WO2006078625A1 - Preservative compositions for materials and method of preserving same - Google Patents

Preservative compositions for materials and method of preserving same Download PDF

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Publication number
WO2006078625A1
WO2006078625A1 PCT/US2006/001546 US2006001546W WO2006078625A1 WO 2006078625 A1 WO2006078625 A1 WO 2006078625A1 US 2006001546 W US2006001546 W US 2006001546W WO 2006078625 A1 WO2006078625 A1 WO 2006078625A1
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WO
WIPO (PCT)
Prior art keywords
preservative composition
methyltrichlorosilane
set forth
containing material
silane
Prior art date
Application number
PCT/US2006/001546
Other languages
French (fr)
Other versions
WO2006078625B1 (en
Inventor
Edwin Neal
Original Assignee
Woodholdings Environmental, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Woodholdings Environmental, Inc. filed Critical Woodholdings Environmental, Inc.
Priority to MX2007008740A priority Critical patent/MX2007008740A/en
Priority to EP20060718599 priority patent/EP1841321A4/en
Priority to CA 2595095 priority patent/CA2595095C/en
Publication of WO2006078625A1 publication Critical patent/WO2006078625A1/en
Publication of WO2006078625B1 publication Critical patent/WO2006078625B1/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/14Boron; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D15/00Woodstains
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612Non-macromolecular compounds
    • C09D5/1625Non-macromolecular compounds organic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00Purpose of the treatment
    • B27K2240/30Fireproofing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00Purpose of the treatment
    • B27K2240/70Hydrophobation treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02Processes; Apparatus
    • B27K3/15Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/156Combined with grafting onto wood fibres
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2525Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]

Definitions

  • the present invention relates generally to preservative compositions and, more particularly, to preservative compositions for materials and to a method for preserving the same.
  • Certain materials are susceptible to damage caused by the elements, especially water and insects (e.g., termites, certain types of ants, and other boring insects). For instance, exposure to water typically causes many materials, such as various wood products, insulation, newsprint, drywall, and masonry bricks, to crack, warp, check, as well as become discolored and mildewed. Also, water and/or insect damage often causes these materials to rot and decay. Typically, water and/or insect damage leads to the eventual replacement of the damaged section of the material at great expense, effort, and inconvenience.
  • preservative composition for various materials. It is also desirable to provide a preservative composition that preserves various materials effectively against water intrusion and damage. Further, it is desirable to provide a preservative composition that preserves materials effectively against insect intrusion and damage. Still further it is desirable to provide a preservative composition that is relatively inexpensive. It is also desirable to provide a preservative composition that is relatively easy to apply. Furthermore, it is desirable to provide a preservative composition that has a relatively short treatment time. Also, it is desirable to provide a preservative composition that provides a relatively long period of protection. Therefore, there is a need in the art to provide a preservative composition and method that meets these desires.
  • the present invention is a preservative composition for materials including at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms.
  • the present invention is a method for preserving a material including the steps of providing a composition having at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms, and contacting the material with the composition.
  • One advantage of the present invention is that a new preservative composition for various materials is provided. Another advantage of the present invention is that the preservative composition preserves various materials effectively against water intrusion and damage. Yet another advantage of the present invention is that the preservative composition preserves materials effectively against insect intrusion and damage. Still another advantage of the present invention is that the preservative composition is relatively inexpensive. A further advantage of the present invention is that the preservative composition is relatively easy to apply. Yet a further advantage of the present invention is that the preservative composition has a relatively short treatment time. Still a further advantage of the present invention is that the preservative composition provides a relatively long period of protection.
  • the present invention includes compositions, and methods of use therefor, for preserving, protecting, and treating subject materials so as to impart protection against various sources of damage, including, but not limited to water and insects.
  • the terms "preserving,” “protecting,” and “treating,” as those terms are used interchangeably herein, are meant to include any methods of, and compositions for, protecting subject materials from damage caused by any source, including, but not limited to water and insects.
  • subject material as used herein is meant to include any object that can be preserved, protected, and treated with the compositions of the present invention, including but not limited to wood products (i.e., products containing any amount of wood), insulation, paper used to coat insulation, drywall, newsprint, and masonry brick.
  • the preservative composition includes at least one silane-containing material and at least one solvent.
  • the preservative composition contains at least one silane-containing material.
  • Silanes are generally defined in a class of silicon-based materials, analogous to alkanes, that is, straight-chain, saturated paraffin hydrocarbons having the general formula Si>jH 2N+2 , wherein N is an integer equal to 1 or higher.
  • the silane-containing material is preferably in the form of trichloromethylsilane (chemical formula: CH 3 Cl 3 Si), although other forms of silane-containing materials are acceptable. Examples of other silane-containing materials useful in practicing the present invention include, without limitation:
  • Chloro(Chloromethyl)Dimethylsilane Chlorodiisopropyloctylsilane;
  • the preservative composition contains at least one solvent.
  • the solvent is in the form of a hydrocarbon.
  • hydrocarbons which are liquid at room temperature are acceptable.
  • hydrocarbons are hydrocarbons having molecules of at least five carbon atoms that include, without limitation, pentane, hexane, and heptane.
  • THF tetrahydrofuran
  • the preservative composition includes at least pesticide-containing material, at least one silane-containing material, and at least one solvent.
  • the pesticide-containing material is preferably in the form of boric anhydride (chemical formula: B 2 O 3 ), although other forms of boron-containing materials are acceptable.
  • borax chemical formula: Na 2 B 4 O 7 -H 2 O
  • disodium octaborate tetrahydrate chemical formula: Na 2 B 8 O 13 -H 2 O
  • Effective fungal and fire resistance can be obtained with a boron loading of 0.1 weight percent, based on the total weight of the subject material.
  • a loading of 1-2 weight percent of boron is generally required.
  • the present invention provides a product, and a method of using the same, to introduce pesticide-containing material such as boron into the subject material at levels of at least about 0.1 to at least about 7 weight percent and seal it to prevent environmental factors (e.g., rain) from leaching it from the interior of the subject material.
  • pesticide-containing material such as boron
  • other organic pesticide-containing materials other than boron may be used.
  • the preservative composition may include other additives.
  • Other additives such as paint or stain may be used.
  • the additives are carried with the hydrocarbon solvent and silane- containing material and penetrate the material being treated.
  • colorant may be an additive to the preservative composition to treat and color wood product. It should be appreciated that other types of organic additives may be used to treat the materials.
  • the preservative composition is prepared. Then, the preservative composition is applied to the material to be preserved. For instance, the preservative composition is topically applied to the material to be preserved.
  • the preservative composition of the present invention can be applied to preserve several types of various materials, including but not limited to the following: 1) wood materials, such as newsprint and other paper products; 2) insulation materials, such as paper-coated polyurethane- filled insulation; 3) drywall materials, such as sheet rock; 4) masonry materials, such as masonry brick; and 5) fibrous material such as cotton. It should be appreciated that, for specific wood products such as telephone poles and railroad ties, a lower hydrocarbon solvent may be used such as diesel fuel may be used in the preservative composition.
  • Example I The preparation of an illustrative preservative composition, in accordance with the general teachings of the present invention, is presented in Example I, below:
  • Example II In order to determine the effectiveness of the illustrative preservative composition prepared in Example I, a comparison test was performed between a treated portion and an untreated portion of a piece of plywood board. The results of the comparison test are presented in Example II, below:
  • Example III In order to further determine the effectiveness of the illustrative preservative composition prepared in Example I, a comparison test was performed between a treated portion and an untreated portion of a piece of hardwood. The results of the comparison test are presented in Example III, below:
  • Example II Several drops of the preservative composition prepared in Example I were applied to a solid piece of hardwood. The sample was allowed to sit for several minutes prior to exposing it to water. Upon drying, no white residue was observed on the surface of the sample. Water was repelled off both sides of the sample even though just one side was treated.
  • Example IV The preparation of another illustrative preservative composition, in accordance with the general teachings of the present invention, is presented in Example IV, below:
  • Example V In order to determine the effectiveness of the illustrative preservative composition prepared in Example IV, a comparison test was performed between a treated portion and an untreated portion of apiece of plywood board. The results of the comparison test are presented in Example V, below:
  • a piece of plywood, 5/8 inches x 5/8 inches x 3-1/2 inches was placed into a beaker and partially submerged into the preservative composition prepared in Example IV.
