WO2006073662A9 - Polyhedral oligomeric silsesquioxanes and polyhedral oligomeric silicates barrier materials for packaging - Google Patents
Polyhedral oligomeric silsesquioxanes and polyhedral oligomeric silicates barrier materials for packagingInfo
- Publication number
- WO2006073662A9 WO2006073662A9 PCT/US2005/044284 US2005044284W WO2006073662A9 WO 2006073662 A9 WO2006073662 A9 WO 2006073662A9 US 2005044284 W US2005044284 W US 2005044284W WO 2006073662 A9 WO2006073662 A9 WO 2006073662A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- silicon containing
- adhesion
- physical property
- incorporation
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1233—Organic substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- This invention relates generally to methods for enhancing the barrier properties of polyethylene, polypropylene, polyamide, polyester terephthalate and natural polymers such as cellulose and polylactic acid polymers. More particularly, it relates to the incorporation of nanostructured chemicals such as polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicates (POS) for gas and moisture barrier control in multilayered polymer laminate packaging or bottles for foods, beverages, pharmaceuticals, and medicines.
- the applications for such materials include replacement of metallized polymer packaging, replacement of metal cans, and replacement of packaging that contains discreet adhesive layers and a discreet silica layer.
- the invention is related to use of polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, silicones or metallized- polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, silicones as alloyable agents in polypropylene (PP), polyamide (PA), polyestererephthalate (PET).
- PP polypropylene
- PA polyamide
- PET polyestererephthalate
- polyhedral oligomeric silsesquioxane, silsesquioxane, polyhedral oligomeric silicate, silicates, silicones are hereafter referred to as "silicon containing agents.” Silicon containing agents have previously been utilized to complex metal atom(s) as reported in U.S. Patent No. 6,441 ,210. As discussed in U.S. Patent No.
- silicon containing agents are useful for the dispersion and alloying of silicon and metal atoms with polymer chains uniformly at the nanoscopic level.
- Silicon containing agents can be converted in the presence of atomic oxygen to form a glass like silica layer.
- the use of such silicon containing agents to form oxidation protective glass layers was discussed in U.S. Patent No. 6,767,930.
- the use of such silicon containing agents to form fire protective surface char coatings has been described in U.S. Patent No. 6,362,279. Silicon containing were also described to be useful in the formation of permeable porous membranes as discussed in U.S. Patent No. 6,425,936.
- silicon containing agents are also useful for the formation of gas and liquid barriers in multilayered thin film packaging products.
- the silicon containing agents are themselves effective when alloyed into a polymer but especially effective for the in situ formation of nanoscopically thin glass barriers upon their exposure to oxygen plasma, ozone, an oxidizing flame, or a hot oxidizing gas such as air.
- Advantages of the use of silicon containing agents include their ability to reduce or plug free volume in polymers, thus reducing permeability, or when converted into a nanoscopically thin glass layer the permeability is reduced by the impermeability of the layer.
- silicon agents containing metals can provide stabilization to the polymers through absorption of photon and particle radiation that could otherwise damage the polymer and accelerate its degradation. All of these factors contribute to a packaging material with superior barrier and transparency properties over those achieved using prior art methods.
- a number of prior art methods are known to produce packaging with low barrier properties to gases and moisture. Such methods include the deposition of metals and thin glass coatings on polymers as described in U.S. Patent 6,720,097. While effective, this approach is not amenable to a wide range of high speed molding and extrusion processing. This method also suffers from poor interfacial bonding between the glass or metal and polymer layers.
- a popular prior art approach has also involved the incorporation of two dimensional platelet materials such as clays, micas, talcs, glass flakes, carbon mesophases and tubes (U.S. Patent Nos. 6,376,591 and 6,387,996).
- This prior art is deficient in the ability to incorporate sufficiently high uniformities of the additive to provide both a high barrier while retaining optical transparency. Therefore, a compromise in barrier level is accepted in order to accommodate transparency and decorative appearance.
- a further limitation of the latter approach has been the use of naturally derived fatty surfactants such as tallows in order to render the two dimensional platelet material compatible with the polymer layer.
- silicon containing agents of most utility in this work are best exemplified by those based on low cost silicon compounds such as silsesquioxanes, polyhedral oligomeric silsesquioxanes, and polyhedral oligomeric silicates.
- Figure 1 illustrates some representative examples of silicon compounds containing siloxane, silsesquioxane, and silicate examples.
