WO2006036294A1 - Compositions de conservation a base d'emulsion de cire et leur procede de fabrication - Google Patents

Compositions de conservation a base d'emulsion de cire et leur procede de fabrication Download PDF

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Publication number
WO2006036294A1
WO2006036294A1 PCT/US2005/027495 US2005027495W WO2006036294A1 WO 2006036294 A1 WO2006036294 A1 WO 2006036294A1 US 2005027495 W US2005027495 W US 2005027495W WO 2006036294 A1 WO2006036294 A1 WO 2006036294A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
alkyl
wax
gypsum
preservative
Prior art date
Application number
PCT/US2005/027495
Other languages
English (en)
Inventor
Steven Joseph Wantling
Original Assignee
Hexion Specialty Chemicals, Inc.
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Filing date
Publication date
Application filed by Hexion Specialty Chemicals, Inc. filed Critical Hexion Specialty Chemicals, Inc.
Priority to JP2007533465A priority Critical patent/JP2008514599A/ja
Priority to EP05778701A priority patent/EP1807376A1/fr
Priority to AU2005290253A priority patent/AU2005290253B2/en
Priority to CA 2581329 priority patent/CA2581329C/fr
Priority to BRPI0516021-9A priority patent/BRPI0516021A/pt
Publication of WO2006036294A1 publication Critical patent/WO2006036294A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/128—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, 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
    • B27K2200/00—Wooden materials to be treated
    • B27K2200/10—Articles made of particles or fibres consisting of wood or other lignocellulosic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, 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
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/343—Heterocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, 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
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/36—Aliphatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, 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
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • gypsum calcium sulfate dihydrate
  • GWF gypsum wood fiber
  • the manufacture of gypsum products generally comprises preparing a gypsum-containing slurry that contains gypsum and other components of the finished product, and then processing the slurry to remove the water and form and dry the remaining solids into the desired form, hi the making of gypsum board, the gypsum slurry must flow onto a paper substrate.
  • the slurry/sx ⁇ bstrate combination is then sized by passing this combination between rollers. Simultaneous with this sizing step, a paper backing is positioned over the sized gypsum slurry.
  • the gypsum slurry must possess sufficient fluidity so that a properly sized gypsum board can be made.
  • Fluidity refers to the ability of the gypsum slurry to flow.
  • Foamability refers to this ability to be foamed.
  • Foamability is important to this ability of the gypsum slurry to back flow at the rollers nip.
  • Forming plates may be used, eliminating the use of a master roll, but foam is important to control density of the finished product.
  • foam is important to control density of the finished product.
  • the time at which the gypsum slurry ceases its flow is referred to as the pre-set tine. Therefore, pre-set time is an important property of the gypsum slurry.
  • the set time of the gypsum slurry is also an important property.
  • the set time refers to the amount of time it takes the gypsum slurry to be dried, under heat, to the finished, solid gypsum board. As is well known in the art, in a continuous gypsum board manufacturing process, it is important that the gypsum slurry possess a consistent set time.
  • gypsum wood fiber (GWF) products is facilitated through a conventional paper making process.
  • the process of water felting dilute aqueous dispersions of various fibrous materials is a well-known commercial process for manufacturing many types of paper and board products.
  • an aqueous dispersion of fiber, binder and other ingredients, as desired or necessary is flowed onto a moving foraminous support wire, such as that of a Fourdrinier or Oliver mat forming machine, for dewatering.
  • the dispersion may be first dewatered by gravity and then dewatered by vacuum suction means; the wet mat is then pressed to a specified thickness between rolls and the support wire to remove additional water.
  • the pressed mat is then dried in heated convection or forced air drying ovens, and the dried material is cut to the desired dimensions.
  • the manufacture of gypsum wood fiber products may be carried out similarly, utilizing a wet end section headbox distribution mechanism distributing the gypsum wood fiber slurry onto a vacuum wire for initial mat formation and dehydration followed by compression through a series of vacuum belt rolls and into a kiln for final dehydration.
  • the gypsum wood fiber product does not incorporate paper face and back paper but rather is a paperless core that has similar performance and uses comparable to conventional sheathing products currently available.
  • Gypsum absorbs water, which reduces the strength of the products in which it is used and enables deleterious biological activity, such as the growth of mildew, mold, etc., to occur therein and thereon.
  • Prior art products like ordinary gypsum board, gypsum tile, gypsum block, gypsum casts, and the like have relatively little resistance to water.
  • ordinary gypsum board for example, is immersed in water, the board quickly absorbs a considerable amount of water, and loses a great deal of its strength. Tests have demonstrated that when a 2 inch by 4 inch cylinder of gypsum board core material was immersed in water at about 70° F. the cylinder showed a water absorption of 36% after immersion for 40 minutes.
  • Attempts to provide water-resistant properties to gypsum board include incorporation of asphalt, metallic soaps, resins, and wax additives into an aqueous gypsum slurry. The resulting materials were difficult to use and the core properties difficult to control. Polysiloxane-based systems have also been used in attempts to impart water resistance to gypsum board. Finished gypsum products have also been coated with water-resistant films or coatings.
  • One specific example of a past attempt to provide a water-resistant gypsum product is the spraying of a molten paraffin, wax or asphalt into an aqueous gypsum slurry.
  • Another example of a prior art attempt to provide a water-resistant gypsum product is the addition of an emulsion of wax, such as paraffin wax, and asphalt, in the relative proportions of from about 1 part to about 10 parts of asphalt per part of wax to the aqueous gypsum slurry.
  • Polyvinyl alcohol has been used in an attempt to provide a room temperature system for use in adding water-resistant properties to gypsum.
  • Some emulsions include generic starch species, e.g., from corn, sago, wheat, rice, etc., with a complexing agent such as sodium borate in combination with other chemical compounds, specifically sodium lignosulfate, C24 and greater polymerized alkyl phenol and various waxes. While this system shows significant advantages over previously available wax emulsions it to suffers from a number of deficiencies, including: degradation of the pH due to bacteriological activity resulting from the decomposition of the sodium lignosulfate in long-term storage, viscosity changes as temperature and age occur manifesting itself as a slight separation at the water/wax interface, and less than predictable use rates at the mixer due to the changes occurring singularly and in combination.
  • the panel board industry includes, but is not limited to, plywood, OSB (Oriented Strand Board) (commonly referred to as flake or wafer board), medium density fiber board, particleboard, and other products, inclusively referred to herein as lignocellulosic composite products.
  • OSB Oriented Strand Board
  • flake or wafer board medium density fiber board
  • particleboard particleboard
  • lignocellulosic composite products In each of these composite products and in lumber (the wood of trees cut and prepared for use as building material) (collectively referred to herein as "lignocellulosic products") it is desirable to control the water absorption or "uptake” and swelling, both of which have detrimental affect on the utility of the product. For example, in plywood used for floor underlay, swelling causes buckling or creep in the final wood or tile overlay.