  • the beaker was covered for approximately 5 minutes. After 5 minutes, the piece of plywood was removed and allowed to air dry.
  • the volume of the preservative composition remaining in the beaker had been reduced by 2-3 ml, or about 10%. There was no visible white deposit on the surface of the plywood.
  • Surface samples were removed from both the treated and untreated portions of the plywood in order to evaluate them under a microscope. There was an observable difference between the samples.
  • the treated plywood appeared as though it had been coated in glass or white cotton coating. There was a difference in the appearance of the heartwood and the sapwood.
  • the cells of the untreated plywood appeared empty, while those of the treated wood appeared to be coated with glass.
  • the treated sample beaded up and looked like a jelly on the surface of the sample.
  • the run off water was readily absorbed on the untreated plywood.
  • a piece (1/2 inch x 1/2 inch x 3/4 inches) of this plywood was placed in a 100 ml beaker containing 10 ml of water and covered with a watch glass. The sample was allowed to sit undisturbed for 24 hours and then the plywood was removed from the water.
  • the FTIR of the water from the leaching experiment showed a slight peak @ 800 cm-1. The peak was not strongly defined as in the case of the silane reference peaks.
  • the treated plywood showed no sign of silanes on the surface after being soaked in water for 24 hours. It did, however, readily repel water on all sides. The cut surface also repelled water even though it was never in direct contact with the preservative composition. It was 1/2 inch to 3/4 inches away from the preservative composition.
  • the solution was stirred for 10 minutes and then stirring was ceased. A small amount of undissolved B 2 O 3 remained on the bottom of the flask.
  • a 500 milliliter aliquot was decanted into each of two 1 liter beakers and covered with a large watch glass.
  • a first set of wood blocks had the dimensions of 1 inch x 2 inches x 5/8 inches.
  • a second set of wood blocks were 3/4 inch cubes. The wood blocks from each sample were placed individually into their respective solutions.
  • a smaller watch glass was placed inside the beaker such that the weight of the watch glass kept the wood block samples completely submerged. The samples were allowed to stand in the solution for 1 hour. Some bubbling took place throughout the entire process. After the 1 hour treatment, the wood blocks were removed from the solution and allowed to air dry overnight.
  • the pieces of wood appeared to "smoke" while drying.
  • the smoke was believed to be hydrochloric acid. It is probably produced from the hydrolysis of the unreacted methyltrichlorosilane present on the surface of the wood.
  • the solution appeared turbid and slightly discolored following the treatment.
  • the appearance of the wood treated with the preservative composition as described above for 1 hour is gray or ashen in appearance. This is probably due to the boron. This feature is not present in the material treated for 5 to 10 minutes with the preservative composition as described above.
  • the boron- containing material is preferably impregnated into the subject material prior to, and separately from, impregnation by the silane-containing material.
  • THF was used initially as a solvent for the boron-containing material because it is commonly used in boron chemistry, the problem is that boron is marginally soluble in THF and repeated treatment cycles must be used in order to reach 1 weight percent boron loading in the untreated wood product. Accordingly, because of the differences in the types of solvents needed, it is preferred that the boron-containing material be introduced into the wood products prior to, and separately from, the introduction of the silane-containing material into the wood product.
  • a preferred concentration of methyltrichlorosilane in pentane, wherein the methyltrichlorosilane is present at 1 to 3 volume percent should be used in the treatment of boron-impregnated wood products.
  • thick wood products such as railroad ties may require higher levels of the methyltrichlorosilane to be present, whereas thinner wood products, such as planking for fences and decks and dimensional lumber, may require lower levels of the methyltrichlorosilane to be present.
  • at least one exposed (untreated or unpainted) surface will generally be necessary in order to introduce boron-containing materials into pre-existing wooden structures.
  • the exterior of the 1 volume percent solution treatment indicated partial waterproofing capability. No observable coating was evident on the surface of the wood. Following a 24 hour drying time, the exterior of the 3 volume percent solution treatment was completely waterproof. Upon breaking the wood in half and exposing an interior surface, the penetration of the silane was evident at the thickness of a human hair. Better results were obtained when additional wood pieces were treated with the 3 volume percent concentration of methyltrichlorosilane/pentane solution in time intervals of 30 minutes, 2.5 hours, 1 week, 2 weeks, and 4 weeks, after removal of the sample wood pieces from the boron-containing treatment vessel. This may indicate that it may not be possible to treat totally wet wood, and it may be necessary to partially dry the wood prior to the application of the methyltrichlorosilane/pentane solution.
  • the methyltrichlorosilane/pentane solution penetrates the paint layer and effectively seals the wood layer below the paint surface.
  • the methyltrichlorosilane/pentane solution penetrates the paint layer and effectively seals the wood layer below the paint surface.
  • a 3 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a 1 -gallon plastic pump sprayer. This solution was then sprayed topically on the surface of latex and oil-based painted blocks of wood. A single pass spraying resulted in the incorporation of the silane beneath the surface of the paint. Extensive spraying appeared to reduce the thickness of the latex paint. The penetration was observed approximately 1 inch deep into the wood matrix. No amount of spraying appeared to diminish the thickness or adhesion of the oil-based paint on the surface of the wood.
  • the waterproofing penetration of the 1 volume percent solution of methyltrichlorosilane in pentane is preferably 0.75 inches, and the waterproofing penetration of the 3 volume percent solution of methyltrichlorosilane in pentane is preferably 1.5 inches.
  • Both of the 1 and 3 volume percent methyltrichlorosilane/pentane solutions were applied to fresh red oak blocks in order to determine the penetration ability of the solutions.
  • a quick single spray pass was applied to each block of wood.
  • the waterproofing penetration of the 1 volume percent solution of methyltrichlorosilane in pentane was 0.75 inches.
  • the waterproofing penetration of the 3 volume percent solution of methyltrichlorosilane in pentane was 1.5 inches.
  • the level of penetration was determined by splitting cross-sectional pieces of wood off of the block and then introducing the wood sample to a small stream of water. The boundary of the treated and untreated wood could then be determined.
  • the 1 and 3 volume percent methyltrichlorosilane/pentane solutions penetrate and waterproof the wood to at least 0.75 inches and to at least about 1.5 inches, respectively, with a steady one-pass application. It may be possible to have to spray and treat only one side of a wooden structure (e.g., a fence), because the wood is generally in the dimension of a 1 inch x 6 inch board.
  • a 5 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a hand-held garden mister.
  • a 10 volume percent solution of methyltrichlorosilane/pentane was also prepared and introduced to a separate hand-held garden mister.
  • Samples of newsprint, paper-coated polyurethane-filled insulation, and paper used to coat the polyurethane-filled insulation were covered with a fine mist of the 5 volume percent solution.
  • Separate samples of newsprint, paper-coated polyurethane-filled insulation, and paper used to coat the polyurethane-filled insulation were covered with a fine mist of the 10 volume percent solution.
  • Each of the samples were allowed to dry for 20 minutes. Then, droplets of water were placed on each sample.
  • a 5 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a hand-pump sprayer.
  • a 10 volume percent solution of methyltrichlorosilane/pentane was also prepared and introduced to a separate hand-pump sprayer. The total volume of each solution was approximately 1 gallon.
  • Example XII In order to determine the effectiveness of the preservative composition prepared in Example XI in treating newsprint, an experiment was carried out as described in Example XII below:
  • Example XI The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of newsprint.
  • the 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of newsprint. The samples were allowed to dry for 20 minutes. Water was then placed on each sample. Each of the two treated samples of newsprint was extremely hydrophobic and the water immediately beaded up. Water was also placed on a control sample of untreated newsprint, and the control sample immediately wetted as a result.
  • Example XIII EXAMPLE XIII
  • Example XI The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of paper-coated polyurethane-filled insulation.
  • the 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of paper-coated polyurethane-filled insulation.
  • a third sample of paper-coated polyurethane-filled insulation was treated with neat methyltrichlorosilane. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. Each of the three treated samples of insulation exhibited strong hydrophobic character. Water was also placed on a control sample of untreated paper-coated polyurethane- filled insulation, and the control sample immediately wetted as a result.
