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Publication numberUSRE40941 E1
Publication typeGrant
Application numberUS 10/714,474
Publication date20 Oct 2009
Filing date13 Nov 2003
Priority date19 Apr 1995
Fee statusPaid
Publication number10714474, 714474, US RE40941 E1, US RE40941E1, US-E1-RE40941, USRE40941 E1, USRE40941E1
InventorsIhab Hekal
Original AssigneeCsp Technologies, Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polymer having interconnecting channels which act as controlled transmission passages through the polymer; hydrophilic agent is blended into the polymer so that it is distributed within the polymer; useful in the manufacture of containers and packaging for items requiring controlled environments
US RE40941 E1
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.
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Claims(96)
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° C. and atmospheric pressure; a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure; a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure; a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure; a hydrophilic agent having a solubility in water above about 1% at 25° C. and atmospheric pressure and is at least about 10%5% by weight of the polymercomposition; 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° C. and atmospheric pressure; a hydrophilic agent having a solubility in water above about 1% at 25° C. and atmospheric pressures and is at least about 10%5% by weight of the polymercomposition; 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° C. and atmospheric pressure; a hydrophilic agent having a solubility in water above about 1% at 25° C. and atmospheric pressure and is at least about 10%5% by weight of the polymercomposition; 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° C. and atmospheric pressure;
(b) a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure;
(b) a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure;
(b) a hydrophilic agent is at least about 10%5% by weight of the polymercomposition 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° C. and atmospheric pressure;
(b) a hydrophilic agent having a solubility in water above about 1% at 25° c. and atmospheric pressure and is at least about 10%5% by weight of the polymercomposition; 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° C. and atmospheric pressure;
(b) a hydrophilic agent having a solubility in water above about 1% at 25° C. and atmospheric pressure and is at least about 10%5% by weight of the polymercomposition; 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° C. and atmospheric pressure;
(b) a hydrophilic agent having a solubility in water above about 1% at 25° C. and atmospheric pressure and is at least about 10%5% by weight of the polymercomposition; 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.
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.
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.
39. The article of manufacture of claim 1, wherein the releasing agent is least about 40% by weight of the polymer composition.
40. The article of manufacture of claim 1 wherein the polymer is about 35% by weight of the polymer composition.
41. The article of manufacture of claim 1 wherein the polymer is about 68% by weight of the polymer composition.
42. The article of manufacture of claim 1 wherein the polymer is about 35% to about 68 % by weight of the polymer mixture.
43. The article of manufacture of claim 1 wherein the hydrophilic agent is about 12% of the polymer composition.
44. The article of manufacture of claim 1 wherein the releasing agent is about 40% by weight of the polymer composition.
45. The article of manufacture of claim 1 wherein the releasing agent is about 60% by weight of the polymer composition.
46. The article of manufacture of claim 1 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
47. The article of manufacture of claim 1 wherein the releasing agent is about 53% by weight of the polymer composition.
48. The article of manufacture of claim 10 wherein the releasing agent is least about 40% by weight of the polymer composition.
49. The article of manufacture of claim 10 wherein the polymer is about 35% by weight of the polymer composition.
50. The article of manufacture of claim 10 wherein the polymer is about 68% by weight of the polymer composition.
51. The article of manufacture of claim 10 wherein the polymer is about 35% to about 68 % by weight of the polymer composition.
52. The article of manufacture of claim 10 wherein the hydrophilic agent is about 12% of the polymer composition.
53. The article of manufacture of claim 10 wherein the releasing agent is about 40% by weight of the polymer composition.
54. The article of manufacture of claim 10 wherein the releasing agent is about 60% by weight of the polymer composition.
55. The article of manufacture of claim 10 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
56. The article of manufacture of claim 10 wherein the releasing agent is about 53% by weight of the polymer composition.
57. The article of manufacture of claim 19 wherein the releasing agent is least about 40% by weight of the polymer composition.
58. The article of manufacture of claim 19 wherein the polymer is about 35% by weight of the polymer composition.
59. The article of manufacture of claim 19 wherein the polymer is about 68% by weight of the polymer composition.
60. The article of manufacture of claim 19 wherein the polymer is about 35% to about 68 % by weight of the polymer composition.
61. The article of manufacture of claim 19 wherein the hydrophilie agent is about 12% of the polymer composition.
62. The article of manufacture of claim 19 wherein the releasing agent is about 40% by weight of the polymer composition.
63. The article of manufacture of claim 19 wherein the releasing agent is about 60% by weight of the polymer composition.