  • Lignocellulosic composite products are conventionally manufactured by hot pressing lignocellulosic materials with wax and thermosetting resin. This is referred to as a conventional bonding process.
  • the wax is a sizing agent to improve the water resistance of the composite.
  • the resin is a bonding agent that holds the materials comprising the composite together, thus forming them into a unitary shape. Resoles are commonly used as the binding resin for lignocellulosic composite products.
  • a lignocellulosic material is combined with a phenolic resin and other components in a blender or mixer.
  • the blend or mixture that results is pressed, typically under pressures above atmospheric and temperatures greater than room temperature, to produce the composite.
  • Lignocellulosic materials used in the production of mats may be selected from the group consisting of wood fiber, wood flake, wood strands, wood chips and wood particles, and mixtures thereof.
  • the lignocellulosic materials listed here are referred to in the art as wood furnish. However, it is well known that other wood furnish, such as straw, bagasse, wood bark, recycled wood fiber, recycled paper fiber, and mixtures thereof, may also be used.
  • the wood furnish once blended or mixed with the phenolic resin, is then formed onto a support material to make a pre-form in the approximate shape of the finished good.
  • the pre-form is then placed on a caul plater in a hot press where the finished, good is produced by applying pressures above atmospheric and temperatures greater than room temperature. The elevated temperatures and pressures cause the phenolic resin to polymerize, thus binding the pre-form into a unitary finished good.
  • the hot press method is further described in U.S. Pat. No. 4,433,120 to Shui-Tung Chiu.
  • An emulsion comprising water as the continuous phase, a wax as the discontinuous phase, an emulsifier and a preservative has the general structure:
  • R 1 can be a heterocycle containing nitrogen and sulfur, such as thiazolyl, isothiazolyl, or thiadiazolyl, which can optionally be substituted with Cj-C 6 alkyl;
  • R 2 can be hydrogen or Ci-C ⁇ alkyl, specifically hydrogen; n is 0, 1, 2, or 3; each instance of R 3 can independently be hydrogen, Ci-C 6 alkyl, phenoxy, Ci-C 6 alkoxy, halo, amino, Ci-C 6 alkylamino, di Ci-C 6 alkyl amino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyrryl, naphthyl, phenyl, halophenyl, Ci-C 6 alkyl phenyl, or Ci-C 6 alkoxyphenyl.
  • a method for making a wax emulsion comprises making the emulsion without a preservative as defined herein, and then adding the preservative thereto.
  • a gypsum product comprises gypsum and a preservative as defined herein.
  • a method, for making a gypsum product comprises forming a slurry from gypsum, water, and a wax -in water emulsion containing a preservative as described herein, and forming the slurry into a solid product.
  • a method for improving the water resistance of a lignocellulosic composite product prepared by mixing lignocellulosic material with a binder to form a mixture and solidifying the mixture in a selected configuration to form the composite product comprises adding to the mixture an emulsion as defined herein.
  • a lignocellulosic composite product made by mixing lignocellulosic material with a binder to form a mixture, adding to the mixture an emulsion as defined herein, and forming the mixture and the emulsion therein into a solid product.
  • a type of preservative has been found to be particularly advantageous in wax emulsions, especially in wax emulsions used in the manufacture of gypsum products and wood fiber board and other lignocellulosic composite products.
  • preservatives disclosed herein are useful for inhibiting biological growth, e.g., the growth of mildew, fungi, etc., on gypsum products.
  • preservative includes biocides such as bactericides, fungicides, algaecides, mildewcides, or a combination thereof.
  • Exemplary preservatives include the compositions disclosed in U.S. Patent No. 3,370,957 to Wagner et al., which is incorporated in its entirety herein, and which discloses preservatives according to the general structure (I):
  • R 1 can be a heterocycle containing nitrogen and sulfur, such as thiazolyl, isothiazolyl, or thiadiazolyl, which can optionally be substituted with C 1 -C 6 alkyl;
  • R 2 can be hydrogen or C 1 -C 6 alkyl, specifically hydrogen;
  • n is 0, 1, 2, or 3;
  • each instance of R 3 can independently be hydrogen, C 1 -C 6 alkyl, phenoxy, C 1 -C 6 alkoxy, halo, amino, C 1 -C 6 alkylamino, di C 1 -C 6 alkyl amino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyrryl, naphthyl, phenyl, halophenyl, Cj-C 6 alkyl phenyl, C 1 -C 6 alkoxyphenyl, and the like.
  • mildewcide include those according to the general structures (II) and (III):
  • R 1 , R 2 , and R 3 are as defined previously.
  • Exemplary mildewcides according to structure (I) include: 2-(4'- thiazolyl) benzimidazole; 2-[3'-(l',2',5'-thiadiazolyl] benzirnidazole; 2-(4'-thiazolyl)- 5-methoxy benzimidazole; 2-(4'-thiazolyl)-5-phenoxy benzimidazole hydrochloride; 2-(2'-methyl-4'-thiazolyl) benzimidazole; 2-[4'-( l',2',3'-thiadiazolyl)] benzimidazole; l-acetyl-2-(4'-thiazolyl)-5-phenyI benzimidazole; 2-(4'-isothiazolyl) benzimidazole; 2-(4'-thiazolyl)-6-fluoro benzimidazole; 2-(4'-thiazolyl)-5-amino benzimi
  • thiabendazole (2-(4' -thiazolyl) benzimidazole) has been found to be effective in inhibiting the growth of biological agents on g ⁇ sum board, thus indicating the advantageous utility of benzimidole compounds generally and the other preservatives indicated herein.
  • the preservative is added as the last ingredient in the wax emulsion, i.e., the preservative is 'post-added' to the already-formed wax emulsion.
  • the preservative may be present in the wax emulsion in an amount of 0.01 to 10% by weight of the wax emulsion (wt.%), optionally 0.1 to 5 wt. %, for example, 0.2 to 4 wt.%.
  • the preservative may be added in any convenient form, including a 100% solids, as a hydrated paste or in a water diluted system, e.g., 25-50% active thiabendazole.
  • the preservative is preferably added with agitation, which is believed to thoroughly disperse the preservative into the discontinuous wax phase of the emulsion.
  • agitation which is believed to thoroughly disperse the preservative into the discontinuous wax phase of the emulsion.
  • one or more of these biocides or the others mentioned below may employed in an amount calculated to be about 0.0025 % to about 0.2 % by weight of the finished gypsum product.
  • the preservative is post-added to the wax emulsion under severe agitation to any desired wax emulsion where the water phase is the continuous phase in amounts ranging from 0.01 to 5% (percent) by volume.
  • the resulting wax emulsion can be used in the preparation of gypsum products and does not have significant affect on the desired properties of the finished products, i.e., strength, facing bonds, and water resistance where applicable.
  • the emulsions may be added to mixtures of gypsum and water without adversely affecting properties of the mixture which are necessary to the manufacture of gypsum products such as gypsum board and GWF.
  • properties include fluidity, formability and set time.
  • the preservative may be used in wax emulsions emulsified with various wax emulsions useful in the production of gypsum products, including emulsions containing stearic/oleic acid amine combinations where the amine structure can be described as TEA, DEA, AMP, Morpoline and other fatty acid amine systems normally considered known art; emulsions where a lignin sulfate or sulfonate acting as the surfactant in combination with various waxes; and emulsions comprising complex combinations consisting of starch compounds and metallic salts and calcium phenates, long branched chain calcium alkyl phenols, long straight chain calcium alkyl phenols, complex polymers of maleic acid with and without an amine attachment, and long chain, C 30 and above alkyl phenols, and wax or a combination of waxes.
  • emulsions Some non-limiting examples of such emulsions are provided below.