  • Example XIV In order to determine the effectiveness of the preservative composition prepared in Example XI in treating the paper that coats the paper-coated polyurethane-filled insulation treated in Example XIII, an experiment was carried out as described in Example XIV below:
  • Example XI The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of the paper used to coat the paper-coated polyurethane-filled insulation treated in Example XIII.
  • the 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of the paper that coats the paper-coated polyurethane-filled insulation treated in Example XIII. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. The treated surfaces of each of the samples exhibited strong hydrophobic character.
  • Example XV In order to determine the effectiveness of the preservative composition prepared in Example XI in treating drywall, an experiment was carried out as described in Example XV below:
  • Example XI The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of drywall.
  • the 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of drywall. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. The treated surfaces of each of the samples exhibited strong hydrophobic character. Water was also placed on a control sample of untreated drywall, and the control sample immediately wetted as a result.
  • Example XVI In order to determine the effectiveness of the preservative composition prepared in Example XI in treating masonry brick, an experiment was carried out as described in Example XVI below:
  • Example XI The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of masonry brick. The sample was allowed to dry for 20 minutes. Water was then placed on the sample. Water immediately beaded up when placed on the sample surface. Water was also placed on a control sample of untreated masonry brick, and the control sample immediately wetted as a result.

Abstract

Preservative composition for various materials and method of preserving the same is disclosed. The preservative composition includes at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms.

Description

PRESERVATIVE COMPOSITIONS FOR MATERIALS AND METHOD
OF PRESERVING SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. Serial No. 10/297,398, entitled "Preservative Compositions for Wood Products," filed May 27, 2003.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates generally to preservative compositions and, more particularly, to preservative compositions for materials and to a method for preserving the same.
2. Description of the Related Art
[0003] Certain materials are susceptible to damage caused by the elements, especially water and insects (e.g., termites, certain types of ants, and other boring insects). For instance, exposure to water typically causes many materials, such as various wood products, insulation, newsprint, drywall, and masonry bricks, to crack, warp, check, as well as become discolored and mildewed. Also, water and/or insect damage often causes these materials to rot and decay. Typically, water and/or insect damage leads to the eventual replacement of the damaged section of the material at great expense, effort, and inconvenience.
[0004] Preservative manufacturers have marketed various treatment products that supposedly prevent, or reduce the likelihood of water and/or insect damage to the material to which the treatment products are applied. However, these treatment products have not been completely satisfactory, especially with regard to effectiveness, cost concerns, ease of application, duration of treatment time, and duration of protection afforded.
[0005] Therefore, it is desirable to provide a preservative composition for various materials. It is also desirable to provide a preservative composition that preserves various materials effectively against water intrusion and damage. Further, it is desirable to provide a preservative composition that preserves materials effectively against insect intrusion and damage. Still further it is desirable to provide a preservative composition that is relatively inexpensive. It is also desirable to provide a preservative composition that is relatively easy to apply. Furthermore, it is desirable to provide a preservative composition that has a relatively short treatment time. Also, it is desirable to provide a preservative composition that provides a relatively long period of protection. Therefore, there is a need in the art to provide a preservative composition and method that meets these desires.
SUMMARY OF THE INVENTION
[0006] It is, therefore, one object of the present invention to provide new preservative compositions for various materials and methods for preserving the same.
[0007] It is another object of the present invention to provide new preservative compositions for various materials that protect the materials against water intrusion and/or insect damage.
[0008] To achieve the foregoing objects, the present invention is a preservative composition for materials including at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms.
[0009] hi addition, the present invention is a method for preserving a material including the steps of providing a composition having at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms, and contacting the material with the composition.
[0010] One advantage of the present invention is that a new preservative composition for various materials is provided. Another advantage of the present invention is that the preservative composition preserves various materials effectively against water intrusion and damage. Yet another advantage of the present invention is that the preservative composition preserves materials effectively against insect intrusion and damage. Still another advantage of the present invention is that the preservative composition is relatively inexpensive. A further advantage of the present invention is that the preservative composition is relatively easy to apply. Yet a further advantage of the present invention is that the preservative composition has a relatively short treatment time. Still a further advantage of the present invention is that the preservative composition provides a relatively long period of protection.
[0011] Other objects, features and advantages of the present invention will be readily appreciated, as the same becomes better understood, after reading the subsequent description taken in conjunction with the accompanying drawings.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
[0012] The present invention includes compositions, and methods of use therefor, for preserving, protecting, and treating subject materials so as to impart protection against various sources of damage, including, but not limited to water and insects. The terms "preserving," "protecting," and "treating," as those terms are used interchangeably herein, are meant to include any methods of, and compositions for, protecting subject materials from damage caused by any source, including, but not limited to water and insects. The term "subject material" as used herein is meant to include any object that can be preserved, protected, and treated with the compositions of the present invention, including but not limited to wood products (i.e., products containing any amount of wood), insulation, paper used to coat insulation, drywall, newsprint, and masonry brick.
[0013] In accordance with one embodiment of the present invention, the preservative composition includes at least one silane-containing material and at least one solvent.
[0014] The preservative composition contains at least one silane-containing material. Silanes are generally defined in a class of silicon-based materials, analogous to alkanes, that is, straight-chain, saturated paraffin hydrocarbons having the general formula Si>jH2N+2, wherein N is an integer equal to 1 or higher. The silane-containing material is preferably in the form of trichloromethylsilane (chemical formula: CH3Cl3Si), although other forms of silane-containing materials are acceptable. Examples of other silane-containing materials useful in practicing the present invention include, without limitation:
[0015] (Chloromethyl) Trichlorosilane;
[0016] [3-(Heptafluoroisoproxy)Propyl]Trichlorosilane;
[0017] 1 ,6-Bis(Trichlorosilyl)Hexane;
[0018] 3-Bromopropyltrichlorosilane;
[0019] Allylbromodimethylsilane;
[0020] Allyltrichlorosilane;
[0021] Bromomethylchlorodimethylsilane;
[0022] Bromothimethylsilane;
[0023] Chloro(Chloromethyl)Dimethylsilane; Chlorodiisopropyloctylsilane;
[0024] Chlorodiisopropylsilane;
[0025] Chlorodimethylethylsilane;
[0026] Chlorodimethylphenylsilane;
[0027] Chlorodimethylsilane;
[0028] Chlorodiphenylmethylsilane;
[0029] Chlorotriethylsilane;
[0030] Chlorotrimethylsilane;
[0031] Dichlorodimethylsilane;
[0032] Dichloromethylsilane;
[0033] Dichloromethylvinylsilane;
[0034] Diphenyldichlorosilane; [0035] Di-t-Butylchlorosilane;
[0036] Ethyltrichlorosilane;
[0037] Iodotrimethylsilane;
[0038] Pentyltrichlorosilane;
[0039] Phenyltrichlorosilane;
[0040] Trichloro(3,3,3-Trifluoroρropyl)Silane;
[0041] Trichloro(Dichloromethyl)Silane; and
[0042] Trichlorovinylsilane.
[0043] The preservative composition contains at least one solvent. The solvent is in the form of a hydrocarbon. For example, hydrocarbons which are liquid at room temperature are acceptable. Examples of these hydrocarbons are hydrocarbons having molecules of at least five carbon atoms that include, without limitation, pentane, hexane, and heptane. It should be appreciated that, although a hydrocarbon solvent is used, other organic solvents such as tetrahydrofuran (THF) may be used.
[0044] In accordance with another embodiment of the present invention, the preservative composition includes at least pesticide-containing material, at least one silane-containing material, and at least one solvent.
[0045] The pesticide-containing material is preferably in the form of boric anhydride (chemical formula: B2O3), although other forms of boron-containing materials are acceptable. By way of a non-limiting example, borax (chemical formula: Na2B4O7-H2O), and disodium octaborate tetrahydrate (chemical formula: Na2B8O13-H2O) may be used as well. Effective fungal and fire resistance can be obtained with a boron loading of 0.1 weight percent, based on the total weight of the subject material. However, in order to prevent wood-boring insect infestation (e.g., by ants and termites), a loading of 1-2 weight percent of boron is generally required. For more problematic insects, such as the Formosan termite, a loading of 7 weight percent of boron is generally required. Therefore, the present invention provides a product, and a method of using the same, to introduce pesticide-containing material such as boron into the subject material at levels of at least about 0.1 to at least about 7 weight percent and seal it to prevent environmental factors (e.g., rain) from leaching it from the interior of the subject material. It should be appreciated that other organic pesticide-containing materials other than boron may be used.