64. The article of manufacture of claim 19 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
65. The article of manufacture of claim 19 wherein the releasing agent is about 53% by weight of the polymer composition.
66. The article of manufacture of claim 28 wherein the releasing agent is least about 40% by weight of the polymer composition.
67. The article of manufacture of claim 28 wherein the polymer is about 35% by weight of the polymer composition.
68. The article of manufacture of claim 28 wherein the polymer is about 68% by weight of the polymer composition.
69. The article of manufacture of claim 28 wherein the polymer is about 35% to about 68 % by weight of the polymer composition.
70. The article of manufacture of claim 28 wherein the hydrophilic agent is about 12% of the polymer composition.
71. The article of manufacture of claim 28 wherein the releasing agent is about 40% by weight of the polymer composition.
72. The article of manufacture of claim 28 wherein the releasing agent is about 60% by weight of the polymer composition.
73. The article of manufacture of claim 28 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
74. The article of manufacture of claim 28 wherein the releasing agent is about 53% by weight of the polymer composition.
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.
76. The article of manufacture of claim 75, wherein the releasing agent is least about 40% by weight of the polymer composition.
77. The article of manufacture of claim 75 wherein the polymer is about 35% by weight of the polymer composition.
78. The article of manufacture of claim 75 wherein the polymer is about 68% by weight of the polymer composition.
79. The article of manufacture of claim 75 wherein the polymer is about 35% to about 68 % by weight of the polymer composition.
80. The article of manufacture of claim 75 wherein the hydrophilic agent is about 12% of the polymer composition.
81. The article of manufacture of claim 75 wherein the releasing agent is about 40% by weight of the polymer composition.
82. The article of manufacture of claim 75 wherein the releasing agent is about 60% by weight of the polymer composition.
83. The article of manufacture of claim 75 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
84. The article of manufacture of claim 75 wherein the releasing agent is about 53% by weight of the polymer composition.
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.
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.
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.
88. The article of manufacture of claim 87 wherein the releasing agent is least about 40% by weight of the polymer composition.
89. The article of manufacture of claim 87 wherein the polymer is about 35% by weight of the polymer composition.
90. The article of manufacture of claim 87 wherein the polymer is about 68% by weight of the polymer composition.
91. The article of manufacture of claim 87 wherein the polymer is about 35% to about 68 % by weight of the polymer composition.
92. The article of manufacture of claim 87 wherein the hydrophilic agent is about 12% of the polymer composition.
93. The article of manufacture of claim 87 wherein the releasing agent is about 40% by weight of the polymer composition.
94. The article of manufacture of claim 87 wherein the releasing agent is about 60% by weight of the polymer composition.
95. The article of manufacture of claim 87 wherein the releasing agent is about 40% to about 60 % by weight of the polymer composition.
96. The article of manufacture of claim 87 wherein the releasing agent is about 53% by weight of the polymer composition.
Description
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.

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° F. and 20% RH and 72° 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° 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° 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° C. to about 170° 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° 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® 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° C. to about 165° 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° C. to about 92° C. to produce a film of about 4 mil.

Film #2: A blend of about 68% (w/w) of polypropylene (Exxon Chemicals, tradename Escorene® 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® 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° C. to about 165° 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° 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® 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® 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° C. to about 165° 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° 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® polypropylene 3505G) was fed through a Leistritz twin screw extruder at temperatures in the sixteen zones ranging from about 145° C. to about 165° 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° C. to about 92° C. to produce a film of about 4 mil.

Film #5: A blend of about 88% (w/w) of polypropylene (Exxon Chemicals tradename Escorene® 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° C. to about 165° 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° C. to about 92° c. to produce a film of about 4 mil.

Film #7: A blend of about 68% (w/w) of polypropylene (Exxon Chemicals, tradename Escorene® 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® 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° C. to about 165° 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° 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° C. at a rate of 10 or 15° C./min, then cooled at the same rate and then heated once again to 250° 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 (° C.) and enthalpy (ΔH, joules/gm) for the first heating ramp (1°) and the second heating ramp (20°). 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° C., the molecular sieve in film samples #2, #3 and #7 was not melted and thus, no melting point date was recorded.