  • the addition of the preservative provides an emulsion which, when incorporated into a gypsum slurry, will provide resistance from mildew and other biological activity from occurring to a finished gypsum product while retaining the desired properties of the finished product, i.e., strength, facing bonds, and water resistance where applicable.
  • the use of these preservatives has been found to result in increased product strength relative to the use of other preservatives.
  • Wax emulsions containing the preservatives described herein may also be added to the resin used in making various kinds of panel board that do not contain gypsum.
  • the preservative may be used in a wax emulsion that contains starch, optionally a complexed starch, hi one embodiment, such an emulsion may include a wax, an alkyl phenol, a polynaphthalenesulfonic acid, an alkali metal hydroxide, and a complexed starch. The polynaphthalenesulfonic acid and the alkali metal hydroxide react to give a salt of polynaphthalenesulfonic acid.
  • Such emulsions may be prepared by (a) mixing the wax and an alkyl phenol to provide a first pre-mix; (b) mixing polynaphthalenesulfonic acid, an alkali metal hydroxide, water, and a complexed starch to provide a second pre-mix; (c) combining the first pre-mix and the second pre-mix to provide a mixture; and (d) homogenizing the mixture.
  • Waxes useful in making the various embodiments of the present invention may be selected from any of the commercially known waxes which have a melting point of from about 120° F to about 150°F, and preferably from about 135 0 F to about 145 0 F. Such waxes are typically of low volatility, exhibiting less than about a 10% loss in weight during standard thermogravimetric analysis. Also, the oil content of these waxes is typically less than about 1% by weight. These waxes are of a relatively high molecular weight, having an average chain length of C36 (that is a 36 carbon chain length), or greater.
  • the saponified wax functions as an added surfactant.
  • Waxes useful in this respect are limited to waxes having an acid value or a saponification value and a melting point greater than about 180° F. Saponification of such waxes may be accomplished by combining the wax with a strongly basic material such as ammonium hydroxide or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • Waxes which may be saponified in the preparation of emulsions described herein include waxes from the liquefication of coal, vegetable waxes and oxidized waxes resulting from the processing and/or refining of slack wax, scale wax or crude petroleum.
  • saponifiable waxes include montan wax, carnauba wax, beeswax, bayberry- myrtle wax, candelilla wax, caranday wax, castor bean wax, esparto grass wax, Japan wax, ouricury wax, retano- (or retamo-) ceri mimbi wax, shellac, spermaceti wax, sugar cane wax, wool-lanolin wax, and others.
  • the alkali metal hydroxide may be provided in the form of a concentrated aqueous solution that may comprise about 45% alkali metal hydroxide, by weight.
  • Ammonium hydroxide may be provided in solid form.
  • Some or all of the saponifier may also react with the dispersant, and/or with other component ingredients of the emulsion, in situ.
  • ammonium hydroxide is sometimes objected to because of the ammonia odor it produces, ammonium hydroxide is believed to be advantageous because, in addition to saponifying the wax, the ammonia can serve as a scavenger for formaldehyde in the resin with which the emulsion is used, and may thus reduce the emission of formaldehyde from the finished composite product.
  • ammonium hydroxide with formaldehyde also ameliorates the ammonium hydroxide odor, so in some embodiments, formaldehyde may be added to the emulsion for this purpose, for example, in an amount of about 0.02 to about 0.1% by weight.
  • ammonium hydroxide is especially advantageous for when the emulsion is used with lignocellulosic materials comprising northern wood species, i.e., Douglas fir, aspen and the like.
  • the amount of strongly basic material needed to saponify a wax may be calculated based on the saponification value of the 5 wax. For example, the saponification value divided by 1000 equals the grams of potassium hydroxide to add per gram of wax.
  • Suitable, non-saponifiable, waxes include a wax having a melting point greater than about 120°F (about 49 0 C), e.g., about 120°F to about 165°F (about 49°C to about 74°C), optionally about 12O 0 F to about 150 0 F (about 49 0 C to about 66 0 C), and preferably about 135°F to about 145 0 F (about 57°C to about 63°C).
  • Suitable nonsaponifiable waxes include paraffin waxes, slack waxes and scale waxes. Such waxes are commercially known to be of low volatility, exhibiting less than about a 10% loss in weight during standard thermo gravimetric analysis.
  • the oil content of these waxes is typically less than about 5% by weight, preferably less than about 1 % by weight.
  • Some of these waxes are of a relatively high molecular weight, having an average chain length of C36, that is a 36 carbon chain length, or greater.
  • Paraffin waxes are typically derived from light lubricating oil distillates and are predominantly straight chain hydrocarbons having an average chain length of 20 to 30 carbon atoms. Suitable paraffin waxes include Wax 3816 available from Honeywell/ Astor of Duluth, Georgia.
  • Slack waxes are petroleum waxes having an oil content of 3 wt.% to 50 wt. %.
  • Suitable slack waxes include Exxon 600 Slack Wax and Ashland 200 Slack Wax, and a combination of 50 parts Exxon 600 Slack Wax and 50 parts Ashland 200 Slack Wax.
  • Starch used in the emulsions of the present invention is complexed starch.
  • the starch may be complexed in situ, during manufacture of the emulsion, or the starch may be pre complexed prior to being added to the emulsion.
  • Starch is preferably complexed by mixing the starch with a complexing agent such as a borate compound, a molybdate compound or a molybdenum compound.
  • a preferred borate compound is sodium tetraborate decahydrate.
  • a preferred molybdate compound is ammonia hepta molybdate.
  • a preferred molybdenum compound is molybdenum disulfide.
  • ammonium biborate ammonium pentaborate, potassium pentaborate, potassium tetraborate, lithium tetraborate, and magnesium borate compounds
  • ammonium dimolybdate ammonium heptamolybbate
  • barium molybdate calcium molybdate
  • lithium molybdate magnesium molybdate
  • sodium molybdate sodium molybdate
  • potassium molybdate and other molybdenum compounds, and the like.
  • the starch useful in making the complexed starch of the present invention includes, but is not limited to, corn, rice, wheat, potato, sago and other starches.
  • the ratio of completing agent (a borate compound, a molybdate compound, or a molybdenum compound) to starch is important to the functionality of the complexed starch in the emulsions. It has been found) that the ratio may be as low as 1:20, of complexing agent (a borate compound, a molybdate; compound, or a molybdenum compound) to starch on a weight per weight basis. The ratio may be as high as 1 :3.5, however it has been found that at this ratio, and higher ratios, a greater amount of completed starch is needed in the emulsion to maintain the balance of desired properties in the gypsum mixture and final gypsum product. These desired properties include fluidity, formability, and water-resistance.
  • Borate compounds, molybdate compounds, and molybdenum compounds are surprisingly effective complexing agents.
  • useful complexing agents include, but are not limited to, sodium borate (borax), magnesium borate, and other borate compounds, ammonium molybdate, sodium molybdate, magnesium molybdate, and other molybdate compounds, molybdenum disulfide and other molybdenum compounds.
  • the ratio of complexing agent (for example, sodium tetraborate decabydrate, sodium molybdate dehydrate, molybdenum disulfide, or other compounds) to the modified starches significantly influences the control of other necessary properties in the board/slurry process, i.e., foam support and slurry additive compatibility.
  • alkyl phenols refer to phenolic compounds having a long chain alkyl group.
  • the long chain alkyl group may be straight or branched.
  • the long chain alkyl group may be C24 - C34 (from 24 to 34 carbon 0 chain length), preferably C24 - C28.