- the R groups in such structures can range from H, to alkane, alkene, alkyne, aromatic and substituted organic systems including ethers, acids, amines, thiols, phosphates, and halogenated R groups.
- the structures and compositions are also intended to include metallized derivatives where metals ranging from high to low Z can be incorporated into the structures.
- the silicon containing agents all share a common hybrid (i.e., organic-inorganic) composition in which the internal framework is primarily comprised of inorganic silicon- oxygen bonds. The incorporation of such agents provides a barrier to moisture and oxygen though the blockage of amorphous regions and free volume contain in the solid state structure of the polymers.
- Barrier properties can be improved further via mild in situ oxidation of the nanoscopic silicon entities into nanoscopically thin silica glasses.
- the glassification process may be carried out during film processing or after processing.
- the exterior of a nanostructure is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic polymers.
- R reactive and nonreactive organic functionalities
- the present invention describes a new series of polymer additives and their utility in the formation of gas and moisture barriers in polymers and on polymer surfaces.
- the resulting nano-alloyed polymers are wholly useful by themselves, in combination with other polymers, or in combination with macroscopic reinforcements such as fiber, clay, glass, metal, mineral, and other particulate fillers, inks, and pigments.
- the nano-alloyed polymers are particularly useful for producing multilayered packaging with enhanced oxygen and moisture barrier properties, printability, stain, acid and base resistance.
- compositions presented herein contain two primary material combinations: (1 ) silicon containing agents including nanostructured chemicals, nanostructured oligomers, or nanostructured polymers from the chemical classes of silicones, polyhedral oligomeric silsesquioxanes, polysilsesquioxanes, polyhedral oligomeric silicates, polysilicates, polyoxometallates, carboranes, boranes; and (2) manmade thermoplastic polymers such as polypropylene, polyamides, and polyesters.
- a preferred method of incorporating nanostructured chemicals into thermoplastics is accomplished via melt mixing of the silicon containing agents into the polymers.
- ком ⁇ онент containing agent can be tailored to show compatibility or incompatibility with selected sequences and segments within polymer chains and coils.
- nanoscopic silicon containing agents can displace gas molecules within a polymer and thereby decrease the solubility of a gas within a polymer.
- in situ glass glazings on articles molded from polymers alloyed with silicon containing agents is carried out by exposure of the articles to oxygen plasma, ozone, or other highly oxidizing mediums. These chemical oxidation methods are desirable as they are current industrial processes and they do not result in heating of the polymer surface. There are no topological constraints, or decorative restrictions on the molded articles. Post processing, the parts contain nanometer thick surface glass layers. The most efficient and thereby preferred oxidation method is oxygen plasma. However for alloys where the R on the silicon containing agent is H, methyl or vinyl, they can be converted to glass upon exposure to ozone, peroxide, or even hot steam.
- a reliable alternate to the above methods is the use of an oxidizing flame.
- the choice of method is dependent upon the chemical agent - polymer alloy system, loading level of the silicon containing chemical agent, surface segregation of agent, the thickness of the silica surface desired and manufacturing considerations.
- a picture of the nanoscopic level dispersion of silicon containing agent in a polymer is shown in Figure 2.
- a nanoscopically thin layer of glass from 1 -500 nm will result, and preferably from 1 -100 nm, depending upon the oxidation conditions used.
- the thickness of the layer formed may vary with the required properties of the glass layer (ex ⁇ impermeability, scratch resistance, transparency, radiation attenuation, etc.) If the silica containing agent contained a metal, then the metal will also be incorporated into the glass layer.
- Advantages derived from the formation of a nanoscopic glass surface layer include barrier properties for gases and liquids, improved chemical and oxidative stability, flammability reduction, improved electrical properties, improved printability, improved stain and scratch resistance.
- the nanoscopically thin layer of silica is seamlessly integrated with the bulk virgin polymer and is both ductile and capable of being stored on rolls and laminated into multilayer packages.
- FIG. 1 shows representative structural examples of nonmetallized silicon containing agents.
- FIG. 2 illustrates the ability to uniformly disperse nanostructured silicon agents at the 1-3 nm level at the surface and the bulk of a polymer.
- FIG. 3 illustrates the ability of metallized silicon agents to selectively absorb damaging radiation.