PEG PEG PP PP
Sample FIG. # Peak° C. ΔH J/g Peak° C. ΔH J/g
100% FIG. 10 63.808 190.362 none None
poly(ethylene
glycol)
Film #4 FIG. 11 none None 162.700 78.462
none None 157.200 96.123
Film #5 FIG. 12 57.700 22.253 161.700 80.524
58.033 20.361 157.366 79.721
Film #6 FIG. 13 none None 159.366 42.385
none None 160.033 42.876
Film #7 FIG. 14 56.366 19.460 162.200 70.073
57.200 17.094 156.866 58.038
Film #2 FIG. 15 58.554 20.845 163.062 60.577
[pre-incubation] 58.779 16.037 157.783 53.706
Film #2 FIG. 16 55.804 0.379 163.062 86.215
[post-incubation] 57.529 0.464 158.533 67.949
Film #3 FIG. 17 59.308 18.849 162.562 40.291
[pre-incubation] 56.529 10.122 158.283 24.980
Film #3 FIG. 18 55.554 0.138 160.562 46.931
[post-incubation] none None 156.033 26.081

The 100% poly(ethylene glycol) sample, exhibits a single melting point at 63° C. while film #4 100% polypropylene has a melting point at 157° C. Film #5 displayed both peaks at 58° C. (poly(ethylene glycol)) and 157° 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° 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° C. and one for polypropylene at 157° 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° C. and one for polypropylene at 158° 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 (Tg) 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 Tg of about −6° C. while pure poly(ethylene glycol) exhibits a Tg at about −30° C. DSC data from film #5 exhibit two distinct Tg's, which correspond to the respective polymers (6° C. for polypropylene and −30° 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°) and 3) the fractured film cross-section at a 90° angle with respect to orientation #2 (90°). 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° F. and 10% relative humidity (“Rh”) and another chamber was preset for 72° 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)×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.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1481971 *17 May 192129 Jan 1924Jasper WhitingMethod of and means for controlling the humidity within containers
US1532831 *17 May 19227 Apr 1925Marion G MastinPreserving and packing of foods
US2202742 *2 Nov 193728 May 1940Jesse C MccorkhillMoisture absorbent
US2511666 *9 Oct 194813 Jun 1950Gen ElectricAir dehumidifier for compartments
US2638179 *6 Jan 195012 May 1953Edward M YardDrying capsule
US2991500 *17 Jun 195811 Jul 1961Hagen NorbertMethod and apparatus for making plastic containers
US3013308 *8 Oct 195719 Dec 1961Plax CorpMethod for molding and assembling dispenser fitment
US3101242 *1 Feb 196120 Aug 1963V L Smithers Mfg CompanyProcess of making flexible absorbent material
US3156402 *3 Jul 196110 Nov 1964Continental Can CoLiquid absorbing and concealing device
US3245946 *29 Apr 195912 Apr 1966Union Carbide CorpRubber and plastic formulations and process
US3256411 *17 Feb 196414 Jun 1966Mahrdt William FTime delay relay
US3322355 *1 Mar 196530 May 1967James G BryantDisintegrating machine
US3326810 *16 Nov 196420 Jun 1967Grace W R & CoDesiccant package
US3375208 *26 Jul 196726 Mar 1968Esb IncMethod for preparing a microporous thermoplastic resin material
US3537676 *20 Dec 19673 Nov 1970Valve Corp Of AmericaMold apparatus for closure with integral cap
US3567085 *2 Dec 19682 Mar 1971Flores James GNeck-supported pill container
US3687062 *13 Mar 197029 Aug 1972William J FrankApparatus for crushing and disposing of cans and glass containers
US3704806 *6 Jan 19715 Dec 1972Le T Im LensovetaDehumidifying composition and a method for preparing the same
US3730372 *19 Nov 19711 May 1973Automatic Liquid PackagingPlastic container
US3750966 *30 Jun 19717 Aug 1973Control Prod CorpSyringe destructing device
US3804282 *24 May 197216 Apr 1974Automatic Liquid PackagingContainer and cap construction
US3833406 *7 Aug 19723 Sep 1974Owens Illinois IncClosed container with desiccant coating on inside surface thereof
US3881026 *14 Jun 197129 Apr 1975Nat Patent Dev CorpPowdered water-insoluble polymers containing absorbed additives
US3926379 *4 Oct 197316 Dec 1975Dryden CorpSyringe disintegrator
US3929295 *1 Nov 197330 Dec 1975Ippolito MadelineApparatus for destroying syringes and like articles
US3931067 *16 Aug 19746 Jan 1976Amerace CorporationHydrophobic microporous materials and process for producing same
US4013566 *7 Apr 197522 Mar 1977Adsorbex, IncorporatedFlexible desiccant body
US4021388 *10 Mar 19763 May 1977Coloroll LimitedBiodegradable
US4029830 *1 May 197514 Jun 1977The Fujikura Cable Works, Ltd.Method of manufacturing insulated electric power cables
US4036360 *12 Nov 197519 Jul 1977Graham Magnetics IncorporatedPackage having dessicant composition
US4081397 *3 Dec 197128 Mar 1978P. R. Mallory & Co. Inc.Elastomeric matrix with alkaline earth oxide
US4165743 *29 Nov 197628 Aug 1979Akzona IncorporatedRegenerated cellulose fibers containing alkali metal or ammonium salt of a copolymer of an alkyl vinyl ether and ethylene dicarboxylic acid or anhydride and a process for making them
US4201209 *24 May 19786 May 1980Leveen Harry HMolded hypodermic plunger with integral shaft and elastomeric head
US4240937 *3 Jan 197823 Dec 1980Akzona IncorporatedTampons
US4243767 *16 Nov 19786 Jan 1981Union Carbide CorporationHydroxy polymer, aminosilicon compound
US4284548 *29 Dec 197818 Aug 1981Union Carbide CorporationAmbient temperature curable hydroxyl containing polymer/silicon compositions
US4284671 *11 May 197918 Aug 1981Clopay CorporationPolyester compositions for gas and moisture barrier materials
US4387803 *21 Nov 198014 Jun 1983Mercil Robert AAbsorbent device for containers for sugar, salt, etc.
