier substance
may be molded about the plug 55 so that at least a portion of the
plug 55 is exposed to an interior of the container 60. A
desiccating plug 55 made according to the present invention may
also be co-molded with a container 60 that is constructed from a
barrier substance so that at least a portion of the plug 55 is
exposed to an interior of the container 60.
In another embodiment, a liner 70 may be formed from the mixture 40
and then be included within a container 60 constructed from a
barrier substance. The liner 70 typically, but not necessarily, has
an exterior surface configured for mating engagement with an
interior surface 65 of the container 60.
The liner 70 may be pressed into mating engagement with the
container 60 so that a container 61 is created wherein at least a
majority of the interior surface 65 of the container is covered by
the liner 70.
The liner 70 may be formed from the mixture 40 and then a container
60 constructed from a barrier substance may be molded about the
liner 70 so that at least a portion of the liner 70 is exposed to
an interior of the container 60 and a majority of an interior
surface 65 of the container 60 is covered by the liner 70.
Alternatively, the liner 70 and container body 60 may be comolded
together into a unified body.
The absorbing sheet 75 is combined with a barrier sheet 80 that is
constructed of a barrier substance for use as a packaging wrap.
The sheets 75, 80 may be laminated by thermal extrusion.
A dimer agent may optionally be added to the mixture to increase
the mixing compatibility of the polymer 25 and the channeling agent
35 thereby increasing the dispersion of the passages within the
solidified mixture.
In still another embodiment of the present invention, a method for
making a releasing material formed in the shape of container 61 is
provided. The method includes forming a container 60 from
substantially air and moisture impermeable material so that an air
and moisture barrier is created between an interior and exterior of
the container. An insert is formed from composition of the present
invention. The insert has an exterior surface that is configured
for mating engagement with at least a portion of an interior
surface 65 of the container 60. The insert is installed into the
interior of the container 60 so that at least a portion of the
exterior surface of the insert abuttingly engages the interior
surface 65 of the container 60. The engagement fixes the insert
relative to the container 60 and resists disengagement of the
insert from the container 60. The insert is exposed to the interior
of the container 60 for releasing the desired property. The insert
is pressed into the interior of the container 60 with sufficient
force that the insert fits tightly within the container 60 thereby
resisting disengagement therefrom. The insert is sized and shaped
so that the insert fits snugly into a receiving location within the
interior of the container for retention at the receiving
location.
In another embodiment, the insert is sized and shaped into a plug
55 that fits snugly into a receiving location at a bottom portion
of the interior of the container 60 for retention at the receiving
location.
In a further embodiment, the insert is configured into a liner 70
having an exterior surface that conforms to the interior surface 65
of the container 60 so that a majority of the liner's 70 exterior
surface is in abutting engagement with the container's 60 interior
surface 65. The container 60 and the liner 70 are similarly
configured so that the interior 65 of the container 60 and the
exterior of the liner 70 fit snugly together so that disengagement
of the liner 70 from the container 60 is resisted.
In another example, the container 60 may be molded from a plastic
that is substantially impermeable and therefore resists the
transmission of the releasing material across the boundary of the
container 60 between its exterior and its interior. Also, the liner
70 may be molded from the composition of the present invention.
In yet another embodiment, a method for making a releasing material
formed in the shape of container 61 is provided. A container is
formed from substantially air and moisture impermeable material so
that a barrier is established between an interior and exterior of
the container 60. A substantially solid tablet or plug 55 is formed
from the composition of the present invention 20, the tablet 55
being suitably sized to fit within the interior of the container
60. The tablet 55 is then deposited into the interior of the
container 60 thereby establishing a means for releasing the desired
material from the interior of the container 60 when the container
60 is closed about the tablet 55.
In another embodiment of the present invention, a method for making
a releasing material in the shape of a package is provided. An
outer skin, sheet, or layer 80 is formed from a substantially air
and moisture impermeable sheet of material so that a barrier is
created between opposite sides of the skin. An inner skin, sheet,
or layer 75 is formed from the composition of the present invention
20 at one side of the outer skin 80. A package is formed about a
product or item by sealing the product or item within the outer
impermeable skin 80 and with the inner releasing material skin 75
located adjacent to the product. A releasing material laminate may
be formed by suction vacuum molding the outer skin 80 and the inner
skin 75 together to form the package.