[0046] The preservative composition may include other additives. Other additives such as paint or stain may be used. The additives are carried with the hydrocarbon solvent and silane- containing material and penetrate the material being treated. For example, colorant may be an additive to the preservative composition to treat and color wood product. It should be appreciated that other types of organic additives may be used to treat the materials. METHOD OF PRESERVING MATERIALS & MATERIALS TO BE PRESERVED
[0047] In order to preserve various materials using the preservative composition of the present invention, the preservative composition is prepared. Then, the preservative composition is applied to the material to be preserved. For instance, the preservative composition is topically applied to the material to be preserved. The preservative composition of the present invention can be applied to preserve several types of various materials, including but not limited to the following: 1) wood materials, such as newsprint and other paper products; 2) insulation materials, such as paper-coated polyurethane- filled insulation; 3) drywall materials, such as sheet rock; 4) masonry materials, such as masonry brick; and 5) fibrous material such as cotton. It should be appreciated that, for specific wood products such as telephone poles and railroad ties, a lower hydrocarbon solvent may be used such as diesel fuel may be used in the preservative composition.
[0048] The preparation of an illustrative preservative composition, in accordance with the general teachings of the present invention, is presented in Example I, below:
EXAMPLE I
[0049] Approximately 50 ml of THF was added to a 250 ml Erlenmeyer flask. Approximately 1.0 gm of boric anhydride (B2O3) was added to the flask and stirred. The mixture was cloudy at first, but gradually cleared upon sitting for 5 minutes. A small amount of B2O3 remained on the bottom of the flask. Approximately 10 to 15 ml of trichloromethylsilane was then slowly added to the solution. No visual evidence of an exothermic reaction was observed. The solution remained clear.
[0050] In order to determine the effectiveness of the illustrative preservative composition prepared in Example I, a comparison test was performed between a treated portion and an untreated portion of a piece of plywood board. The results of the comparison test are presented in Example II, below:
EXAMPLE II
[0051] An eyedropper was used to deposit several drops of the preservative composition prepared in Example I to apiece of plywood board. No evidence of an exothermic reaction or the evolution of foul smelling HCl gas was observed with the addition of the prepared solution to the wood sample. The composition diffused laterally across the surface of the board in addition to vertically through the board. Water was poured onto the treated area and it effectively repelled the water. The water was immediately absorbed in the untreated portion. Several drops were also deposited on the edge of the board to determine the effect of the solvent (i.e., THF) on the glue. A screwdriver and a spatula were used to try to separate the layers. This effort was unsuccessful. [0052] In order to further determine the effectiveness of the illustrative preservative composition prepared in Example I, a comparison test was performed between a treated portion and an untreated portion of a piece of hardwood. The results of the comparison test are presented in Example III, below:
EXAMPLE III
[0053] Several drops of the preservative composition prepared in Example I were applied to a solid piece of hardwood. The sample was allowed to sit for several minutes prior to exposing it to water. Upon drying, no white residue was observed on the surface of the sample. Water was repelled off both sides of the sample even though just one side was treated.
[0054] The preparation of another illustrative preservative composition, in accordance with the general teachings of the present invention, is presented in Example IV, below:
EXAMPLE IV
[0055] 20 ml of THF was added to a 100 ml beaker. Approximately 1 gm Of B2O3 and 1 ml of trichloromethylsilane was added to the THF solvent. The total volume was approximately 22 ml.
[0056] In order to determine the effectiveness of the illustrative preservative composition prepared in Example IV, a comparison test was performed between a treated portion and an untreated portion of apiece of plywood board. The results of the comparison test are presented in Example V, below:
EXAMPLE V
[0057] A piece of plywood, 5/8 inches x 5/8 inches x 3-1/2 inches was placed into a beaker and partially submerged into the preservative composition prepared in Example IV. The beaker was covered for approximately 5 minutes. After 5 minutes, the piece of plywood was removed and allowed to air dry. The volume of the preservative composition remaining in the beaker had been reduced by 2-3 ml, or about 10%. There was no visible white deposit on the surface of the plywood. Surface samples were removed from both the treated and untreated portions of the plywood in order to evaluate them under a microscope. There was an observable difference between the samples. The treated plywood appeared as though it had been coated in glass or white cotton coating. There was a difference in the appearance of the heartwood and the sapwood. The cells of the untreated plywood appeared empty, while those of the treated wood appeared to be coated with glass. When drops of methanol were added to the plywood samples, the treated sample beaded up and looked like a jelly on the surface of the sample. Whereas, the run off water was readily absorbed on the untreated plywood. A piece (1/2 inch x 1/2 inch x 3/4 inches) of this plywood was placed in a 100 ml beaker containing 10 ml of water and covered with a watch glass. The sample was allowed to sit undisturbed for 24 hours and then the plywood was removed from the water. The FTIR of the water from the leaching experiment showed a slight peak @ 800 cm-1. The peak was not strongly defined as in the case of the silane reference peaks. The treated plywood showed no sign of silanes on the surface after being soaked in water for 24 hours. It did, however, readily repel water on all sides. The cut surface also repelled water even though it was never in direct contact with the preservative composition. It was 1/2 inch to 3/4 inches away from the preservative composition.
[0058] There were several benefits that were observed for using a solvent, such as THF, over just a neat application of methyltrichlorosilane, including: (1) costs were reduced by dilution (e.g., with THF) of the neat methyltrichlorosilane solution; (2) no evidence of an exothermic reaction was observed; (3) no white residue was left on the surface of the treated subject material; (4) boron and silane readily penetrated into and diffused through the subject material and were delivered in one step; (5) little or no drying time was necessary prior to use; (6) cycle treatment time was drastically reduced over the CCA process; (7) no delamination or degradation of plywood was observed; (8) the treated subject material was rendered waterproof; (9) the treated subject material was rendered insect resistant (by virtue of the boron present); (10) the treated subject material was rendered fire resistant (by virtue of the boron present); and (11) the treated subject material resisted leaching.
[0059] In order to determine the boron penetration and retention characteristics of the preservative composition of the present invention, an experiment was carried out as described in Example VI, below:
EXAMPLE VI
[0060] In a 2 liter Erlenmeyer flask, 800 milliliters of THF was added. A magnetic stirring bar began stirring at a low rate. To this stirred solution, 6.895 grams (0.7 percent by weight of solvent) of B2O3 was slowly added. The mixture was allowed to stir for 20 to 30 minutes. The solution was clear, although some undissolved B2O3 did remain on the bottom of the flask. To this stirred solution, 200 milliliters of methyltrichlorosilane was transferred via nitrogen pressurized canula, over a 10 minute period. The system was well behaved and no evidence of an exothermic reaction was observed. This resulted in an approximate 20 volume percent methyltrichlorosilane solution. The solution was stirred for 10 minutes and then stirring was ceased. A small amount of undissolved B2O3 remained on the bottom of the flask. A 500 milliliter aliquot was decanted into each of two 1 liter beakers and covered with a large watch glass. A first set of wood blocks had the dimensions of 1 inch x 2 inches x 5/8 inches. A second set of wood blocks were 3/4 inch cubes. The wood blocks from each sample were placed individually into their respective solutions. A smaller watch glass was placed inside the beaker such that the weight of the watch glass kept the wood block samples completely submerged. The samples were allowed to stand in the solution for 1 hour. Some bubbling took place throughout the entire process. After the 1 hour treatment, the wood blocks were removed from the solution and allowed to air dry overnight. The pieces of wood appeared to "smoke" while drying. The smoke was believed to be hydrochloric acid. It is probably produced from the hydrolysis of the unreacted methyltrichlorosilane present on the surface of the wood. The solution appeared turbid and slightly discolored following the treatment.
[0061] It was observed that one hour is probably too long to expose wood to the preservative composition as described above. The treated wood has a tendency to smoke (i.e., evolve HCl) due to excess silane on the surface of the wood. A 5 to 10 minute exposure to the preservative composition as described above is probably more than sufficient to achieve the aforementioned benefits.
[0062] Additionally, the appearance of the wood treated with the preservative composition as described above for 1 hour is gray or ashen in appearance. This is probably due to the boron. This feature is not present in the material treated for 5 to 10 minutes with the preservative composition as described above.