US4394144 *3 Sep 198119 Jul 1983Kaken Chemical Co., Ltd.Dehumidifying container
US4405360 *24 Jul 198020 Sep 1983Environmental Chemicals, Inc.Controlled release of herbicide compounds utilizing a thermoplastic matrix
US4407897 *10 Dec 19794 Oct 1983American Can CompanyFood packaging
US442541015 Sep 198210 Jan 1984American Can CompanyDrying agent in multi-layer polymeric structure
US4447565 *7 Dec 19818 May 1984The United States Of America As Represented By The United States Department Of EnergyBlending and curing mixture of thermosetting resin, microspheres, and dessicant
US4464443 *3 Oct 19837 Aug 1984American Can CompanyDrying agent in multi-layer polymeric structure
US4485204 *26 Aug 198127 Nov 1984Phillips Petroleum CompanyRecycling polyethylene terephthalate bottles
US4533576 *3 Aug 19836 Aug 1985Toyo Seikan Kaisha LimitedComposite material for packaging containers
US4547536 *30 Jul 198415 Oct 1985Phillips Petroleum CompanyPolyalkylene terephthalate, poly (1-alkene), mineral oil and a dessicant; beverage bottles
US4554297 *18 Apr 198319 Nov 1985Personal Products CompanyBody fluid absorbers
US4573258 *9 Jan 19854 Mar 1986Atsugi Motor Parts Co., Ltd.Method of manufacturing motor
US4665050 *13 Aug 198412 May 1987Pall CorporationThermoplastic resin
US4686093 *13 Apr 198411 Aug 1987Union Carbide CorporationMolecular sieve compositions with aluminum, phosphorus and at least two other elements
US4725393 *30 Sep 198616 Feb 1988Kabushiki Kaisha Kawakami SeisakushoMethod for vacuum compression of laminated sheet material
US4770944 *3 Oct 198313 Sep 1988American Can CompanyPolymeric structure having improved barrier properties and method of making same
US4772300 *4 Apr 198520 Sep 1988Multiform Desiccants, Inc.Adsorbent cartridge
US4783056 *10 Nov 19868 Nov 1988Abrams Robert SProcess for making an aseptic vial and cap
US4783206 *18 Sep 19878 Nov 1988Multiform Desiccants, Inc.For containers of pills, medicinal capsules
US4792484 *13 May 198720 Dec 1988Kuraray Co., Ltd.Composition, process for producing the same and multi-layer structure
US4834234 *2 May 198830 May 1989Boehringer Mannheim GmbhContainer for test strips
US4969998 *23 Apr 198413 Nov 1990W. L. Gore & Associates, Inc.Composite semipermeable membrane
US4994312 *27 Dec 198919 Feb 1991Eastman Kodak CompanyShaped articles from orientable polymers and polymer microbeads
US507890922 May 19907 Jan 1992Sasaki Chemicals Co., Ltd.Moisture-absorbent compositions and molded items
US5114003 *28 Mar 199119 May 1992E. I. Du Pont De Nemours And CompanyTablet vial with desiccant in bottom
US5118655 *20 Mar 19912 Jun 1992Western Water International, Inc.Water treatment; purification by using mixture of aluminum silicate, diatomite, activated charcoal, catalytic chlorine removal media, tri-sodium phosphate and bone charcoal
US5128182 *12 Sep 19917 Jul 1992The James River CorporationFor food packaging
US5130018 *22 Sep 198814 Jul 1992Dewatering Systems International, Inc.Desiccation system with coupled tether and protective cage
US5143763 *11 Jul 19911 Sep 1992Toray Industries, Inc.Oxygen absorbant composition and a permeable film covering the composition
US5154960 *21 Jun 199013 Oct 1992Eileen MucciDrapeable soft odor absorbing sheet material
US5228532 *22 Jan 199220 Jul 1993Itw-NifcoBattery hold down strap
US5242652 *4 Dec 19917 Sep 1993Entre PrisesUsing a flexible molding skin having an imprint face arranged inside an airtight compartment
US5267646 *28 Oct 19917 Dec 1993Otsuka Pharmaceutical Factory, Inc.Containers having plurality of chambers