In one embodiment of the present invention, a releasing material in
the form of an enclosure 61 is provided. The enclosure includes a
container 60 formed from substantially moisture and air impermeable
material so that a barrier is created between an interior and
exterior of the container 60. A liner 70 is formed from the
composition of the present invention 20 so that the liner 70 has an
exterior surface configured for mating engagement with at least a
portion of an interior surface 65 of the container 60. The liner 70
is inserted into the interior of the container 60 so that at least
a portion of the exterior surface of the liner abuttingly engages
the interior surface 65 of the container 60. The engagement fixes
the liner 70 relative to the container 60 and resists disengagement
of the liner 70 from the container 60.
In another embodiment of the present invention, a releasing
material in the form of an insert for a closable container 60
includes an insert made from the composition of the present
invention is configured for installation into a closable container
60. The insert 25 is constructed from the composition of the
present invention. The insert 25 has passages extending from its
exterior surface into its interior.
The present invention will be illustrated in greater detail by the
following specific examples. It is understood that these examples
are given by way of illustration and are not meant to limit the
disclosure or claims. For example, although the following examples
were tested at 10% Rh and 20% Rh at 72.degree. F., the composition
of the present invention is also suited for other conditions.
Moreover, these examples are meant to further demonstrate that the
present invention has interconnecting channels and that the
hydrophilic agents reside in the interconnecting channels. All
percentages in the examples or elsewhere in the specification arc
by weight unless otherwise specified.
EXAMPLE 1
The purpose of the following example is to demonstrate that the
composition of the present invention has interconnecting channels
by subjecting the following materials to a swelling and weight loss
analysis. In addition, the following example demonstrates that the
composition of the present invention is able to release a substance
(e.g., poly(ethylene glycol)).
A. Preparation of Samples
Film #1: A blend of about 93% (w/w) of polypropylene (Exxon
Chemicals, tradename Escorene.RTM. polypropylene 3505G) and about
7% (w/w) of poly(ethylene glycol) (Dow Chemical, tradename E-4500)
was sufficiently mixed to produce a uniform blend. The blend was
then fed through a Leistritz twin screw extruder at temperatures in
the sixteen zones ranging from about 145.degree. C. to about
165.degree. C., at a feed rate of about 40 lbs/hr, at a screw speed
of about 460 rpm and a six inch die. The extruded composition was
then fed through a three roll hot press at temperatures ranging
from about 85.degree. C. to about 92.degree. C. to produce a film
of about 4 mil.
Film #2: A blend of about 68% (w/w) of polypropylene (Exxon
Chemicals, tradename Escorene.RTM. polypropylene 3505G) and about
3505G), about 12% (w/w) of poly (ethylene glycol) (Dow Chemical,
tradename E-4500) and about 20% (w/w) of a desiccant of molecular
sieve (Elf Atochem, tradename Siliporite.RTM. molecular sieve, 4
Angstrom) was sufficiently mixed to produce a uniform blend. The
blend was then fed through a Leistritz twin screw extruder at
temperatures in the sixteen zones ranging from about 145.degree. C.
to about 165.degree. C., at a feed rate of about 40 lbs/hr at a
screw speed of about 460 rpm and a six inch die. The extruded
composition was then fed through a three roll hot press at
temperatures ranging from about 85 to about 92.degree. C. to
produce a film of about 4 mil.
Film #3: A blend of about 34.88% (w/w) of polypropylene (Exxon
Chemical, tradename Escorene.RTM. polypropylene 3505G), about
11.96% (w/w) of poly(ethylene glycol) (Dow Chemical, tradename
E-4500), about 52.82% (w/w) of a desiccant of molecular sieve (Elf
Atochem, tradename Siliporite.RTM. molecular sieve, 4 Angstrom) and
about 0.34% (w/w) of a grey colorant was sufficiently mixed to
produce a uniform blend. The blend was then fed through a Leistritz
twin screw extruder at temperatures in the sixteen zones ranging
from about 145.degree. C. to about 165.degree. C., at a feed rate
of about 50 lbs/hr at a screw speed of about 460 rpm and a six inch
die. The extruded composition was then fed through a three roll hot
press at temperatures ranging from about 85 to about 92.degree. C.
to produce a film of about 4 mil.
