[go: up one dir, main page]

WO2005061228A1 - Isolation antimicrobienne - Google Patents

Isolation antimicrobienne Download PDF

Info

Publication number
WO2005061228A1
WO2005061228A1 PCT/US2004/019360 US2004019360W WO2005061228A1 WO 2005061228 A1 WO2005061228 A1 WO 2005061228A1 US 2004019360 W US2004019360 W US 2004019360W WO 2005061228 A1 WO2005061228 A1 WO 2005061228A1
Authority
WO
WIPO (PCT)
Prior art keywords
antimicrobial
insulation
antimicrobial agent
composition
agent
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2004/019360
Other languages
English (en)
Inventor
Stephen A. Payne
Howard Wayne Swofford
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Microban Products Co
Original Assignee
Microban Products Co
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 Microban Products Co filed Critical Microban Products Co
Priority to MXPA06014847A priority Critical patent/MXPA06014847A/es
Priority to AU2005262841A priority patent/AU2005262841A1/en
Priority to PCT/US2005/015506 priority patent/WO2006007044A1/fr
Priority to CNA2005800196497A priority patent/CN1989005A/zh
Priority to BRPI0512072-1A priority patent/BRPI0512072A/pt
Priority to EP05742871A priority patent/EP1755887A4/fr
Priority to CA2569871A priority patent/CA2569871C/fr
Publication of WO2005061228A1 publication Critical patent/WO2005061228A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B32B5/265—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi

Definitions

  • the present invention relates generally to insulation and methods for making insulation.
  • the present invention relates to an efficient and economical method for producing insulation that possesses antimicrobial (e.g., antibacterial and antifungal) properties.
  • antimicrobial e.g., antibacterial and antifungal
  • Insulation is a ubiquitous construction material. It is found in practically all residential and commercial construction and its importance in the construction of new structures cannot be over emphasized.
  • the primary function of insulation is to act as a heat transfer barrier between the interior of a structure and the outside environment. Thus insulation, if properly installed, can greatly reduce heating and air conditioning costs. Insulation can also serve as a sound barrier, moisture barrier, and vapor/air barrier.
  • Wallboard is a construction material used to form interior walls that also has a paper component.
  • the present invention derives from research directed at developing a commercially viable process for making insulation that exhibits antimicrobial characteristics.
  • One result of this research was the development of insulation which exhibits antimicrobial characteristics and resists the growth of microbes.
  • the insulation according to the invention comprises an insulating material such as fiberglass, a non-woven covering adjacent the insulating material, and an antimicrobial composition.
  • the insulating material will be attached to the non-woven covering by an adhesive.
  • the antimicrobial composition is preferably intimately associated with the non-woven covering, the adhesive or both.
  • the invention also encompasses a method for producing insulation that exhibits antimicrobial characteristics and resists the growth of microbes.
  • the method comprises the steps of contacting a non-woven covering to an insulating material, and applying an antimicrobial composition to the non- woven covering.
  • the method also comprises adding an antimicrobial composition to the insulation or to a component thereof at levels sufficient to exhibit efficacy against microbes.
  • the invention is insulation that exhibits antimicrobial characteristics and resists the growth of microbes.
  • microbes encompasses bacteria, fungi, and other such forms of life that are generally considered by those skilled in the art to fall within the realm of microbiology.
  • Fungus i.e., mold and mildew
  • this detailed description will often make reference to fungus and antifungal agents. This method of presentation should not be interpreted as limiting the scope of the invention in any way.
  • efficacy is defined as the characteristic of inhibiting the growth of a microbe on a substrate.
  • antimicrobial composition includes individual antimicrobial agents (e.g., silver, triclosan, zinc oxide, etc.) and various combinations of antimicrobial agents and other additives.
  • the insulation according to the invention comprises an insulating material, a non-woven covering adjacent the insulating material and an antimicrobial composition.
  • the non-woven covering will be connected to the insulating material using an adhesive.
  • the adhesive is an asphalt or tar-like adhesive that is well known in the industry.
  • the insulating material may be any of the commonly known insulating materials. Perhaps the most commonly known and used insulating material is fiberglass batting. This type of insulating material is found in most commercially available lines of insulation including the well known pink colored insulation available from Owens-Corning. Fiberglass batting is the preferred insulating material for use in the practice of the invention.
  • the non-woven covering used in the practice of the invention may be any type of non- woven material capable of attachment to and support of insulating material.
  • Synthetic polymer non-woven mats are examples of acceptable non-woven material.
  • the non-woven covering used in the practice of the invention is made from natural polymers such as cellulose.