US5286407 *24 Apr 199115 Feb 1994Mitsubishi Gas Chemical Company, Inc.Oxygen absorbent composition and method of preserving article with same
US528853227 Oct 199222 Feb 1994Viskase CorporationTransferable modifier-containing film
US5304419 *9 Mar 199219 Apr 1994Alpha Fry LtdElectronics; pressure sensitive adhesive and desiccant
US5320778 *14 Oct 199314 Jun 1994Cortec CorporationVapor phase corrosion inhibitor-desiccant material
US5344589 *14 Oct 19936 Sep 1994Cortec CorporationVapor phase corrosion inhibitor-desiccant material
US5393457 *14 Oct 199328 Feb 1995Miksic; Boris A.Vapor phase corrosion inhibitor-desiccant material
US5399609 *23 Jul 199321 Mar 1995E. I. Du Pont De Nemours And CompanyMoisture indicating molding resins
US5415907 *18 Oct 199016 May 1995Mitsubishi Gas Chemical Company, Inc.Inhibitor parcel and method for preserving electronic devices or electronic parts
US543221419 Nov 199311 Jul 1995Airsec Industries, Societe AnonymePolymer-based dehydrating materials
US549415529 Jun 199427 Feb 1996Pilkington Barnes Hind, Inc.Incorporation of absorbents during extraction and/or hydration of hydrogel materials used as ophthalmic devices
US5496397 *7 Dec 19945 Mar 1996Semco IncorporatedDesiccant-coated substrate and method of manufacture
US5518761 *5 Jun 199521 May 1996Nippon Shokubai Co., Ltd.Spreading a resin in a layer on a substrate and treatment with steam and water the resin containing sodium acrylate and acrylic acid crosslinked with trimethylolpropane triacrylate
US5551141 *8 Sep 19943 Sep 1996Carnaudmetalbox PlcMethod of injection moulding a polymeric material insert into a metal shell
US5580369 *30 Jan 19953 Dec 1996Laroche Industries, Inc.Adsorption air conditioning system
US5596051 *24 Jun 199421 Jan 1997Basf AktiengesellschaftMicrocapsules, the production and use thereof
US5633351 *1 Nov 199427 May 1997Neorx CorporationTargeting protein-diagnostic/therapeutic agent conjugates having Schiff base linkages
US5656503 *15 Sep 199412 Aug 1997Unilever Patent Holdings B.V.Test device for detecting analytes in biological samples
US5773105 *7 Mar 199630 Jun 1998United Catalysts Inc. - DesiccantsAbsorbent packet
US5814136 *15 Apr 199729 Sep 1998Stanhope Products CompanyDesiccant container
US59119375 Mar 199615 Jun 1999Capitol Specialty Plastics, Inc.Packaging material having a desiccant contained therein
US608035029 May 199827 Jun 2000Capitol Specialty Plastics, Inc.Blending a functionalized polymer and a hydrophilic channeling agent, reacting, blending silica gel disiccant into polymeric reaction product, solidifying the desiccant agent entrained polymer-channeling agent, forming the shaped article
US61240056 Jun 199726 Sep 2000Chisso CorporationFluoro-substituted alkyl ether compounds, liquid crystal compositions and liquid crystal display devices
US612400629 May 199826 Sep 2000Capitol Specialty Plastics, Inc.Modified polymer having channels which act as controlled transmission passages through polymer; packaging materials which provide controlled environment
US61302635 Mar 199710 Oct 2000Capitol Specialty Plastics, Inc.Desiccant entrained polymer
US617495218 Sep 199816 Jan 2001Capitol Specialty Plastics, Inc.Water soluble polymer, dessicating agent and hydrophilic agent
US617718318 Sep 199823 Jan 2001Capitol Specialty Plastics, Inc.Used to form desired shaped article such as plug type inserts and liners for closed containers, or it may be formed into film, sheet, bead or pellet