B. Swelling and Weight Loss Analysis
Circular disks (OD 1.1 cm) were cut from each of the three samples.
Initial dry weights of each sample was recorded. Samples were
subsequently incubated in 2.0 ml distilled water and left shaking
at room temperature. Periodically at 1, 2, 3, and 34 days, the
disks were removed, the surface blotted dry and the sample weighed,
to determine the extent of swelling. At each timepoint, the
distilled water was replaced to provide for sink conditions. At the
end of the study, the samples were lyophilized to remove the water
and the sample weighed to determine mass loss. FIG. 9 is a graph of
the result of the analysis. Percent swelling is defined as the wet
weight at a time point (t), divided by initial dry weight (zero)
and multiplied by 100. `Dry` indicates the final lyophilized sample
weight following the 34 day incubation.
FIG. 9 shows film #1 did not swell or lose weight over the course
of 34 days. Thus, it is believed that this result shows that the
poly(ethylene glycol) (i.e., hydrophilic agent) was completely
entrapped in the polypropylene (i.e., water-insoluble polymer).
Film #2 gained approximately 3% of its initial weight by swelling
and lost approximately 9% of its initial weight at the end of the
34 days of incubation. Film #3 gained approximately 6% of its
initial weight and lost approximately 8% of its initial weight at
the end of the 34 day incubation period. These results demonstrate
that interconnecting channels from the exterior through the
interior exist in the composition of the present invention because
water penetrated films #2 and #3 and a substantial portion of the
water soluble component (e.g., poly(ethylene glycol)) of films #2
and #3 was extracted from the polymer.
EXAMPLE 2
The purpose of the following example is to demonstrate that the
composition of the present invention has two separate phases
consisting of a water-insoluble polymer and a hydrophilic
agent.
A. Preparation of Samples
Film #4: 100% polypropylene (Exxon Chemicals, tradename
Escorene.RTM. polypropylene 3505G) was fed through a Leistritz twin
screw extruder at temperatures in the sixteen zones ranging from
about 145.degree. C. to about 165.degree. C., at a feed rate of
about 40 lbs/hr, at a screw speed of about 460 rpm and a six inch
die. The extruded composition was then fed through a three roll hot
press at temperatures ranging from about 85.degree. C. to about
92.degree. C. to produce a film of about 4 mil.
Film #5: A blend of about 88% (w/w) of polypropylene (Exxon
Chemicals tradename Escorene.RTM. polypropylene 3505G), about 12%
(w/w) of poly(ethylene glycol) (Dow Chemical, tradename E-4500) was
sufficiently mixed to produce a uniform blend. The blend was then
fed through a Leistritz twin screw extruder at temperatures in the
sixteen zones ranging from about 145.degree. C. to about
165.degree. C., at a feed rate of about 40 lbs/hr, at a screw speed
of about 460 rpm and a six inch die. The extruded composition was
then fed through a three roll hot press at temperatures ranging
from about 85.degree. C. to about 92.degree. c. to produce a film
of about 4 mil.
Film #7: A blend of about 68% (w/w) of polypropylene (Exxon
Chemicals, tradename Escorene.RTM. polypropylene 3505G), about 12%
(w/w) of poly(ethylene glycol) (Dow Chemical, tradename E-4500) and
about 20% (w/w) of a desiccant of molecular sieve (Elf Atochem,
tradename Siliporite.RTM. molecular sieve, 4 Angstrom) was
sufficiently mixed to produce a uniform blend. The blend was then
fed through a Leistritz twin screw extruder at temperatures in the
sixteen zones ranging from about 145.degree. C. to about
165.degree. C., at a feed rate of about 12 lbs/hr, at a screw speed
of about 460 rpm and a six inch die. The extruded composition was
then fed through a three roll hot press at temperatures of about
105.degree. C. to produce a film of about 4 mil.