  • Paper is the non- woven material of choice used in the insulation industry. Accordingly, a particularly preferred non-woven covering for use with the invention is paper.
  • the antimicrobial composition and the various methods of applying the antimicrobial composition to the non-woven covering represent the most diverse aspect of the invention. If synthetic polymer non-woven material is used then the antimicrobial composition can be added to the polymer melt prior to formation of the non-woven mat.
  • the antimicrobial compositions that may be used in conjunction with synthetic polymer non- woven coverings include all of the antimicrobial agents, or combinations of agents, commonly used with synthetic polymers.
  • Such agents include, but are not limited to chlorinated phenols (e.g., triclosan), quaternary ammonium compounds, azoles, and metals (e.g., silver zeolites, silver ions).
  • chlorinated phenols e.g., triclosan
  • quaternary ammonium compounds e.g., azoles
  • metals e.g., silver zeolites, silver ions
  • the antimicrobial agents utilized in the practice of the invention may include any antimicrobial composition capable of imparting antimicrobial characteristics to insulation and particularly the non-woven (e.g., paper) covering.
  • any antimicrobial composition capable of imparting antimicrobial characteristics to insulation and particularly the non-woven (e.g., paper) covering.
  • antimicrobial agents are discussed or cited in priority document U.S. Patent Application Serial Number 10/250,143, which is incorporated herein by reference.
  • Such agents include, but are not limited to chlorinated phenols (e.g., triclosan), quaternary ammonium compounds, azoles, and metals(e.g., silver zeolites).
  • the antimicrobial composition may be applied to the paper in any of several ways.
  • the paper may be treated by adding antimicrobial compositions to the fiber/pulp slurry during formation of the paper. Although this method can be effective, it tends to be cost prohibitive.
  • the paper may be surface treated with an antimicrobial composition.
  • Spraying the paper covering with the antimicrobial composition is within the scope of the invention.
  • Those skilled in the art of papermaking are very familiar with spraybars and their use and how they can be easily adopted for use with the present invention.
  • Another method of treating the paper surface is to apply the antimicrobial composition as a uniform coating on one side or both sides of the paper covering as the paper covering is made.
  • the antimicrobial composition could be applied to the paper at the calendar stack rolls using a water bath that is sometimes present in papermaking processes.
  • all embodiments of the invention contain a quantity of antimicrobial composition sufficient to exhibit efficacy against microbes and particularly various species of fungi. More specifically, the preferred embodiments of the invention contain a quantity of antimicrobial composition sufficient to inhibit microbial growth on a substrate tested in accordance with AATCC (American Association of Chemists & Colorists) Test Method 30, Part III , ASTM G21, and/or ASTM 3273. Those skilled in the art are familiar with these test methods and their parameters.
  • AATCC American Association of Chemists & Colorists
  • the papermaking process may determine both the method of application and the antimicrobial composition used. Each papermaking process is unique in some respect and those skilled in the art can determine which application method and antimicrobial composition is best for their particular process.
  • Papermaking processes are often considered to be among the most complicated and sensitive of industrial processes. Operators are generally loathe to alter an existing process in any way. The uniqueness of each production line necessarily means that what is optimal for one line may not be optimal for another. Accordingly, those skilled in the art know that some degree of fine tuning and optimization will be encountered during practice of the invention.
  • Antimicrobial Composition #1 specifically, different antimicrobial compositions that may be used with different application techniques. These embodiments are exemplary of the diversity of the invention and should not be construed to limit the scope of the invention.
  • Antimicrobial Composition #1 is exemplary of the diversity of the invention and should not be construed to limit the scope of the invention.
  • the antimicrobial composition is an antimicrobial system that comprises a first antimicrobial agent in a first carrier and a second antimicrobial agent in a second carrier.
  • the first and second carriers are at least partly soluble in each other. This adds to the stability of the antimicrobial system by minimizing the formation of two liquid phases or solid particulate sedimentation.
  • one antimicrobial agent suitable for use in the practice of the invention is propiconazole which is commercially available from Janssen Pharmaceutica under the trade name WOCOSEN.
  • Another antimicrobial agent suitable for use in the present invention is diiodomethyl-4-tolylsulfone which is commercially available from Dow Chemical under the trade name AMICAL. Both commercial embodiments can be obtained in carriers that are soluble in each other which improve the system's stability.
  • antimicrobial agents suitable for use in the antimicrobial system can come in surfactant based carriers. Although surfactant based carriers can be used in the practice of the invention care should be taken when using such carriers to ensure that the application system does not become burdened with foam. Foam can sometimes develop if the application system provides for the agitation of the antimicrobial composition. Foam can detrimentally effect the smooth and uniform distribution/application of the active ingredients. In some instances asmall quantity of an anti- foaming agent can be added to the antimicrobial composition to reduce the potential for excessive foam build-up. Preferred anti-foaming agents are ethoxylated co-polymers of polyethylene glycol.