US621425527 Jul 199810 Apr 2001Capitol Specialty Plastics, Inc.Desiccant entrained polymer
US622144629 May 199824 Apr 2001Capitol Specialty Plastics, IncModified polymers having controlled transmission rates
US627973615 Jun 199928 Aug 2001Capitol Specialty Plastics, Inc.Barrier pack having an absorbing agent applied to the interior of the pack
US648623114 Feb 200026 Nov 2002Csp Technologies, Inc.Co-continuous interconnecting channel morphology composition
US661340530 Mar 20012 Sep 2003Csp Technologies, Inc.Monolithic composition having the capability of maintaining constant relative humidity in a package
DE4013799A1 *28 Apr 199031 Oct 1991Gaplast GmbhBehaelter und behaelterverschluss aus kunststoff, insbesondere fuer arznei- und genussmittel
EP0172774A2 *20 Aug 198526 Feb 1986Kabushiki Kaisha TOPCONOphthalmologic photographing apparatus
EP0225593A2 *3 Dec 198616 Jun 1987Kaken Pharmaceutical Co., Ltd.Dehumidifying material
EP0560410A2 *26 Apr 198815 Sep 1993Unilever N.V.A test device for performing specific binding assays
EP0824480A117 Apr 199625 Feb 1998Capitol Vial, Inc.Desiccant material included in a closed container
WO1996029603A1 *23 Feb 199626 Sep 1996Unipath LtdAssay devices
WO1996033108A1 *17 Apr 199624 Oct 1996Capitol Vial IncDesiccant material included in a closed container
WO1997027483A1 *24 Jan 199731 Jul 1997Multisorb Tech IncMedical diagnostic test strip with desiccant
WO1997032663A1 *5 Mar 199712 Sep 1997Capitol Vial IncDesiccant entrained polymer
WO1998039231A1 *5 Mar 199811 Sep 1998Capitol Vial IncDesiccant entrained polymer
Non-Patent Citations
Reference
1"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.
213p-Sep. 29, 2004-CSP Technologies Inc. 's Corrected First Supplemental Response To Interrogatory No. 5.
3Consent Judgment And Dismissal With Prejudice Feb. 9, 2007-4pgs.
4Counterclaims Of Defendant CSP Technologies, Inc. dated Apr. 20, 2005-10 Pgs.
5Cover Sheet For The Deposition and Deposition Of Edith Mathiowitz Oct. 29, 2004-152pgs.
6Cover Sheet For The Deposition and Deposition Of Ihab Hekal Sep. 24, 2004-90pgs.
7Cover Sheet For The Deposition Designation and Deposition Of Barry Schindler Jul. 7, 2004-121pgs.
8Cover Sheet For The Deposition Designation and Deposition Of David Holbrook Dec. 3, 2004 85pgs.
9Cover Sheet For The Deposition Designation and Deposition of Didier Lancesseur Oct. 28, 2004-85pgs.
10Cover Sheet For The Deposition Designation and Deposition Of Eric Judek Dec. 21, 2004-122pgs.
11Cover Sheet For The Deposition Designation and Deposition Of Ihab Hekal Sep. 23, 2004-147pgs.
12Cover Sheet For The Deposition Designation and Deposition Of Jonathan Freedman Jul. 13, 2004-71pgs.
13Cover Sheet For The Deposition Designation and Deposition Of Jonathan Freedman Jul. 13, 2004-77pgs.
14Cover Sheet For The Deposition Designation and Deposition Of Klaus Langer Apr. 26, 2006-78 pgs.
15Cover Sheet For The Deposition Designation and Deposition Of Klaus Langer-Oct. 27, 2004-93pgs.
16Cover Sheet For The Deposition Designation and Deposition Of Klaus Langer-Oct. 28, 2004-57pgs.
17Cover Sheet For The Deposition Designation and Deposition Of Peter Sagona-Sep. 23, 2004-79pgs.
18Cover Sheet For The Deposition Designation and Deposition Of Pierre Rousseau-Dec. 1, 2004-51pgs.
19Cover Sheet For The Deposition Designation and Deposition Of Sumeet Kumar-Sep. 8, 2004-35pgs.
20Cover Sheet For The Deposition Designation and Deposition Of William Spano Oct. 11, 2005-123 pgs.
21Cover Sheet For The Deposition Designation Of Didier Lancesseur Apr. 25, 2006 84pgs.