  • alkyl phenols include long chain, C24 - C34 (from 24 to 34 carbon chain length) polymerized methylene-coupled alkyl phenol, phenate salts, calcium phenates, long branched chain calcium alkyl phenols, long straight chain calcium alkyl phenols and complex polymers of maleic acid with and without an amine group substitution.
  • the alkyl group of the alkyl phenol can be derived from a corresponding olefin; for example, a C26 alkyl group is derived from a C26 alkene, preferably a 1 -alkene, a C34 alkyl group is derived from a C34 alkene, and mixed length groups are derived from the corresponding mixture of olefins.
  • the alkyl group is an alkyl group having at least about 30 carbon atoms, however, it may be an aliphatic group (or a mixture of such groups) made from homo- or interpolymers (e.g., copolymers, terpolymers) of mono- and di- olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene- 1, isobutene, butadiene, isoprene, 1-hexene, and 1- octene.
  • Aliphatic hydrocarbyl groups can also be derived from halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers.
  • Such groups can, however, be derived from other sources, such as monomelic high molecular weight alkenes (e.g., 1-tetracontene) and chlorinated analogs and hydrochlorinated analogs thereof, aliphatic petroleum fractions, particularly paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) greases) and other sources known to those skilled in the art.
  • Unsaturation in the hydrocarbyl groups can be reduced or eliminated, if desired, by hydrogenation according to procedures known in the art. Preparation by methods and materials that are substantially free from chlorine or other halogens is sometimes preferred for environmental reasons.
  • More than one alkyl group can be present, but usually no more than 2 or 3 are present for each aromatic nucleus in the aromatic group. Most typically only one hydrocarbyl group is present per aromatic moiety, particularly where the hydrocarbyl-substituted phenol is based on a single benzene ring.
  • alkyl phenol useful in the emulsions described herein is available from Lubrizol Chem. Corp. Wycliffe, Ohio, under the trade designation 319H, described as a C 24 - C 34 polymerized methylene- coupled alkyl phenol.
  • Various other, commercially available alkyl phenols that may be used in these emulsions, include the following (identified by arbitrary identifier numbers in the following Table 1 :
  • alkyl phenol and product of the reaction of an alkyl phenol with a saponifier or with any other component of the emulsion is referred to herein as the alkyl phenol component.
  • Such emulsions provide an alternative to the use of sodium lignosulfate or lignosulfonate previously used as both a co-surfactant and a dispersing aid, further reducing the need for a biocide to control biological activity.
  • the preservatives disclosed herein could, however, be used in emulsions comprising lignosulfate or lignosulfonate.
  • the ratios of starch:borate, or starch: molybdate, or starch: molybdenum compound may be about 4:1 to about 20:1 on a weight/weight basis.
  • Emulsions may be prepared by heating the wax and surfactants ("wax mixture”) in one vessel and the water, complexing agent (a borate compound, a molybdate compound, or a molybdenum compound) and corn starch ("water mixture”) in another vessel. Both mixtures were heated, with mixing, to about 185° (85° C). Next, the wax mixture was poured into the water mixture under mixing. The resultant mixture was then placed in a homogenizer.
  • wax mixture wax and surfactants
  • complexing agent a borate compound, a molybdate compound, or a molybdenum compound
  • corn starch corn starch
  • a distribution of micelle diameters ranging from about 0.6 micron to about 1.8 micron be achieved.
  • the distribution of micelle diameters may range from about 0.5 micron to about 2.5 micron.
  • This level of homogenization may be attained, for example, by using a dual orifice homogenizer operating at from about 2,000 to about 4,000 psi.
  • the homogenized mixture be cooled after the homogenization step.
  • the homogenized mixture be cooled from approximately 185° F to about 100° F. This may be accomplished by running the homogenized mixture through a cooling coil immersed in water maintained at room temperature.
  • an emulsion may be prepared by combining water, a complexing agent (that is, a borate compound, a molybdate compound, or a molybdenum compound) and a starch to make the complexed starch useful in certain embodiments.
  • a complexing agent that is, a borate compound, a molybdate compound, or a molybdenum compound
  • Polynaphthalenesulfonic acid and potassium hydroxide are added to the aqueous solution of complexed starch. This mixture is brought to a temperature of about 185 °F to about 205 °F and held until the starch reaches its maximum state of gelation, which typically occurs in about 20 to about 30 minutes.
  • the wax compounds are incorporated with the polymerized alkyl phenol and brought to a temperature of about 185 0 F to about 205 0 F.
  • the wax phase is added to the water phase and reacted to form an in situ surfactant.
  • a detergent/dispersant is formed by the combination and reaction of the polymerized aUcyl phenol and the polynaphthalenesulfonic acid, which acts to modify the wax crystal and allows the wax crystals to resist plating and linking with themselves and instead remain in a disassociated state until they are transferred due to polarity to the gypsum.
  • the reacted system is then passed through a homogenizer at a pressure of about 2,000 to about 4,000 psi and then cooled at a prescribed rate to control the stability and viscosity of the finished wax emulsion.
  • the homogenized composition exits the homogenizer at a temperature of about 135 °F to about 145 0 F.
  • the mixture is then cooled to about 80 °F to about 110 °F.
  • the cooling rate is controlled to avoid causing the wax to recrystallize and breakout of solution.
  • a low viscosity system can be developed allowing a broader range of solids, from about 40 % to about 60 % by weight to be available and usable.
  • a dual surfactant system provides a stable emulsion at both room temperature and elevated temperatures.
  • Such stable emulsions may be added, for example, to hot or boiling water, without the emulsion separating or curdling.
  • One example of dual surfactants is a combination of dodecylisopropanolamine benzene sulfonate and a nonionic ethoxylated aryl phenol.
  • Dodecylisopropanolamine benzene sulfonate may be obtained from Unichema, Wilmington, Delaware, under the trade name SDl 121.
  • One nonionic ethoxylated aryl phenol is Ethox 2938, available from Ethox Corp., Greenville, South Carolina.
  • an alkoxylated fatty acid ester may be combined with the of dodecylisopropanolamine benzene sulfonate to form the dual surfactant system.
  • One alkoxylated fatty acid ester is Ethox 2914, also available from Ethox Corp.
  • a dispersing aid or fluidity modifier, is useful for the maintenance of the fluidity of the gypsum/emulsion mixture.
  • Such dispersing agents are strong lipophiles, which are, consequently, good defoamers.
  • One sucli dispersing agent is poly(oxy-l,2-ethanedyl), alpha phenyl- omega-hydroxy styrenate.
  • An emulsion can be formed by combining and homogenizing a single wax, a dual surfactant system, an alkyl phenol and a complexed starch.
  • Table 1 below provides examples.
  • wax emulsions that may include the preservatives disclosed herein include those that contain (1) simple stearic/oleic acid amine combinations where the amine structure can be described as TEA, DEA, AMP, Morpoline and other fatty acid amines, and (2) a lignin sulfate or sulfonate acting as the surfactant in combination with various waxes.
  • An emulsion can be formed by combining and homogenizing two or more waxes, a co surfactant, an alkyl phenol and a complexed starch.
  • Typical composition ranges for two-wax emulsions are provided in Table 2 below. TABLE 2.
  • Table 3 below provides examples of emulsions made according to a dual-wax embodiment.
  • the emulsions of Table 3 maybe mixed with water, and gypsum may be added to the water emulsion mixture.
  • the water/emulsion/gypsum mixture may then be formed into a gypsum product.
  • a wax emulsion useful in making gypsum products may include lignosulfonate or lignosulfate, as illustrated in the following Table 4.
  • a useful wax emulsion may contain carboxymethylcellulose.
  • Such emulsions are useful with lignocellulosic products.