[0063] In accordance with an alternative embodiment of the present invention, the boron- containing material is preferably impregnated into the subject material prior to, and separately from, impregnation by the silane-containing material.
[0064] It was observed that the most effective method for introducing boron into wood products, at a concentration of 1 weight percent or greater (based on the total weight of the treated wood product), is with the use of water as the solvent, as opposed to hydrocarbons such as THF, and preferably under the influence of a pressurized treatment vessel.
[0065] Although THF was used initially as a solvent for the boron-containing material because it is commonly used in boron chemistry, the problem is that boron is marginally soluble in THF and repeated treatment cycles must be used in order to reach 1 weight percent boron loading in the untreated wood product. Accordingly, because of the differences in the types of solvents needed, it is preferred that the boron-containing material be introduced into the wood products prior to, and separately from, the introduction of the silane-containing material into the wood product.
[0066] Following a four hour treatment period with the boron-containing material/water solution, this should result in a final boron concentration of 2 weight percent. It should be noted that higher boron loading concentrations could be achieved by varying (e.g., increasing) the boron concentration in the boron-containing treatment solution and/or by varying (e.g., increasing) the treatment period. It was then determined whether the wet, treated wood product (i.e., boron-impregnated) could be subsequently treated with the silane-containing material (e.g., methyltrichlorosilane solution) to yield acceptable results.
[0067] hi accordance with an alternative embodiment of the present invention, it was observed that the performance and cost of the pentane solvent is superior to that of THF for the purpose of applying the methyltrichlorosilane to wet, boron-impregnated wood products.
[0068] By way of a non-limiting example, a preferred concentration of methyltrichlorosilane in pentane, wherein the methyltrichlorosilane is present at 1 to 3 volume percent, should be used in the treatment of boron-impregnated wood products. For example, thick wood products such as railroad ties may require higher levels of the methyltrichlorosilane to be present, whereas thinner wood products, such as planking for fences and decks and dimensional lumber, may require lower levels of the methyltrichlorosilane to be present. However, at least one exposed (untreated or unpainted) surface will generally be necessary in order to introduce boron-containing materials into pre-existing wooden structures.
[0069] In order to determine the silane penetration characteristics of the alternative methodology on treated (i.e. boron-impregnated) wood products, an experiment was carried out as described in Example VII, below:
EXAMPLE VII
[0070] Initially, a 1 volume percent solution of metliyltrichlorosilane/pentane was prepared and applied to a piece of wood saturated with water. A second solution, with a 3 volume percent concentration of methyltrichlorosilaiie/pentane, was also prepared and tested. Two separate pieces of water-saturated wood were sprayed immediately following the removal of the wood from a boron-containing treatment vessel. The wood pieces had been previously treated with the pressurized aqueous solution of boron-containing material for 2 hours. The wood did not appear to repel or bead water immediately following the treatment. However, as the wood dried, it displayed evidence of complete water repulsion. Following a 24 hour drying time, the exterior of the 1 volume percent solution treatment indicated partial waterproofing capability. No observable coating was evident on the surface of the wood. Following a 24 hour drying time, the exterior of the 3 volume percent solution treatment was completely waterproof. Upon breaking the wood in half and exposing an interior surface, the penetration of the silane was evident at the thickness of a human hair. Better results were obtained when additional wood pieces were treated with the 3 volume percent concentration of methyltrichlorosilane/pentane solution in time intervals of 30 minutes, 2.5 hours, 1 week, 2 weeks, and 4 weeks, after removal of the sample wood pieces from the boron-containing treatment vessel. This may indicate that it may not be possible to treat totally wet wood, and it may be necessary to partially dry the wood prior to the application of the methyltrichlorosilane/pentane solution.
[0071] The performance of the solvent pentane appeared to be superior to THF when applying the methyltrichlorosilane to the treated wood. The reactivity of the methyltrichlorosilane was reduced and no appreciable amounts of hydrochloric acid (HCl) gas was observed following treatment. This may be due, in part, to the fact that the silane was present in concentrations of 3 volume percent or less.
[0072] Furthermore, when sprayed topically on the surface of a latex painted piece of wood, the methyltrichlorosilane/pentane solution penetrates the paint layer and effectively seals the wood layer below the paint surface. When sprayed topically on the surface of an oil-based painted piece of wood, the methyltrichlorosilane/pentane solution penetrates the paint layer and effectively seals the wood layer below the paint surface.
[0073] In order to determine the silane penetration characteristics of the alternative methodology on a subject material having painted surfaces, an experiment was carried out as described in Example VIII, below:
EXAMPLE VIII
[0074] A 3 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a 1 -gallon plastic pump sprayer. This solution was then sprayed topically on the surface of latex and oil-based painted blocks of wood. A single pass spraying resulted in the incorporation of the silane beneath the surface of the paint. Extensive spraying appeared to reduce the thickness of the latex paint. The penetration was observed approximately 1 inch deep into the wood matrix. No amount of spraying appeared to diminish the thickness or adhesion of the oil-based paint on the surface of the wood.
[0075] The waterproofing penetration of the 1 volume percent solution of methyltrichlorosilane in pentane is preferably 0.75 inches, and the waterproofing penetration of the 3 volume percent solution of methyltrichlorosilane in pentane is preferably 1.5 inches. [0076] In order to determine the silane penetration characteristics of the alternative methodology on untreated subject materials, an experiment was carried out as described in Example IX, below:
EXAMPLE IX
[0077] Both of the 1 and 3 volume percent methyltrichlorosilane/pentane solutions were applied to fresh red oak blocks in order to determine the penetration ability of the solutions. A quick single spray pass was applied to each block of wood. The waterproofing penetration of the 1 volume percent solution of methyltrichlorosilane in pentane was 0.75 inches. The waterproofing penetration of the 3 volume percent solution of methyltrichlorosilane in pentane was 1.5 inches. The level of penetration was determined by splitting cross-sectional pieces of wood off of the block and then introducing the wood sample to a small stream of water. The boundary of the treated and untreated wood could then be determined.
[0078] Accordingly, it is preferred that the 1 and 3 volume percent methyltrichlorosilane/pentane solutions penetrate and waterproof the wood to at least 0.75 inches and to at least about 1.5 inches, respectively, with a steady one-pass application. It may be possible to have to spray and treat only one side of a wooden structure (e.g., a fence), because the wood is generally in the dimension of a 1 inch x 6 inch board.
EXAMPLE X
[0079] A 5 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a hand-held garden mister. A 10 volume percent solution of methyltrichlorosilane/pentane was also prepared and introduced to a separate hand-held garden mister. Samples of newsprint, paper-coated polyurethane-filled insulation, and paper used to coat the polyurethane-filled insulation were covered with a fine mist of the 5 volume percent solution. Separate samples of newsprint, paper-coated polyurethane-filled insulation, and paper used to coat the polyurethane-filled insulation were covered with a fine mist of the 10 volume percent solution. Each of the samples were allowed to dry for 20 minutes. Then, droplets of water were placed on each sample. The entire surface was not hydrophobic for any of the samples. Not enough of the preservative composition could be placed on the surfaces of the samples of newsprint or paper to make them hydrophobic. Similarly, the texture of the paper covering the insulation was pocketed and wetted immediately when water was applied to the surface. [0080] In order to determine a more effective way of applying the preservative composition of the present invention, another illustrative preservative composition, in accordance with the present invention, was prepared as detailed in Example XI, below:
EXAMPLE XI
[0081] A 5 volume percent solution of methyltrichlorosilane/pentane was prepared and introduced to a hand-pump sprayer. A 10 volume percent solution of methyltrichlorosilane/pentane was also prepared and introduced to a separate hand-pump sprayer. The total volume of each solution was approximately 1 gallon.
[0082] In order to determine the effectiveness of the preservative composition prepared in Example XI in treating newsprint, an experiment was carried out as described in Example XII below:
EXAMPLE XII
[0083] The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of newsprint. The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of newsprint. The samples were allowed to dry for 20 minutes. Water was then placed on each sample. Each of the two treated samples of newsprint was extremely hydrophobic and the water immediately beaded up. Water was also placed on a control sample of untreated newsprint, and the control sample immediately wetted as a result.