22Cover Sheet For The Deposition Of Robert Garren-Jul. 8, 2004-135pgs.
23CSP Technologies' Answer, Affirmative Defenses And Counterclaims To Sud-Chemie Inc.'s Second Amended Complaint dated May 2, 2005-83pgs.
24CSP 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.
25CSP Technologies Memorandum In Support Of Its Motion For Partial Summary Judgment Of Infringement dated Oct. 21, 2005 22 pgs.
26CSP Technologies, Inc. Drug Master File No. 14789 Feb. 3, 2003 66pgs.
27CSP Technologies, Inc. 's Proposed Findings Of Fact And Conclusions Of Law, dated Jun. 21, 2006 52pgs.
28CSP 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.
29CSP Technologies, Inc.'s Opposition to Süd-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.
30CSP 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.
31CSP's Opposition To SCI's Motion For Reconsideration dated Sep. 18, 2006 6pgs.
32CSP's Response To SCI's Post-Trial Reply Brief dated Aug. 8, 2006, 4pgs.
33CSP's Response To SCI's Trial Brief And Proposed Findngs Of Fact And Conclusions Of Law, dated Jul. 17, 2006 29 pgs.
34CSP's Responses to SCI's Third Set of Interrogatories (Nos. 7-11) Mar. 31, 2004.
35CSP's Second Supplemental Objections And Responses To SCI's Second Set Of Interrogatory (No. 6) dated Dec. 3, 2004 6pgs.
36CSP's Sur-Reply to SCI's Second Motion for Summary Judgment of Invalidity, dated Dec. 16, 2005 11pgs.
37CSP's Trial Brief, dated Jun. 21, 2006, 60pgs.
38CV Of Donald R. Paul 37pgs May 17, 2005.
39CV of Edith Mathiowitz Jun. 19, 1998.
40Declaration of Donald R. Paul, PhD, In Support of SCI's Second Motion for Summary Judgment of Non-Infringement, 4pgs Oct. 25, 2004.
41Declaration Of Jean Pierre Giraud 4pgs Jul. 6, 2005.
42Deposition Of Glenn H. Fredrickson dated Aug. 24, 2005 10pgs.
43Deposition Transcript of Donald Paul, PhD Sep. 8, 2005-7pgs.
44Deposition Transcript of Robert Abrams, Nov. 17, 2004.
45Deposition Transcript Of Sherman David Winters dated Sep. 7, 2005.
46Entry On Claim Construction dated Mar. 14, 2005.
47Expert Report Of Christopher W. Macosko Dated May 20, 2005 155 Pgs.
48Expert Report of Donald R. Paul, PhD, on behalf of Plaintiff Süd-Chemie Inc. Pursuant to Fed.R.Civ.Pro.26(a)(2)(B), 4pgs dated May 20, 2005.
49First Supplemental Expert Report Of Christopher W. Macosko 51pgs Aug. 22, 2005.
50Frederickson et al., "Project on Morphology Control in Polymer-Polymer-Particle Alloys" undated, 2 pgs Mar. 2000.
51Fredrickson, "A New Method For Stabilizing Co-Continuous Polymer Blend Morphologies", For Capitol Specialty Plastics, 21 Pgs Mar. 2000.
52Galloway, 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.
53Giles, David, "Differential Scanning Calorimetry (DSC) tests done at the University of Minnesota" results for CSP Technologies, Inc. May 20, 2005, 8pgs.
54Kärger Et Al., "Intracrystalline Self-Diffusion Of Water And Short-Chain-Length Paraffins In A-Type Zeolites", Zeolites, vol. 9, May 1989, 3pgs.
55Letters 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.
56Massey, "Permeability Properties Of Plastics And Elastomers, A Guide To Packaging And Barrier Materials", 2nd Ed., 2003, Plastics Design Library, 6pgs.
57Mathiowitz Et Al., "Novel Desiccants Based On Designed Polymeric Blends", Journal Of Applied Polymer Science, vol. 80, 317-327 2001.
58MVTR 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.
59Nago et al., "Microporous Polypropylene Sheets Containing Caco3 Filter : Effects Of Stretching Ratio And Removing Caco3 Filler", Tokuyama Corp. Dec. 3, 1996.
60Official Reporters Transcript Of Markman Hearing-105pgs Mar. 4, 2004.
61Order Declaring The Defendant's Patents Valid And Infringed By Aug. 4, 2006.
62Plaintiff Süd-Chemie Inc.'s Reply To The Second Amended May 2, 2005.
63Plaintiff Süd-Chemie Inc.'s Reply To The Third Amended Counterclaims Of Defendant CSP Technologies, Inc. dated May 2, 2005-16pg.