B. Thermal Analysis Using Differential Scanning Calorimetry
("DSC")
The processed film samples were analyzed using a Perkin Elmer DSC7
equipped with a TAC 7DX thermal controller. Data were analyzed
using Perkin Elmer Pyris software (version 2.01). Samples were
heated from -50 to 250.degree. C. at a rate of 10 or 15.degree.
C./min, then cooled at the same rate and then heated once again to
250.degree. C. at the same rate. The following table is the date
collected from the DSC. The melting point data is given as the
melting point peak (.degree. C.) and enthalpy (.DELTA.H, joules/gm)
for the first heating ramp (1.degree.) and the second heating ramp
(20.degree.). The column referring to FIGS. 10 through 18 is the
graphical output from the DSC that corresponds to the date from the
table. Since the samples are only heated to 250.degree. C., the
molecular sieve in film samples #2, #3 and #7 was not melted and
thus, no melting point date was recorded.
TABLE-US-00001 PEG PEG PP PP Sample FIG. # Peak.degree. C. .DELTA.H
J/g Peak.degree. C. .DELTA.H J/g 100% FIG. 10 1.degree. 63.808
190.362 none None poly(ethylene glycol) Film #4 FIG. 11 1.degree.
none None 162.700 78.462 2.degree. none None 157.200 96.123 Film #5
FIG. 12 1.degree. 57.700 22.253 161.700 80.524 2.degree. 58.033
20.361 157.366 79.721 Film #6 FIG. 13 1.degree. none None 159.366
42.385 2.degree. none None 160.033 42.876 Film #7 FIG. 14 1.degree.
56.366 19.460 162.200 70.073 2.degree. 57.200 17.094 156.866 58.038
Film #2 FIG. 15 1.degree. 58.554 20.845 163.062 60.577
[pre-incubation] 2.degree. 58.779 16.037 157.783 53.706 Film #2
FIG. 16 1.degree. 55.804 0.379 163.062 86.215 [post-incubation]
2.degree. 57.529 0.464 158.533 67.949 Film #3 FIG. 17 1.degree.
59.308 18.849 162.562 40.291 [pre-incubation] 2.degree. 56.529
10.122 158.283 24.980 Film #3 FIG. 18 1.degree. 55.554 0.138
160.562 46.931 [post-incubation] 2.degree. none None 156.033
26.081
The 100% poly(ethylene glycol) sample, exhibits a single melting
point at 63.degree. C. while film #4 100% polypropylene has a
melting point at 157.degree. C. Film #5 displayed both peaks at
58.degree. C. (poly(ethylene glycol)) and 157.degree. C.
(polypropylene), which indicates that the two polymers were phase
separated. If the polymers were not phase separated but mixed, then
the peaks would not be at the melt temperatures of the pure
polymers, but shifted. Film #6 shows only the distinct
polypropylene peak at 160.degree. C. The molecular sieves do not
melt in this temperature range or affect the melting temperature of
pure polypropylene. Film #7 again shows two distinct peaks: one for
poly(ethylene glycol) at 57.degree. C. and one for polypropylene at
157.degree. C. indicating that in the three component mixture, all
are phase separated.
Film samples #2 and 3 were part of the swelling and weight loss
analysis presented in Example 1. Once again two distinct peaks were
evident: one for poly(ethylene glycol) at 59.degree. C. and one for
polypropylene at 158.degree. C. indicating that in the three
component mixture, all components were phase separated. However
when the polymer film was incubated in water for 34 days at room
temperature (File #2: post-incubation) and tested by DSC, the
positions of the peaks remained the same indicating the components
were still phase-separated. However the area of the poly(ethylene
glycol) peak (indicated by delta H, enthalpy) was greatly reduced.
This result indicated that poly(ethylene glycol) had been extracted
by the prolonged water incubation. Also, the result provided
further confirmation for the weight loss data presented in Example
1 and demonstrated that the poly (ethylene glycol) component was
mostly extracted by means of interconnecting channels in the bulk
polypropylene matrix.