[0084] Both samples of newsprint turned yellow initially when sprayed. This was not unexpected, due to the presence of lignin in paper. (When exposed to a strong acid, like the HCl formed from the reaction of the silane with the paper, the lignin in the paper will turn yellow. If sufficient primary, secondary, and tertiary amines are present in the paper, the paper will remain yellow.) Here, the yellowness faded over time as the samples of newsprint dried, indicating that little or no amines were present on the surface of the respective samples.
[0085] Also, the treated samples of newsprint appeared white, indicating an excess of methyltrichlorosilane was present on each. Thus, a more dilute solution could probably be used, such as a 2 to 3 volume percent solution of methyltrichlorosilane/pentane.
[0086] In order to determine the effectiveness of the preservative composition prepared in Example XI in treating paper-coated polyurethane-filled insulation, an experiment was carried out as described in Example XIII below: EXAMPLE XIII
[0087] The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of paper-coated polyurethane-filled insulation. The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of paper-coated polyurethane-filled insulation. A third sample of paper-coated polyurethane-filled insulation was treated with neat methyltrichlorosilane. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. Each of the three treated samples of insulation exhibited strong hydrophobic character. Water was also placed on a control sample of untreated paper-coated polyurethane- filled insulation, and the control sample immediately wetted as a result.
[0088] It was observed that neither the methyltrichlorosilane nor the pentane degraded the polyurethane foam of the samples. Moreover, the treated surfaces of the samples of insulation appeared white, indicating an excess of methyltrichlorosilane was present. Thus, a more dilute solution could probably be used, such as a 2 to 3 volume percent solution of methyltrichlorosilane/pentane.
[0089] It was determined that neither of the 5 volume percent nor the 10 volume percent of the methyltrichlorosilane/pentane permeated through the insulation samples. Thus, both sides of the sample of the insulation should be treated to prevent water damage. Furthermore, it was observed that it may not be possible to treat a required minimum of 140 board feet of the paper- coated insulation using only 1 gallon of the preservative solution because its surface area is higher compared to that of wood products.
[0090] In order to determine the effectiveness of the preservative composition prepared in Example XI in treating the paper that coats the paper-coated polyurethane-filled insulation treated in Example XIII, an experiment was carried out as described in Example XIV below:
EXAMPLE XIV
[0091] The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of the paper used to coat the paper-coated polyurethane-filled insulation treated in Example XIII. The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of the paper that coats the paper-coated polyurethane-filled insulation treated in Example XIII. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. The treated surfaces of each of the samples exhibited strong hydrophobic character. Water was also placed on a control sample of untreated paper that coats the paper-coated polyurethane-filled insulation treated in Example XIII, and the control sample immediately wetted as a result. [0092] It was observed that the samples of paper appeared white, indicating an excess of methyltrichlorosilane was present. Thus, a more dilute solution could probably be used, such as a 2 to 3 volume percent solution of methyltrichlorosilane/pentane.
[0093] In order to determine the effectiveness of the preservative composition prepared in Example XI in treating drywall, an experiment was carried out as described in Example XV below:
EXAMPLE XV
[0094] The 5 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of drywall. The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a separate sample of drywall. Each sample was allowed to dry for 20 minutes. Water was then placed on each sample. The treated surfaces of each of the samples exhibited strong hydrophobic character. Water was also placed on a control sample of untreated drywall, and the control sample immediately wetted as a result.
[0095] The treated surfaces of the drywall samples appeared white, indicating an excess of methyltrichlorosilane was present. Thus, a more dilute solution could probably be used, such as a 2 to 3 volume percent solution of methyltrichlorosilane/pentane. Also, it was determined that neither of the 5 volume percent nor the 10 volume percent of the methyltrichlorosilane/pentane permeated through the drywall samples. Thus, both sides of the sample of drywall should be treated to prevent water damage.
[0096] In order to determine the effectiveness of the preservative composition prepared in Example XI in treating masonry brick, an experiment was carried out as described in Example XVI below:
EXAMPLE XVI
[0097] The 10 volume percent solution of methyltrichlorosilane/pentane prepared in Example XI was sprayed topically on a sample of masonry brick. The sample was allowed to dry for 20 minutes. Water was then placed on the sample. Water immediately beaded up when placed on the sample surface. Water was also placed on a control sample of untreated masonry brick, and the control sample immediately wetted as a result.
[0098] The treated surfaces of the masonry brick samples appeared white, indicating an excess of methyltrichlorosilane was present. Thus, a more dilute solution could probably be used, such as a 2 to 3 volume percent solution of methyltrichlorosilane/pentane. Also, the treated sample of masonry brick was treated only on one surface, and the methyltrichlorosilaiie/pentane did not appear to permeate the entire surface. The untreated portion of the sample wetted immediately with the presence of water. Thus, in order to make masonry brick completely hydrophobic, the entire brick would have to be sprayed.
[0100] The present invention has been described in an illustrative manner. It is to be understood that the terminology, which has been used, is intended to be in the nature of words of description rather than of limitation.
[0101] Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, the present invention may be practiced other than as specifically described.

Claims

WHAT IS CLAIMED IS:
1. A method for preserving a material comprising: providing a preservative composition comprising at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms; and applying the preservative composition to the material.
2. A method as set forth in claim 1 wherein the at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
3. A method as set forth in claim 1 wherein the at least one silane-containing material is methyltrichlorosilane.
4. A method as set forth in claim 1 wherein the preservative composition further comprises at least pesticide-containing material.
5. A method as set forth in claim 4 wherein the at least one pesticide- containing material is boric anhydride.
6. A method for preserving an insulation material comprising: providing a preservative composition comprising at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms; and applying the preservative composition to the insulation material.
7. A method as set forth in claim 6 wherein the at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
8. A method as set forth in claim 6 wherein the at least one silane-containing material is methyltrichlorosilane.
9. A method as set forth in claim 6 wherein the preservative composition further comprises at least one pesticide-containing material.
10. A method as set forth in claim 9 wherein the at least one pesticide- containing material is boric anhydride.
11. A method for preserving a drywall material comprising: providing a preservative composition comprising at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms; and applying the preservative composition to the drywall material.
12. A method as set forth in claim 11 wherein the at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
13. A method as set forth in claim 11 wherein the at least one silane- containing material is methyltrichlorosilane.
14. A method as set forth in claim 11 wherein the preservative composition further comprises at least one pesticide-containing material.
15. A method as set forth in claim 14 wherein the at least one pesticide- containing material is boric anhydride.
16. A method for preserving a masonry material comprising: providing a preservative composition comprising at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms; and applying the preservative composition to the masonry material.
17. A method as set forth in claim 11 wherein the at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
18. A method as set forth in claim 11 wherein the at least one silane- containing material is methyltrichlorosilane.
19. A method as set forth in claim 11 wherein the preservative composition further comprises at least one pesticide-containing material.
20. A method as set forth in claim 19 wherein the at least one pesticide- containing material is boric anhydride.
21. A method for preserving a wood material comprising: providing a preservative composition comprising at least one silane-containing material and at least one hydrocarbon solvent containing molecules of at least five carbon atoms; and applying the preservative composition to the wood material.
22. A method as set forth in claim 21 wherein the at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
23. A method as set forth in claim 21 wherein the at least one silane- containing material is methyltrichlorosilane.
24. A method as set forth in claim 21 wherein the preservative composition further comprises at least one pesticide-containing material.
25. A method as set forth in claim 24 wherein the at least one pesticide- containing material is boric anhydride.
26. A preservative composition comprising: at least one silane-containing material; and at least one hydrocarbon solvent containing molecules of at least five carbon atoms.
27. A preservative composition as set forth in claim 26 wherein said at least one hydrocarbon solvent is at least one of pentane, heptane, hexane, and combinations thereof.
28. A preservative composition as set forth in claim 26 wherein said at least one silane-containing material is methyltrichlorosilane. T/US2006/001546
29. A preservative composition as set forth in claim 26 further comprising at least one pesticide-containing material.
30. A preservative composition as set forth in claim 26 wherein said at least one pesticide-containing material is boric anhydride.