64Plaintiff, Aug. 4, 2006-108 pgs.
65Pötschke 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.
66Provisional Application for "Absorbent Polymeric Composition", Certificate of Express Mail, Provisional Application Transmittal Sheet, 20 pgs. Specification, 7 sheets drawings, 2 postcards Apr. 22, 2002.
67Rebuttal Of Expert Report Of Christopher W. Macosko, Jul. 7, 2005, 147 Pgs.
68SCI'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.
69SCI's Fourth Supplemental Objections and Responses to CSP's First Set of Interrogatories Nos. 1-11, 85pgs, Oct. 21, 2004.
70SCI's Objections And Responses To CSP's First Set Of Requests For Admissions Nos. 1-26-Oct. 21, 2004-11pgs.
71SCI's Objections And Responses To CSP's Second Set Of Interogatories Nos. 12-23 dated Dec. 3, 2004 24pgs.
72SCI'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.
73SCI'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.
74SCI's Opposition to CSP's Motion in Limine to Exclude SCI's Allegedly Untimely Expert Reports Apr. 6, 2006 12 pgs.
75SCI's Post-Trial Brief, dated Jun. 26, 2006 60pgs.
76SCI's Post-Trial Reply, dated Jul. 17, 2006 27pgs.
77SCI's Proposed Findings Of Fact And Conclusions Of Law, dated Jun. 21, 2006 80 pgs.
78SCI's Reply Brief in Support of its Motion for Summary Judgment of Patent Invalidity, dated Dec. 2, 2005-30 pgs.
79SCI'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.
80SCI's Sixth Supplemental Objections And Responses To CSP's First Set Of Interrogatories Nos. 1-11 dated May 3, 2005 95pgs.
81Süd-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.
82Süd-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.
83Trial Transcript May 15, 2006 48pgs.
84Trial Transcript May 17, 2006 47pgs.
85Trial Transcripts May 16, 2006 48pgs.
86Trial Transcripts May 18, 2006 53pgs.
87Trial Transcripts May 19, 2006 42pgs.
88U.S. Patent Office File Wrapper, U.S. Appl. 09/086,880, Filed May 29, 1990, 143 Pgs.
89U.S. Patent Office File Wrapper, U.S. Appl. No. 08/161,298 Filed Mar. 5, 1996-193 Pgs.
90U.S. Patent Office File Wrapper, U.S. Pat. 6,124,006 Issued Sep. 26, 2000, 146Pgs.
91U.S. Patent Office File Wrapper, U.S. Pat. 6,177,183 Issued Jan. 23, 2000, 246 Pgs.
92U.S. Patent Office File Wrapper, U.S. Pat. 6,194,079 Issued Feb. 27, 2001, 254 Pgs.
93U.S. Patent Office File Wrapper, U.S. Pat. 6,214,255 Issued Apr. 10, 2001, 160 Pgs.
94U.S. Patent Office File Wrapper, U.S.Appl. No. 08/424,996 Filed Apr. 19, 1995-317 Pgs.
95U.S. Patent Office Technology Fair, Jul. 27, 2000, Patent Center 1700, Presentation Abstracts and Presenter Biographies, 28pgs.
96U.S. Patent Office Wrapper, U.S. Pat. 6,488,231 Issued Nov. 26, 2002, 121 Pgs.
97US 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.
98US Patent Office File Wrapper, US Pat. 6,130,263 Issued Oct. 26, 2000 200Pgs.
99USPTO File Wrapper of US Publication No. 2005/0089687-211 pgs. Dec. 24, 2002.
Classifications
U.S. Classification523/102, 524/503, 523/122, 524/387, 523/132
International ClassificationC08L101/00, C08L23/10, C08L77/00, B01J20/28, C08J9/26, C08L23/08, C08L29/04, F26B21/08, C08L71/02, B29C45/16, C08L69/00, B65D81/26, C08L23/02, A01N25/00, A61L9/01
Cooperative ClassificationC08L77/00, C08L23/02, C08L71/02, B29C45/16, B01J20/28042, F26B21/083, C08L101/00, C08L23/0861, B65D81/264, C08L69/00, B01J20/28033, C08J9/26, B01J20/28014, B65D81/266, C08L29/04, C08L23/10
European ClassificationB01J20/28D28, B01J20/28D, B01J20/28D24, C08L69/00, C08L23/10, C08L23/02, C08L77/00, B65D81/26F, B65D81/26E, B29C45/16, F26B21/08B, C08J9/26
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