  • the first antimicrobial agent used in the antimicrobial system is selected from the group consisting of propiconazole, sodium pyrithione, and mixtures thereof. Both agents are commercially available in various concentrations and can be diluted to the extent necessary by those skilled in the art.
  • the second antimicrobial agent used in the antimicrobial system is selected from the group consisting of tolyl diiodomethyl sulfone; tebuconazole, thiabendazole; and 3-iodo-2-propynyl butylcarbamate, and mixtures thereof. These agents are commercially available as well.
  • a preferred embodiment of the antimicrobial system is an emulsion comprising by weight about 0.1% to 0.8% propiconazole, about 0.1% to 0.5% tolyl diiodomethyl sulfone, and about 0.05% - 0.15% 3-iodo-2- propynyl butylcarbamate, in water.
  • Emulsions using by weight about 0.20% propiconazole, 0.175% tolyl diiodomethyl sulfone, and 0.10% 3-iodo-2-propynyl butylcarbamate, in water, applied to 50 lb. per square foot paper showed acceptable efficacy when applied to the surface of the paper at between about 5% and about 20% wet pickup based on the dry weight of the paper. Wet pickup between about 5% and about 7% showed acceptable results and would be preferable due to cost considerations.
  • the quantity picked up by the paper can be adjusted in several ways known to those skilled in the art.
  • the antimicrobial agents are applied such that the total pickup or retention of agents in the paper (and/or the adhesive) is between about 100 ppm and 20,000 ppm. Of course, additional antimicrobial agent can be applied but anything above 20,000 ppm would likely be cost prohibitive. Examples [0037] Various combinations of the following antimicrobial agents were thoroughly mixed together at ambient conditions in water as shown in Table below. Table 1
  • DITS diiodmethyl-4-tolysulfone
  • IPBC 3-iodo-2-propynyl butylcarbamate
  • Zn Pyrithione Zinc Pyrithione
  • Prop. propiconazole (Wocosen Technical from Janssen)
  • TDS tolyl diiodomethyl sulfone (Amical Flowable from Dow)
  • IPBC iodo-2-propynyl-butylcarbamate (Polyphase CST from Troy)
  • Tri. triclosan (Ingrasan DP300 from Ciba) Table 4
  • Prop. propiconazole (Wocosen 250EC from Janssen)
  • TDS tolyl diiodomethyl sulfone (Amical Flowable from Dow)
  • TDS2 tolyl diiodomethyl sulfone (Amical 48 from Dow)
  • IPBC iodo-2-propynyl-butylcarbamate (Omacide IPBC40 from Arch)
  • Teb. tebuconazole (Preventol A8 from Bayer)
  • the antimicrobial system is applied to the non-woven covering (i.e., paper) such that the first antimicrobial agent is present in or on the non-woven covering in a concentration between about 50 ppm and about 1200 ppm, more preferably between about 200 ppm and 1200 ppm.
  • the first antimicrobial agent is propiconazole and is present in a concentration between about 80 ppm and 1000 ppm; more preferably between about 500 ppm and 1000 ppm.
  • the second antimicrobial agent preferably is present in the non-woven covering at a concentration between about 50 ppm and 1600 ppm; more preferably between about 60 ppm and 1400 ppm.
  • the second antimicrobial agent is tolyl diiodomethyl sulfone (Amical Flowable from Dow) and is present in a concentration between about 40 ppm and 1600 ppm; more preferably between about 60 ppm and 1400 ppm.
  • Antimicrobial Composition #2 is tolyl diiodomethyl sulfone (Amical Flowable from Dow) and is present in a concentration between about 40 ppm and 1600 ppm; more preferably between about 60 ppm and 1400 ppm.
  • the antimicrobial composition used in the practice of the invention comprises a microemulsion of a quaternary ammonium antimicrobial agent.
  • this embodiment of the antimicrobial composition comprises an aqueous microemulsion.
  • the microemulsion comprises a quaternary ammonium antimicrobial agent, a phenol, and water.
  • the composition need not contain the volatile alcohols (e.g., ethanol) that are usually used to form emulsions of quaternary ammonium antimicrobial agents.