  • a carboxymethylcellulose-containing wax emulsion for use in a gypsum slurry useful for the manufacture of gypsum products comprises a nonsaponif ⁇ able wax, a saponified wax, an alkyl phenol component, a dispersant/surfactant, a carboxymethylcellulose component, and water.
  • the nonsaponif ⁇ able wax may comprise about 33% to about 35% of the emulsion, by weight, the saponified wax may comprise about 3% to about 5% of the emulsion, by weight, the alkyl phenol component may comprise about 0.5% to about 2.5% of the emulsion, by weight, the dispersant may comprise about 0.5% to about 2% of the emulsion, by weight, and the carboxymethylcellulose component may comprise about 0.2% to about 5% of the emulsion, by weight.
  • Emulsions described herein comprise a wax component comprising a nonsaponifiable wax and a saponifiable wax.
  • a suitable saponifiable wax has an acid value or a saponification value and a melting point greater than about 180 0 F (about 82°C).
  • the waxes do not contain more than about 5% (by weight) polar compounds as impurities.
  • the wax component may be present in an amount of about 25 percent by weight (wt. %) to about 50 wt. %, based on the total weight of the emulsion, preferably about 30 wt. % to about 40 wt. %.
  • the wax component comprises a combination of a nonsaponifiable wax having a melting point of greater than or equal to about 120 0 F and a saponifiable wax.
  • the nonsaponifiable wax may comprise about 25 wt. % to about 44 wt. % of the total weight of the emulsion, and the saponifiable wax may comprise about 0.5 wt. % to about 5 wt.
  • a preferred combination of waxes is a combination of a paraffin wax such as Honeywell 3816 as the first wax and a saponifiable wax such as montan wax.
  • the wax component comprises paraffin wax in an amount of about 25 wt. % to about 45 wt. %, preferably about 30 wt. % to about 40 wt. %, and saponifiable wax in an amount of about 2.5 wt. % to about 5 wt. %, preferably about 3.5 wt. % to about 4.5 wt. %, based on the total weight of the emulsion.
  • a strongly basic compound as described herein is added to the emulsion mixture to saponify the saponifiable wax.
  • the saponifier may be provided in an amount of about 0.15% to about 4.5%, optionally about 0.5% to about 3%, of the emulsion, by weight.
  • concentrated aqueous saponifier may be provided in an amount of about 0.5 to about 3% by weight of the emulsion; ammonium hydroxide maybe added in solid form in an amount of about 0.15 to about 3% by weight of the emulsion.
  • the amount of saponifier may be varied with the type of saponifiable wax used, or with the type of wood.
  • an emulsion as described herein may have a pH of about 8.5 to about 12.5, for example, apH of about 8.5 to about 9.5.
  • Exemplary carboxymethylcellulose materials useful in these emulsions have molecular carbon chain lengths of about 20 to about 50 carbons.
  • An example of a suitable carboxymethylcellulose is carboxymethylcellulose sodium, available from Perm Carbose, Somerset, Pennsylvania, under the trade designation LT-30, which is described as having carbon chain lengths of about 26 to 30 carbons.
  • Other suitable carboxymethylcellulose materials include Perm Carbose LT-20 and LT-42.
  • the carboxymethylcellulose and the product of its reaction with the saponifier or with any other component in the emulsion are referred to herein as the "carboxymethylcellulose component".
  • a salt of polynaphthalenesulfonic acid is useful in the emulsions described herein and, without wishing to be bound by theory, is believed to act as a dispersant/surfactant.
  • the salt may be the product of an in-situ reaction of polynaphthalenesulfonic acid and a saponifier, e.g., an alkali metal hydroxide.
  • a saponifier e.g., an alkali metal hydroxide.
  • One commercially available polynaphthalenesulfonic acid is DISAL GPS which may be obtained from Handy Chemical, Montreal, Quebec, Canada.
  • the acid and acid salt are referred to collectively as a polynaphthalenesulfonic acid component or, more broadly (to include substitute materials), as the dispersant/surfactant.
  • the dispersant/surfactant may comprise about 0.1% to about 5% of the emulsion, by weight, optionally about 0.25 wt. % to about 5 wt
  • an alkyl phenol is chosen so that the average carbon chain length of the alkyl portion matches, i.e., is approximately the same as or is close to, the average carbon chain length of the carboxymethylcellulose.
  • an alkyl phenol of average chain length in the range of about C 24 to about C 34 may be used in an emulsion comprising carboxymethylcellulose having an average chain length of about 26 to about 32 carbons, e.g., Carbose LT-30 carboxymethylcellulose.
  • the amount of alkyl phenol component present in the emulsion may be about 0.25 wt. % to about 10 wt. %, optionally about 0.5 wt. % to about 2.5 wt. % based on the total weight of the emulsion.
  • One method of manufacture for the emulsions described herein results in time, energy, operator, and production efficiencies.
  • the method involves mixing the ingredients of the emulsion in a single vessel and then conveying the mixture of a homogenizer under conditions such as the following.
  • An advantage of this method is that the emulsion mixture is prepared in a single vessel; it is not necessary to prepare and separately store partial mixtures of the ingredients of the emulsion in separate vessels before combining them together.
  • the nonsaponifiable wax e.g., 3816 wax, further described below
  • molten form e.g., at about 10°F above its melt point temperature
  • water is provided at a temperature that will not cause the wax to solidify.
  • the vessel is then charged in the following illustrative manner: a. Charge the melted nonsaponifiable wax, e.g., 3816 wax, at a temperature of about 189 0 F to about 192°F (about 87°C to about 89 0 C); b. Start heat and agitation; c.
  • the dispersant/surfactant e.g., DISAL polynaphthalenesulfonic acid, further described elsewhere herein
  • carboxymethylcellulose and saponifier e.g. Charge the remaining water - preferably including the water used to rinse the tubes calculated
  • the emulsion composition is passed from the homogenizer to a cooler to achieve a first exotherm of, e.g., about 10°F to about 20°F degrees lower than the homogenizer exit temperature, and then to a cooling tank to achieve a second exotherm of, e.g., about an additional 5°F to about 15°F lower, optionally under agitation.
  • the first exotherm may occur by cooling from about 130°F to about HO 0 F
  • the second exotherm may occur by cooling from about 11O 0 F to about 70 0 F.
  • using a two- exotherm cooling process allows a phasing process of the formation of the emulsion to proceed to completion.
  • the viscosity of the emulsion is more stable over time and the emulsion is more stable when subject to shear agitation than if a single exotherm cooling process is used.
  • a batch process may be used in which a first premix comprising the molten waxes and alkylphenol may be prepared, and a second premix (an aqueous premix) comprising the water, carboxymethylcellulose and polynaphthalenesulfonic acid and saponifier may be prepared, and the first and second premixes may then be combined in a mixing tank for a time sufficient at least for the waxes to become saponified, e.g., for one to three hours, and the resulting mix may then be passed to a homogenizer and cooled as described above.
  • Such an emulsion may have a viscosity of about 10 to about 100 centipoise, measured on a Brookf ⁇ eld viscometer. One sample emulsion had a viscosity of 9 cps at about 40% solids.
  • the emulsions described herein, and others, when incorporated into a gypsum slurry, are useful in the production of gypsum products, and the preservatives disclosed herein may be used with all of them.
  • a wax emulsion formulation was prepared with the following components: G Wax (a paraffin wax) 33%, Montan wax 3.3%, alkyl phenol 0.5%, Disal 0.5%, potassium hydroxide 0.75%, ammonium hepta molybdonate 0.01%, starch 0.09%, polyfon H (lignosulfonic acid, sodium salt) 0.5%, water 61.35%.
  • G Wax a paraffin wax
  • Montan wax 3.3% Montan wax 3.3%
  • alkyl phenol 0.5% alkyl phenol 0.5%
  • Disal 0.5% potassium hydroxide 0.75%
  • ammonium hepta molybdonate 0.01%
  • starch 0.09% polyfon H (lignosulfonic acid, sodium salt) 0.5%
  • MC-2 polyfon H
  • a sample of the subject material such as a gypsum board