PCT/US2006/001546 2005-01-19 2006-01-17 Preservative compositions for materials and method of preserving same WO2006078625A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008289026A (en) * 2007-05-21 2008-11-27 Kyocera Corp Search interval control server and radio terminal
EP2144712A1 (en) * 2007-05-09 2010-01-20 Woodholdings Environmental, Inc. and Dow Corning Corporation Apparatus and method for treating materials with compositions
US7964031B2 (en) 2000-06-06 2011-06-21 Dow Corning Corporation Compositions for treating materials and methods of treating same
US7964287B2 (en) 2000-06-06 2011-06-21 Dow Corning Corporation Preservative compositions for wood products
US8721783B2 (en) 2000-06-06 2014-05-13 Dow Corning Corporation Compositions for treating materials and methods of treating same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7192470B2 (en) * 2003-05-27 2007-03-20 Woodholdings Environmental, Inc. Preservative compositions for materials and method of preserving same
US20130189530A1 (en) 2010-02-19 2013-07-25 Stl Sustainable Technologies, Llc Preservative composition and method
CA2823754C (en) 2011-01-18 2018-07-03 Dow Corning Corporation Method for treating substrates with halosilanes
WO2016161250A2 (en) * 2015-04-01 2016-10-06 University Of Houston System Wood drying and preservation methods
ES2962248T3 (en) * 2017-03-08 2024-03-18 Silana Gmbh Thermal insulation materials

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637570A (en) * 1969-02-25 1972-01-25 Us Air Force Process for producing protective coating of siloxane resin and product produced
US4002800A (en) * 1972-12-01 1977-01-11 Dynamit Nobel Aktiengesellschaft Impregnation of masonry having a neutrally or acidly reaction surface
JPS5638366A (en) * 1979-09-04 1981-04-13 Kanegafuchi Chem Ind Co Ltd Primer composition
US4491669A (en) * 1980-11-12 1985-01-01 Petrarch Systems Inc. Mixed alkoxyaminosilanes, methods of making same and vulcanizing silicons prepared therefrom
JPH01305006A (en) * 1988-06-02 1989-12-08 Nippon Soda Co Ltd Antifouling agent for fishing net
JPH026488A (en) * 1988-06-24 1990-01-10 Shin Etsu Chem Co Ltd Omega-alkynylsilane compound
JPH1192694A (en) * 1997-09-25 1999-04-06 Toshiba Silicone Co Ltd Emulsion composition
JP2000080354A (en) * 1998-09-03 2000-03-21 Ge Toshiba Silicones Co Ltd Rustproof and stain resistant coating agent composition

Family Cites Families (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE465549A (en) 1940-11-16 1900-01-01
US2386259A (en) * 1942-07-30 1945-10-09 Gen Electric Waterproofing treatment of materials
US2412470A (en) 1943-02-22 1946-12-10 Gen Electric Production of water-repellent materials
US2615824A (en) * 1948-02-17 1952-10-28 Francis W Minor Method and composition for imparting water resistance to textile material
US2782090A (en) * 1954-07-21 1957-02-19 Robbart Edward Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors
US2824778A (en) * 1954-09-28 1958-02-25 Robbart Edward Process for imparting water repellency to cellulosic material comprising cellulosic fibers by reaction with an aerosol containing organo silicon halide
US2802850A (en) * 1954-11-01 1957-08-13 Gen Electric Hydrophobic silicas
DE1277192B (en) 1957-02-19 1968-09-12 Edward Robbart Method and apparatus for making webs of cellulosic fiber-containing fabrics water repellent
US2961338A (en) * 1958-05-07 1960-11-22 Robbart Edward Process for treating wool and other fibrous materials to impart water repellency and resistance to shrinkage
US2995470A (en) * 1958-07-16 1961-08-08 Robbart Edward Method and apparatus for treating continuous lengths of material with gaseous compositions
US3856558A (en) * 1966-01-24 1974-12-24 E Robbart Treatment of cellulose
US4339479A (en) * 1966-01-24 1982-07-13 Edward Robbart Treatment of cellulose
US3418312A (en) * 1966-09-09 1968-12-24 Gen Electric Process for producing soluble trimethylsilylated cellulose
US3607901A (en) * 1967-09-20 1971-09-21 Gen Electric Method of making isocyanatoalkyl-substituted silanes
US3682675A (en) 1969-10-28 1972-08-08 Welsh Corp The Method of producing fire retardance in a prefinished panel
US3806549A (en) * 1971-11-03 1974-04-23 Owens Corning Fiberglass Corp Method of preparing organooxy silanes
DE2333966C3 (en) 1973-07-04 1979-10-11 Bayer Ag, 5090 Leverkusen Plastic, fungicidal organopolysiloxane molding compounds which can be stored under exclusion of water
US4013474A (en) 1975-05-06 1977-03-22 The United States Of America As Represented By The Secretary Of The Army Wood preservative compositions
US4109032A (en) * 1976-11-23 1978-08-22 Armstrong Cork Company Method for treating lightweight, non-cementitious building material
US4170690A (en) * 1977-03-18 1979-10-09 Rohm And Haas Company Process of coating weatherable, abrasion resistant coating and coated articles
US4151327A (en) * 1978-02-24 1979-04-24 Lawton William R Complex amine/silane treated cellulosic materials
US4349610A (en) * 1979-04-09 1982-09-14 Beloit Corporation Method for waterproofing paper
JPS56500407A (en) 1979-04-24 1981-04-02
JPS5719736A (en) 1980-07-10 1982-02-02 Ricoh Co Ltd Developer for diazo copying
JPS5736168A (en) 1980-08-13 1982-02-26 Showa Electric Wire & Cable Co Ltd Electrical insulating coating compound having heat resistance
JPS5765758A (en) 1980-10-09 1982-04-21 Toray Silicone Co Ltd Primer composition for bonding
US4423112A (en) 1980-12-08 1983-12-27 Dynamit Nobel Aktiengesellschaft Impregnating agent for materials containing cellulose
US4544413A (en) 1981-08-24 1985-10-01 Boots Byron R Solution for cleaning and preserving plastic and metallic surfaces
US4567221A (en) * 1983-03-31 1986-01-28 Kuraray Co., Ltd. Water resistant compositions
US4498538A (en) * 1983-06-21 1985-02-12 Union Oil Company Of California Method for maintaining the permeability of fines-containing formations
US4551385A (en) * 1983-11-16 1985-11-05 Edward Robbart Method for printing cellulosic substrates using modified reactive siloxanes to form an oleophilic layer thereon and impregnating thereafter with an ink
US4554215A (en) 1983-11-16 1985-11-19 Edward Robbart Coating of cellulosic base stocks and the product thereof
DE3635260A1 (en) * 1986-10-16 1988-04-28 Wacker Chemie Gmbh METHOD FOR MAKING WATER REPELLENT OF SUCTIONABLE INORGANIC CONSTRUCTION MATERIALS
PL148704B1 (en) 1986-11-18 1989-11-30 Polysiloxane composition and method of making the same
JP2558284B2 (en) * 1987-06-12 1996-11-27 東芝シリコ−ン株式会社 Method for producing alkoxysilane
US4859359A (en) 1988-03-25 1989-08-22 Dyna-5, Inc. Hard surface cleaning and polishing compositions
US4847088A (en) 1988-04-28 1989-07-11 Dow Corning Corporation Synergistic antimicrobial composition
DE3900303A1 (en) 1989-01-07 1990-07-12 Degussa METHOD FOR IMPREGNATING WOOD
CA2018325C (en) 1989-07-05 1995-07-04 Jay S. Wyner Method and apparatus for preserving masonry structures
US5204186A (en) 1989-10-13 1993-04-20 Advanced Chemical Technologies Co. Method for reducing the combustibility of combustible materials
US5120581A (en) 1989-10-13 1992-06-09 Advanced Chemical Technologies, Co. Method for reducing the combustibility of combustible materials
US5073195A (en) 1990-06-25 1991-12-17 Dow Corning Corporation Aqueous silane water repellent compositions
CA2022039A1 (en) * 1990-07-26 1992-01-27 Julio O. Gun Composition for producing a monomolecular film on the surfaces of various materials
EP0493747B1 (en) * 1990-12-25 1996-07-10 Matsushita Electric Industrial Co., Ltd. Anti-contaminating adsorbed film and method of manufacturing the same
US5466766A (en) * 1991-05-09 1995-11-14 Phillips Petroleum Company Metallocenes and processes therefor and therewith
SE502117C2 (en) 1991-07-08 1995-08-21 Probatum Ab Wood protection method - involves treatment with mixt. of boron cpd. and organic protective prepn.