Film sample #3, showed the same effect as Film sample #2. The
polypropylene delta H peak was not detectable (Film #3:
post-incubation), demonstrating nearly complete extraction of
poly(ethylene glycol) during water incubation. This confirmed the
weight loss result of Example 1 in which the same film lost
approximately 8% of it's initial weight. The poly(ethylene glycol)
composition of the sample was approximately 12% (w/w).
In addition, the glass transition (T.sub.g) analysis from the DSC
data of the samples of the present invention also demonstrate that
the water-insoluble polymer and the material exist in separate
phases. Pure polypropylene exhibits a T.sub.g of about -6.degree.
C. while pure poly(ethylene glycol) exhibits a T.sub.g at about
-30.degree. C. DSC data from film #5 exhibit two distinct
T.sub.g's, which correspond to the respective polymers (6.degree.
C. for polypropylene and -30.degree. C. for poly(ethylene glycol)
and thus, indicates, further that the two components are phase
separated.
EXAMPLE 3
The purpose of the following example is to demonstrate that the
composition of the present invention has interconnection channels
and has the water absorbing material intermixed within the
hydrophilic agent.
A. Scanning Electron Microscopy ("SEM") Method
The structural properties of the films was imaged using a Hitachi
S-2700 microscope operating at 8 kV accelerating voltage to
minimize irradiation damage. Each film sample was visualized in
three perspectives: 1) the film surface; 2) the fractured film
cross-section (0.degree.) and 3) the fractured film cross-section
at a 90.degree. angle with respect to orientation #2 (90.degree.).
Pre-incubation film samples were directly sputter coated with a
5-10 nm layer of gold-palladium with a Polaron Instruments Sputter
Coater E5100. Post-incubation samples were incubated at room
temperature for 24 hrs in 10 ml of 70% ethanol (w/v) with
agitation. The ethanol was discarded and the samples were air-dried
overnight. Samples were then frozen and lyophilized overnight to
remove any residual moisture and then sputter coated.
B. Morphology of Film Samples
FIGS. 19a-c are scanning electro photomicrographs of film sample
#4--100% polypropylene. FIGS. 19a-c illustrate that a
water-insoluble polymer is typically a dense, homogenous morphology
with substantially no porosity. The outer surface is shown in FIG.
19a FIG. 19a shows an outer surface that is dense and displaying
substantially no porosity. The cross-sectional view is shown in
FIG. 19b at a magnification of 200 times. FIG. 19b shows plate-like
domains of polymer that were revealed during brittle facture of the
film. Another cross-sectional view is shown in FIG. 19c at a
magnification of 1000 times. FIG. 19c shows a dense, fibrillar
morphology.
FIGS. 20a-c are scanning electron photomicrographs of film samples
#5--about 88% polypropylene and 12% poly (ethylene glycol). FIGS.
20a-c illustrate that a two phase system consisting essentially of
a water-insoluble polymer and hydrophilic agent has a heterogeneous
morphology with dense fibrallar matrix interspersed with domains of
lamellar structures, which is the poly(ethylene glycol). FIGS.
20a-c further show voids between lamellar fibrillar and fibrillar
structures that are channels and are oriented in the same
direction. The outer surface is shown in FIG. 20a at a
magnification of 1000 times. FIG. 20a shows an outer surface that
is dense and displaying substantially no porosity. The
cross-sectional view is shown in FIG. 20b at a magnification of
2,500 times. FIG. 20b shows fibrillar domains of polymer coated
with lamellar strands of poly (ethylene glycol). FIG. 20c is a
cross-sectional view of film sample #5 fractured a perpendicular
angle and at a magnification of 1,500 times. FIG. 20c shows the
fibrillar polypropylene matrix interspersed with solid, amorphous
cylinder of poly(ethylene glycol).