  • potting soil and mold cultures at a constant temperature of about 90°F (32.2 0 C) and relative humidity of 95% to 98%.
  • the condition of the test sample is monitored weekly to determine the extent, if any, of mold growth.
  • the sample prepared as described above exhibited no biological growth during the first weeks of the test.
  • test emulsions as described above was used to prepare sample particle board coupons comprising a urea- formaldehyde binder. Some test emulsions contained 1% thiabendazole, others 2%, by weight of the wax in the emulsions. The emulsion was added to the furnish from which the coupons were formed in an amount of 0.4 % solids, by weight of the furnish. Some of the coupons were soaked in water for twenty-four hours before testing.
  • the preservative is impregnated into, and may be bonded to, the gypsum crystal structures, rather than merely residing on the surface of the product or being limited to residing in discrete agglomerations of wax that may remain after the wax emulsions are broken.
  • the incorporation of the preservative into the gypsum extends the effective life of the preservative because the preservative is less likely to leech from the internal structure of the gypsum crystals than from the surface of the gypsum product or from wax agglomerations therein. It may also be a contributing factor to the increased product strength noted in sample gypsum products containing this preservative.
  • any effective amounts of other preservatives may also be used in the gypsum products.
  • Such preservatives include e.g., bactericides/fungicides, mildewcides, or other biocides, may optionally be included in a gypsum product by incorporating the preservative into the emulsion or into the gypsum-containing slurry.
  • a preservative suitable for gypsum products is a bactericide/fungicide known commercially as METASOL D3TA, which comprises 3,5-dimethyl- tetrahydro-1, 3,5,2 H thiadiazine-2-thione.
  • METASOL D3TA may be obtained from Ondo-Nalco, Houston, Texas. Mildewcide can include any commercially available rnildewcide including formaldehyde. Other suitable biocides include bis-thio- benzene, propiconazole and bis(tributyltin) oxide.
  • Preservatives useful in lignocellulosic products including, e.g., GWF products and other gypsum products that contain wood fibers or other lignocellulosic material, and which might optionally be used in addition to thiabendizole and/or the preservatives related thereto as disclosed herein, may be inorganic or organic, and may include, for example, biocides such as insecticides, fungicides, bactericides, and combinations comprising one or more of the foregoing biocides.
  • the biocide may be chosen according to (1) the target organism; (2) solubility characteristics; (3) stability to the temperature and pH; and other conditions found in the manufacture of the composites.
  • Biocides include substances that kill or inhibit the growth of microorganisms such as molds, slimes, fungi, bacteria, etc. Insecticides, fungicides and bactericides are all examples of biocides. Fungicides include substances that kill or inhibit the growth of fungi. Bactericides include agents that kill bacteria. Insecticides are agents that kill insects. More specific examples of biocides include, but are not limited to, chlorinated hydrocarbons, organometallics, halogen-releasing compounds, metallic salts, organic sulfur compounds, and phenolics.
  • Preferred biocides include " but are not limited to chromated copper arsenate (CCA); such as ammoniacal copper quaternary ammonium (ACQ), ammonial copper zinc arsenate (ACZA), copper bis(dimethyldithiocarbamate) (CDDC), ammoniacal copper citrate and copper azole, copper naphthenate, zinc naphthenate, quaternary ammonium salts, pentachlorophenol, tebuconazole (TEB), chlorothalonil (CTL), chlorpyrifos, isothiazolones, propiconazole, other triazoles, pyrethroids, and other insecticides, imidichloprid, oxine copper and the like, and combinations comprising one or more of the foregoing biocides.
  • CCA chromated copper arsenate
  • ACQ ammoniacal copper quaternary ammonium
  • ACZA ammonial copper zinc arsenate
  • CDDC copper
  • Suitable general microbicides include, for example, 3-isothiazolones, 3 -iodo-2-propynylbutylcarbamate, 1 ,2-dibromo-2,4-dicyanobutane, methyl ene-bis- thio-cyanate (MBT), 2-thiocyano-methylthiobenzothiazole, tetrachloroisophthalo- nitrile, 5-bromo-5-nitro-l,3-dioxane, 2-bromo-2- nitropropane-l,3-diol, 2,2-di-bromo- 3-nitrilopropionamide (DBNPA), N,N'- dimethylhydroxyl-5,5'-dimethyl-hydantoin, bromochlorodimethylhydantoin, 1, 2-benzisothiazolin-3-one, 4,5-tri-methylene-2- methyl-3-isothiazolone, 5- chloro-2
  • Suitable fungicides include, for example, zinc dimethyl dithiocarbamate, 2-methyl-4-t-bxitylamino-6-cyclopropylammo-s-triazine, 2, 4,5,6- tetrachloroisophthalonitrile, N,N-dimethyl dichlorophenyl urea, copper thiocyanate, N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl- N'-phenyl-N'- fiuorodichloromethylthiosulfamide; copper, sodium and zinc salts of 2-pyridinethiol- 1 -oxide; tetraethylthiuram disulfide, 2,4,6- trichlorophenyl-maleimide, 2,3,5,6- tetrachloro-4-(methylsulfonyl)- pyridine, diiodomethyl p-tolyl sulfone, phenyl (bispyr
  • the fungicide may be an agricultural fungicide such as, for example, dithiocarbamate and derivatives such as ferbam, ziram, maneb (manganese ethylenebisdithio-carbamate), rr ⁇ ancozeb, zineb (zinc ethylenebisdithiocarbamate), propineb, metham, thiram, the complex of zineb and polyethylene thiuram disulfide, dazomet, and mixtures of these ⁇ vith copper salts; nitrophenol derivatives such as dinocap, binapacryl and 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic structures such as captan folpet, glyodine, dithianon, thioquinox, benomyl, thiabendazole, vinolozolin, iprodione, procymidone, triadimenol, triadimefon, biter
  • Combination bactericides/fungicides can be included in the preservative compositions.
  • An example of a bactericide/fungicide is METASOL D3TA, which is 3,5-dimethyl-tetrahydro-l,3,5,2H-thiadiazine-2-thione available from Ondo-Nalco, Houston, Texas.
  • Suitable insecticides include, fo ⁇ example, acephate, aldicarb, a - cypermethrin, azinphos-methyl, bifenthrin, binapacryl, buprofezin, carbaryl, carbofuran, cartap, chlorpyrifos, chlorpyrifos methyl, clofentezine, cyfluthrin, cyhexatin, cypermethrin, cyphenothrin, deltanxethrin, demeton, demeton-S-methyl, demeton-O-methyl, demeton-S, demeton-S-methyl sulfoxide, demephion-O, demephion-S, dialifor, diazinon, dicofol, dicrotophos, diflubenzuron, dimethoate, dinocap, endosulfan, endothion, esfenvalerate, ethiofen
  • Antitermite agents may be used in addition to other insecticides as long as they do not detract from the properties of the other insecticides.
  • Antitermite agents include Permetorin, Imidachlopride, Etpfenplox, and combinations comprising one or more of the foregoing agents.
  • suitable preservatives include alkylammonium compounds such as didecyldimethylammonium chloride (DDAC), BARDAP (N 5 N- didecyl-N-methylpolyoxyethylammonium propionate), copper benzalconium chloride or N-alkylbenzyldimethylammonium chloride (BKC); metal salts of naphthetic acid such as copper naphthenate (NCU) or zinc naphthenate (NZN); metal salts of versatic acid such as zinc versatate; triazole type compounds such as Cyproconazole [(2RS,3RS;2RS,3SR)-2-(4-chlorophenyl)-3- (cyclopropyl-l-(lH-l,2,4-triazol-l- yl)butan-2-01], Tebuconazole [(RS)-l-p- chlorophenyl-4,4-dimethyl-3-(lH-l,2,4-
  • the lignocellulosic preservatives may be used in combination.
  • Preferred combinations include Cyproconazole and DDAC; Cyproconazole and BARDAP; Tebuconazole and Propiconazole; and the like.
  • a compound which is effective to inhibit or prevent growth of wood rot soil bacteria and wood soft rot fungi may also be used as a preservative.
  • Such compounds include p-cumylphenol (PCP), and its salts such as the sodium salt of p-cumylphenol, the ethylamine salt of p-cumylphenol, and combinations comprising one or more of the foregoing wood preservatives.
  • PCP inhibits the growth of wood rot soil bacteria, ascomycetes and imperfect fungi, and it is effective as an antimold agent and antitermite agent. Therefore, PCP is particularly preferable.
  • PCP can exhibit a sufficient effect to wood materials in the treatment amount (application amount) of about 200-1,000 grams per cubic meter of wood (g/m3).