- FIG. 4 illustrates the chemical process of oxidative conversion of a silicon containing agent into a fused nanoscopically thin glass layer.
- FIGS. 5(A) to 5(F) illustrate preferred methods of incorporating nanostructured silicon containing agents into plastic multilaminate packaging.
- Polysilsesquioxanes may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.
- POSS and POS nanostructure compositions are represented by the formula: [(RSiOi .5) n ] ⁇ # for homoleptic compositions
- R is the same as defined above and X includes but is not limited to OH, Cl 1 Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR 2 )
- isocyanate NCO
- R isocyanate
- M metallic elements within the composition that include high and low Z metals and in particular Al, B, Ce, Ni, Ag, Ti.
- composition forms a nanostructure and the symbol # refers to the number of silicon atoms contained within the nanostructure.
- the value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It should be noted that ⁇ # is not to be confused as a multiplier for determining
- the present invention teaches the use of silicon containing agents as alloying agents for the design and preparation of polymers and polymer laminate packages with barrier properties toward oxygen and water. It is recognized that additional barrier can be obtained through the in situ formation of glass layers on the polymeric materials through the in situ oxidation of the nanoscopic silicon containing agents.
- the keys that enable silicon containing agents such as nanostructured chemicals to function in this capacity include: (1 ) their unique size with respect to polymer chain dimensions, and (2) their ability to be compatibilized and uniformly dispersed at the nanoscopic level with polymer systems to overcome repulsive forces that promote incompatibility and expulsion of the nanoreinforcing agent by the polymer chains, (3) the hybrid composition and its ability glassify upon exposure to selective oxidants, (4) the ability to chemically incorporate metals into the silica agent and into the corresponding glass rendered therefrom.
- the factors to effect selection of a silicon containing agent for permeability control and glassification include the nanosizes of nanostructured chemicals, distributions of nanosizes, and compatibilities and disparities between the nanostructured chemical and the polymer system, the loading level of the silica agent, the thickness of the silica layer desired, and the optical and physical properties of the polymer.
- Silica agents such as the polyhedral oligomeric silsesquioxanes illustrated in Figure 1 , are available as solids and oils and with or without metals. Both forms dissolve in molten polymers or in solvents, or can be reacted directly into polymers or can themselves be utilized as a binder material. For POSS, dispersion appears to be
- thermodynamically governed by the free energy of mixing equation ( ⁇ G ⁇ H-T ⁇ S).
- thermodynamic forces driving dispersion are also contributed to by kinetic mixing forces such as occur during high shear mixing, solvent blending or alloying.
- the kinetic dispersion is also aided by the ability of some silica agents to melt at or near the processing temperatures of most polymers. Therefore, by controlling the chemical and processing parameters, nanoreinforcement and the alloying of polymers at the 1 .5 nm level can be achieved for virtually any polymer system as illustrated in Figure 2.
- Silica containing agents can also be utilized in combination with macroscopic fillers to render similar desirable benefits relative to enhancements of physical properties, barrier, stain resistance, acid and base resistance, and radiation absorption.
- metallized silica containing agents such as nickel, titanium, cerium, or boron
- Such metallized systems are of high value for stabilization of polymers against environmental degradation and degradation of contents such as vitamins, flavorants, colorant and other nutrients.
- the present invention shows that barrier property enhancements can be realized by the direct blending of silicon containing agents, preferably nanostructured chemicals, directly into polymers. This greatly simplifies the prior art processes. Furthermore, because silicon containing agents like nanostructured chemicals possess spherical shapes (per single crystal X-ray diffraction studies), like molecular spheres, and because they dissolve, they are also effective at reducing the viscosity of polymer systems.
- FIG. 4 illustrates the oxidation of silicones such as silsesquioxanes to glass.
- Silicon containing agents can be added to a vessel containing the desired polymer, prepolymer or monomers and dissolved in a sufficient amount of an organic solvent (e.g. hexane, toluene, dichloromethane, etc.) or fluorinated solvent to effect the formation of one homogeneous phase.
- an organic solvent e.g. hexane, toluene, dichloromethane, etc.
- fluorinated solvent e.g. hexane, toluene, dichloromethane, etc.
- the resulting formulation may then be used directly or for subsequent processing.
- Example 1 Solvent Assisted Formulation.
- Typical oxygen plasma treatments range from 1 second to 5 minutes under 100% power.