FIGS. 21a-c are scanning electron photomicrographs of film sample
#6--about 50% polypropylene and 50% molecular sieve. FIGS. 21a-c
illustrate a typically homogeneous dense matrix and discrete
molecular sieves can only occasionally be seen and are deeply
embedded in the polymer despite the high loading of molecular
sieves. FIG. 21a shows the outer surface at a magnification of
1,000 times that is covered with long channels measuring 5-30
microns. The outline of the molecular sieves (1-10 microns) can be
seen embedded beneath the surface of the polymer. The
cross-sectional view is shown in FIG. 21b at a magnification of 200
times. FIG. 21b shows plate-like domains of polymer and a grainy
appearance due to the high loading of molecular sieves. FIG. 21c is
a cross-sectional view at a magnification 1,500 times and shows a
dense morphology, substantially no porosity and many small
particles embedded in the polymer.
FIGS. 22a-d are scanning electron photomicrographs of film samples
#3-about 52% molecular sieve, about 34% polypropylene and about 12%
poly(ethylene glycol). FIGS. 22a-d show a three phase system with a
highly porous morphology. FIG. 22a shows the outer surface at a
magnification of 500 times that is covered with long channels,
measuring 5-30 microns, and that is filled with numerous discrete
molecular sieve particles. A cross-sectional view is shown in FIG.
22b at a magnification of 350 times. FIG. 22b shows a very porous
morphology with long channels running in the fracture orientation.
FIG. 22c is a cross-sectional view in the perpendicular orientation
at a magnification of 350 times and appears to show holes. FIG. 22
is at higher magnifications--1,500 times. FIG. 22d shows channels
containing discrete molecular sieves as well as agglomerates of
many sieves embedded in the poly(ethylene glycol). Consequently,
based on FIG. 22b, it is believed that the holes seen in FIGS. 22b
and 22c are locations where the molecular sieve fell out during
fracture preparation for SEM.
In conclusion, Examples 1, 2 and 3 further confirm the theory for
the formation of interconnecting channels. Since, in one
embodiment, the process begins at a temperature at which the
hydrophilic agent is in molten form while the water-insoluble
polymer is in solid form, it is believed that the third component
(e.g. molecular sieve) is interacting with the liquid hydrophilic
agent. Consequently, it is believed that, at this point, the
interconnecting channels are formed because the hydrophilic agent
flows easily and fills the gaps between the solid water-insoluble
polymer and the molecular sieve components. As the process
continues and the temperature increases, the water-insoluble
polymer melts and thus, the composition becomes more uniform.
EXAMPLE 4
The purpose of the following example is to demonstrate the water
absorption properties of the compositions of the present invention.
Samples of film with similar processing conditions as film #1 were
made having about 50% (w/w) of molecular sieve [4 Angstrom], about
12% (w/w) poly (ethylene glycol) and about 38% (w/w) polypropylene
and were evaluated for moisture adsorption of its total weight by
using the following test method (a) one environmental chamber was
preset for 72.degree. F. and 10% relative humidity ("Rh") and
another chamber was preset for 72.degree. F. and 20% Rh; (b) the
dish was weighed and the weight recorded; (c) the scale was then
tared to remove the weight of the dish from the balance; (d) the
film was then added to the weighed dish; (e) the material was then
weighed and the weight recorded; (f) the weigh dish with the sample
was placed in the environment chamber; (g) the sample was left in
the chamber for the desired time; (h) after the desired time was
reached, the dish with the sample was removed, re-weighed and the
weight recorded; and (i) the precent moisture gained per gram of
molecular sieve was calculated by (total weight gain of
sample)/(weight of molecular sieve in sample).times.100. The
results are presented in FIGS. 23a [10% RH] and 23b [20% Rh] The
maximum theorectical precent moisture gained per weight of a 4
Angstrom molecular sieve is about 24 to 25%. FIGS. 23a and 23b
demonstrate that the high transmission rate (e.g., moisture
absorption rate) of the present invention.
Monolithic compositions and their constituent compounds have been
described herein. As previously stated, detailed embodiments of the
present invention are disclosed herein; however, it is to be
understood that the disclosed embodiments are merely exemplary of
the invention that may be embodied in various forms. It will be
appreciated that many modifications and other variations that will
be appreciated by those skilled in the art are within the intended
scope of this invention as claimed below without departing from the
teachings, spirit and intended scope of the invention.
* * * * *