JPH0543838A (en) 1991-08-21 1993-02-23 Sekisui Chem Co Ltd Zro2-sio2-cao coating composition
NZ244803A (en) 1993-01-13 1996-01-26 Nz Forest Research Inst Ltd Timber preservation process comprising drying the timber, then contacting with a liquid reactive boron compound
US5689754A (en) * 1993-10-28 1997-11-18 Minolta Co., Ltd. Regenerating apparatus for recording medium
DE4409039A1 (en) 1993-12-21 1995-06-22 Bayer Ag Antifouling agents
US5374761A (en) * 1994-04-29 1994-12-20 Corning Corporation Process for preparation of organooxysilanes
EP0747183A3 (en) 1995-05-25 1997-10-15 Shinetsu Chemical Co Modification of wood
JP2962191B2 (en) 1995-05-25 1999-10-12 信越化学工業株式会社 Method for producing modified wood
DE19520906A1 (en) 1995-06-08 1996-12-12 Feinchemie Gmbh Sebnitz Modified material from renewable raw materials
DE19524286A1 (en) 1995-07-06 1997-01-09 Weyl Gmbh Preventive wood preservatives
JPH0987115A (en) 1995-09-20 1997-03-31 Dainippon Jochugiku Co Ltd Termite-controlling agent for treating soil
US6706875B1 (en) * 1996-04-17 2004-03-16 Affyemtrix, Inc. Substrate preparation process
JP3185664B2 (en) 1996-05-13 2001-07-11 信越化学工業株式会社 Method for producing modified wood
JPH10251599A (en) 1997-03-07 1998-09-22 Mitsubishi Chem Corp Coating agent
US5954869A (en) 1997-05-07 1999-09-21 Bioshield Technologies, Inc. Water-stabilized organosilane compounds and methods for using the same
DE19900494A1 (en) * 1999-01-08 2000-07-13 Creavis Tech & Innovation Gmbh Hydrophobicization process for polymeric substrates
US6432181B1 (en) * 2000-03-03 2002-08-13 Resource Development, L.L.C. Silicone compositions, methods of making and using VOC free, non-flammable creams, pastes and powders to render nonporous surfaces water, soil and stain repellent
US7192470B2 (en) * 2003-05-27 2007-03-20 Woodholdings Environmental, Inc. Preservative compositions for materials and method of preserving same
DE60135649D1 (en) * 2000-06-06 2008-10-16 Woodholdings Environmental Inc PRESERVATIVE FOR WOOD PRODUCTS
US6902767B2 (en) * 2000-06-21 2005-06-07 D & L, Llc Process for treating wood and products from treated wood
US20030059545A1 (en) 2000-06-21 2003-03-27 Kelsoe Darrell W. Process for treating wood and products from treated wood
US20080075874A1 (en) * 2001-06-20 2008-03-27 Kelsoe Darrell W Process for treating wood and products from treated wood
US6663979B2 (en) * 2001-12-19 2003-12-16 United States Gypsum Company Coating for gypsum board face with uniform gloss intensity
JP2003193370A (en) * 2001-12-25 2003-07-09 Daikin Ind Ltd Water- and oil-repelling processing of textile product
US20050186348A1 (en) * 2002-10-17 2005-08-25 D & L Llc. Process for treating wood and products from treated wood
US20060068118A1 (en) 2003-08-13 2006-03-30 Reeve John A Silicon-containing treatments for solid substrates
US7463572B2 (en) * 2003-08-29 2008-12-09 International Business Machines Corporation High density data storage medium
US7425367B2 (en) * 2003-10-23 2008-09-16 O'rear Iii Edgar A Method for making an article water resistant and articles made therefrom
TWI297369B (en) * 2004-06-04 2008-06-01 Taiwan Textile Res Inst A method for treating surfaces of textile
KR101186732B1 (en) * 2004-07-21 2012-09-28 닛키 쇼쿠바이카세이 가부시키가이샤 Silica-based fine particles, method for production thereof, coating for forming coating film and base material having coating film formed thereon
CN100522977C (en) * 2004-08-24 2009-08-05 东亚合成株式会社 Process for producing organosilicon compound
EP1840113B1 (en) 2004-12-22 2017-05-31 Tayca Corporation Layered double hydroxide peelable in water, and production process and use thereof
US7205422B2 (en) * 2004-12-30 2007-04-17 Air Products And Chemicals, Inc. Volatile metal β-ketoiminate and metal β-diiminate complexes
EP1712956A3 (en) * 2005-04-13 2007-05-30 Ricoh Company, Ltd. Image bearing member, and image forming apparatus and process cartridge using the same
US20060284951A1 (en) * 2005-06-17 2006-12-21 Fuji Xerox Co., Ltd. Process and apparatus for forming pattern
US20070121535A1 (en) 2005-09-30 2007-05-31 Wanshi Chen Dynamic transmit power for non-canonical transmission formats
US20070275275A1 (en) * 2006-05-23 2007-11-29 Mesa Scharf Fuel cell anode purge systems and methods
KR100756676B1 (en) * 2006-11-23 2007-09-07 제일모직주식회사 Silicone bead, method for preparing the same, and thermoplastic resin composition using the same
US20080276970A1 (en) * 2007-05-09 2008-11-13 John Christopher Cameron Apparatus and method for treating materials with compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637570A (en) * 1969-02-25 1972-01-25 Us Air Force Process for producing protective coating of siloxane resin and product produced
US4002800A (en) * 1972-12-01 1977-01-11 Dynamit Nobel Aktiengesellschaft Impregnation of masonry having a neutrally or acidly reaction surface
JPS5638366A (en) * 1979-09-04 1981-04-13 Kanegafuchi Chem Ind Co Ltd Primer composition
US4491669A (en) * 1980-11-12 1985-01-01 Petrarch Systems Inc. Mixed alkoxyaminosilanes, methods of making same and vulcanizing silicons prepared therefrom
JPH01305006A (en) * 1988-06-02 1989-12-08 Nippon Soda Co Ltd Antifouling agent for fishing net
JPH026488A (en) * 1988-06-24 1990-01-10 Shin Etsu Chem Co Ltd Omega-alkynylsilane compound
JPH1192694A (en) * 1997-09-25 1999-04-06 Toshiba Silicone Co Ltd Emulsion composition
JP2000080354A (en) * 1998-09-03 2000-03-21 Ge Toshiba Silicones Co Ltd Rustproof and stain resistant coating agent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1841321A4 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7964031B2 (en) 2000-06-06 2011-06-21 Dow Corning Corporation Compositions for treating materials and methods of treating same
US7964287B2 (en) 2000-06-06 2011-06-21 Dow Corning Corporation Preservative compositions for wood products
US8721783B2 (en) 2000-06-06 2014-05-13 Dow Corning Corporation Compositions for treating materials and methods of treating same
EP2144712A1 (en) * 2007-05-09 2010-01-20 Woodholdings Environmental, Inc. and Dow Corning Corporation Apparatus and method for treating materials with compositions
EP2144712A4 (en) * 2007-05-09 2010-07-07 Woodholdings Environmental Inc Apparatus and method for treating materials with compositions
EP2206563A1 (en) * 2007-05-09 2010-07-14 Dow Corning Corporation Apparatus and method for treating materials with compositions
EP2556899A1 (en) 2007-05-09 2013-02-13 Dow Corning Corporation Apparatus and method for treating materials with compositions
US8940366B2 (en) 2007-05-09 2015-01-27 Petra International Holdings, Llc Apparatus and method for treating materials with compositions
CN101743068B (en) * 2007-05-09 2015-04-01 伍德控股环境公司 Apparatus and method for treating materials with compositions
JP2008289026A (en) * 2007-05-21 2008-11-27 Kyocera Corp Search interval control server and radio terminal

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US7846505B2 (en) 2010-12-07
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US7192470B2 (en) 2007-03-20
US20070107630A1 (en) 2007-05-17
TWI488924B (en) 2015-06-21
EP1841321A4 (en) 2013-04-24
US20060088605A1 (en) 2006-04-27
MX2007008740A (en) 2007-09-11
WO2006078625B1 (en) 2007-08-02
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CA2595095A1 (en) 2006-07-27

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