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une émulsion comprenant de l'eau comme phase continue, une cire comme phase discontinue, un émulsifiant et un agent conservateur ayant la structure générale (I), dans laquelle R1 peut représenter un hétérocycle contenant de l'azote et du soufre, par exemple thiazolyl, isothiazolyl, ou thiadiazolyl, que l'on peut substituer avec alkyle C1-C6 ; R2 peut représenter hydrogène ou alkyle C1-C6, spécifiquement hydrogène ; n représente 0, 1, 2, ou 3 ; chaque instance de R3 peut indépendamment représenter hydrogène, alkyle C1-C6, phénoxy, alcoxy C1-C6, halo, amino, alkylamino C1-C6, dialkylamino C1-C6, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thiényle, furyle, pyrryle, naphtyle, phényle, halophényle, alkyle phényle C1-C6, ou alcoxyphényle C1-C6. L'agent conservateur peut être ajouté à l'émulsion une fois cette dernière formée. L'émulsion peut être incorporée dans un produit en plâtre, par exemple une plaque en plâtre ou une plaque en plâtre avec fibre de bois. On peut fabriquer le produit en plâtre en formant en un produit solide une pâte contenant du plâtre, de l'eau, et l'émulsion. L'invention concerne en outre un procédé qui améliore la résistance à l'eau d'un produit composite lignocellulosique préparé en mélangeant un matériau lignocellulosique avec un liant pour former un mélange et en solidifiant ledit mélange en une configuration choisie pour obtenir le produit composite, ledit procédé pouvant consister notamment à ajouter au mélange une émulsion telle que décrite ci-dessus.
PCT/US2005/027495 2004-09-27 2005-08-03 Compositions de conservation a base d'emulsion de cire et leur procede de fabrication WO2006036294A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2007533465A JP2008514599A (ja) 2004-09-27 2005-08-03 ワックス乳剤防腐剤組成物および製造方法
EP05778701A EP1807376A1 (fr) 2004-09-27 2005-08-03 Compositions de conservation a base d'emulsion de cire et leur procede de fabrication
AU2005290253A AU2005290253B2 (en) 2004-09-27 2005-08-03 Wax emulsion preservative compositions and method of manufacture
CA 2581329 CA2581329C (fr) 2004-09-27 2005-08-03 Compositions de conservation a base d'emulsion de cire et leur procede de fabrication
BRPI0516021-9A BRPI0516021A (pt) 2004-09-27 2005-08-03 emulsão, método para produção de uma emulsão de cera, produto de gesso, método para a produção do mesmo, método para aperfeiçoar a resistência à água de um produto compósito lignocelulósico, e, produto compósito lignocelulósico