- Typical ozonolysis treatments range from 1 second to 5 minutes with ozone being administered through a CH 2 CI 2 solution with 0.03 equivalents O 3 per vinyl group.
- Typical steam treatments range from 1 second to 5 minutes.
- Typical oxidizing flame treatments range from 1 second to 5 minutes.
- Example 3 Packaging Performance Based on Design A series of silicon containing additives were incorporated into silicone and epoxy thermosets, polyolefin and polycarbonate thermoplastics and their absorption characteristics were measured relative to incident dosages of UV-Vis, neutron, gamma and low energy photons.
- the primary advantage for the low Z alloyed polymers was observed for low energy photons ( ⁇ 1000 ev). The improvement is attributed to an increase in electron density in the material which provides shielding against the damaging effects of the incident radiation.
- the primary advantage for the high Z alloyed polymers was blockage of the high energy UV radiation from damaging and discoloring silicon and polycarbonates. The improvement is attributed to extension of the UV absorption characteristics of the glass layer to the 90-390 nm range.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Nanotechnology (AREA)
- Wrappers (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05857055A EP1838458A2 (en) | 2004-12-08 | 2005-12-07 | Polyhedral oligomeric silsequioxanes and polyhedral oligomeric silicates barrier materials for packaging |
JP2007545593A JP2008523219A (en) | 2004-12-08 | 2005-12-07 | Polyhedral oligomeric silsesquioxane and polyhedral oligomeric silicate barrier materials for containers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63449504P | 2004-12-08 | 2004-12-08 | |
US60/634,495 | 2004-12-08 |
Publications (3)
Publication Number | Publication Date |
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WO2006073662A2 WO2006073662A2 (en) | 2006-07-13 |
WO2006073662A3 WO2006073662A3 (en) | 2006-09-14 |
WO2006073662A9 true WO2006073662A9 (en) | 2006-10-12 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/044284 WO2006073662A2 (en) | 2004-12-08 | 2005-12-07 | Polyhedral oligomeric silsesquioxanes and polyhedral oligomeric silicates barrier materials for packaging |
Country Status (6)
Country | Link |
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EP (1) | EP1838458A2 (en) |
JP (1) | JP2008523219A (en) |
KR (1) | KR20070112112A (en) |
RU (1) | RU2007125640A (en) |
TW (1) | TW200635771A (en) |
WO (1) | WO2006073662A2 (en) |
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JP6137335B2 (en) * | 2013-01-03 | 2017-05-31 | 信越化学工業株式会社 | Water dispersion of hydrophilized silicone particles and method for producing the same |
JP6439684B2 (en) * | 2013-04-23 | 2018-12-19 | 三菱瓦斯化学株式会社 | Polyamide resin composition and molded body |
CN114716814B (en) * | 2022-05-13 | 2023-07-21 | 安徽康采恩包装材料有限公司 | High-barrier packaging material and preparation process thereof |
CN116144284B (en) * | 2023-04-24 | 2023-08-18 | 宁波长阳科技股份有限公司 | Raw material package, integrated adhesive film backboard, preparation method of integrated adhesive film backboard and photovoltaic module |
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TW436837B (en) * | 1998-11-16 | 2001-05-28 | Matsushita Electric Works Ltd | Field emission-type electron source and manufacturing method thereof and display using the electron source |
CN101427182B (en) * | 2004-04-27 | 2011-10-19 | 伊利诺伊大学评议会 | Composite patterning devices for soft lithography |
-
2005
- 2005-12-07 JP JP2007545593A patent/JP2008523219A/en not_active Withdrawn
- 2005-12-07 KR KR1020077015513A patent/KR20070112112A/en not_active Application Discontinuation
- 2005-12-07 TW TW094143125A patent/TW200635771A/en unknown
- 2005-12-07 EP EP05857055A patent/EP1838458A2/en not_active Withdrawn
- 2005-12-07 WO PCT/US2005/044284 patent/WO2006073662A2/en active Application Filing
- 2005-12-07 RU RU2007125640/12A patent/RU2007125640A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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TW200635771A (en) | 2006-10-16 |
KR20070112112A (en) | 2007-11-22 |
WO2006073662A3 (en) | 2006-09-14 |
EP1838458A2 (en) | 2007-10-03 |
JP2008523219A (en) | 2008-07-03 |
RU2007125640A (en) | 2009-01-20 |
WO2006073662A2 (en) | 2006-07-13 |
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