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61357704P 2004-09-27 2004-09-27
US60/613,577 2004-09-27

Publications (1)

Publication Number Publication Date
WO2006036294A1 true WO2006036294A1 (fr) 2006-04-06

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PCT/US2005/027495 WO2006036294A1 (fr) 2004-09-27 2005-08-03 Compositions de conservation a base d'emulsion de cire et leur procede de fabrication

Country Status (8)

Country Link
EP (1) EP1807376A1 (fr)
JP (1) JP2008514599A (fr)
CN (1) CN100457665C (fr)
AR (1) AR050803A1 (fr)
AU (1) AU2005290253B2 (fr)
BR (1) BRPI0516021A (fr)
CA (1) CA2581329C (fr)
WO (1) WO2006036294A1 (fr)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2008155979A1 (fr) * 2007-06-19 2008-12-24 Yoshino Gypsum Co., Ltd. Plaque de plâtre résistant aux moisissures
EP3808179A1 (fr) * 2019-10-16 2021-04-21 LANXESS Deutschland GmbH Mélanges fongicides
EP3808178A1 (fr) * 2019-10-16 2021-04-21 LANXESS Deutschland GmbH Mélanges fongicides

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN105199272A (zh) * 2015-07-28 2015-12-30 苏州新区特氟龙塑料制品厂 一种防霉改性聚四氟乙烯配方

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WO2004033581A1 (fr) * 2002-10-11 2004-04-22 Borden Chemical, Inc. Additifs servant a rendre des produits gypseux resistants a l'eau

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008155979A1 (fr) * 2007-06-19 2008-12-24 Yoshino Gypsum Co., Ltd. Plaque de plâtre résistant aux moisissures
JP5520603B2 (ja) * 2007-06-19 2014-06-11 吉野石膏株式会社 防カビ性を有する石膏ボード
CN105565757A (zh) * 2007-06-19 2016-05-11 吉野石膏株式会社 具有防霉特性的石膏板
EP3808179A1 (fr) * 2019-10-16 2021-04-21 LANXESS Deutschland GmbH Mélanges fongicides
EP3808178A1 (fr) * 2019-10-16 2021-04-21 LANXESS Deutschland GmbH Mélanges fongicides
WO2021074149A1 (fr) * 2019-10-16 2021-04-22 Lanxess Deutschland Gmbh Mélanges fongicides
WO2021074133A1 (fr) * 2019-10-16 2021-04-22 Lanxess Deutschland Gmbh Mélanges fongicides

Also Published As

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AU2005290253A1 (en) 2006-04-06
JP2008514599A (ja) 2008-05-08
CN100457665C (zh) 2009-02-04
BRPI0516021A (pt) 2008-08-19
CN101039885A (zh) 2007-09-19
AU2005290253B2 (en) 2011-04-14
EP1807376A1 (fr) 2007-07-18
CA2581329C (fr) 2009-05-19
CA2581329A1 (fr) 2006-04-06
AR050803A1 (es) 2006-11-22

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