  • volatile alcohols e.g., ethanol
  • Quaternary ammonium antimicrobial agents suitable for use in the antimicrobial composition include, but are not limited to, N-alkyldimethyl benzyl ammonium saccharinate, 1,3,5-Triazine- 1,3,5(2 H,4H,6H)-triethanol; 1-Decanaminium, N-decyl-N, N-dimethyl-, chloride (or) Didecyl dimethyl ammonium chloride; 2-(2-(p-(Diisobuyl) cresosxy)ethoxy)ethyl dimethyl benzyl ammonium chloride; 2-(2-(p- (Diisobutyl)phenoxy)ethoxy)ethyI dimethyl benzyl ammonium chloride; alkyl 1 or 3 benzyl- l-(2-hydroxethyl)-2- imidazolinium chloride; alkyl bis(2- hydroxyethyl) benzyl ammonium chloride; alkyl bis
  • the quaternary ammonium antimicrobial agent comprises a dimethylbenzyl ammonium compound such as N-alkyl dimethylbenzyl ammonium saccharinate.
  • N-alkyl dimethylbenzyl ammonium saccharinate is commercially available from Stepan Chemical Company of Northfield, Illinois, under the trade name ONYXCIDETM 3300. This particular form of ONYXIDETM is approximately 95% active and is a solid at room temperature but will form a liquid at elevated temperature. It is light yellow-orange in color and is insoluble in water.
  • the phenol utilized in the practice of the invention is preferably an alkyl phenol, a styrenated phenol, or a combination of the two. Such phenols are commercially available from a number of sources. [0048] The precise phenol utilized in the practice of the invention will likely be determined by the overall process. If it is determined that an alkyl phenol is best for a particular process, the alkyl phenol utilized in this embodiment preferably comprises at least one alkyl phenol having at least one alkyl group selected from the group consisting of C 7 alkyls, C 8 alkyls, C 9 alkyls, Cio alkyls, and Cn alkyls.
  • the alkyl phenol comprises an alkyl phenol having a C 9 alkyl group.
  • Alkyl phenols suitable for use in this embodiment are commercially available from a number of sources. Particularly preferred commercially available alkyl phenols include TRITONTM X-207 sold by Dow Chemical Company.
  • the particular styrenated phenol utilized in the practice of the invention will depend upon the overall process.
  • the styrenated phenol is preferably non-ionic.
  • Preferred styrenated phenols include CHROMASISTTM WEZ and STAND APOL HSTM, both of which are commercially available from Cognis Corporation whose North American office is in Cincinnati, Ohio.
  • Water makes up the other primary component of this embodiment of the antimicrobial composition.
  • the antimicrobial composition may contain other additives. Two such additives are anti-foaming agents and anti-freezing agents.
  • the alkyl phenols and styrenated phenols used in this embodiment of the antimicrobial composition can be susceptible to foaming depending upon the particular application. Therefore, it is envisioned that some commercial applications will contain anti-foaming agents.
  • this embodiment of the antimicrobial composition according to the invention may be used to treat paper.
  • One method of treating this type of paper is to add the antimicrobial composition to the water box, a device toward the end of the paper process that returns a certain quantity of water to the paper after the paper has undergone heat based drying.
  • the water box is often agitated due to the continuous movement of paper through it. This agitation can cause foaming upon the addition of the claimed antimicrobial composition. Generally, the presence of foam is detrimental to the water box portion of a paper process. Therefore an anti- foaming agent is added to the composition according to the invention when the invention is used to treat paper at the water box.
  • Preferred anti-foaming agents are ethoxylated co-polymers of polyethylene glycol.
  • the commercial formulations of stryrenated phenols and alkyl phenols may contain a quantity of an antifbaming agent.
  • TRITONTM X-207 contains a small quantity of polyethylene glycol. Accordingly, if TRITONTM X-207 is the source of the phenol additional antifoaming agent may not be needed.
  • anti-freezing agents may be added to the composition according to the invention.
  • the anti-freezing agents are not thought to be critical to the actual performance of the invention. Instead they are used to keep the composition from freezing or becoming too viscous during transport in cold weather.
  • the anti-freezing agents may be left out of the composition if they are found to interfere with the addition of the antimicrobial agent in any particular process.
  • a preferred anti-freezing agent is dipropylene glycol.
  • the quaternary ammonium antimicrobial agent is present in the antimicrobial composition in an amount between about 1 wt. % and 30 wt. %. In particularly preferred embodiments the quaternary ammonium antimicrobial agent is present between about 15 wt. % and 20 wt. % of the overall composition. [0061] As an example of how the invention may be tailored to meet specific process requirements, it was determined that a composition having approximately 17 wt. % ONYXIDETM 3300 successfully and efficiently imparted antimicrobial characteristics to paper in one particular papermaking process.
  • the total phenol content of the antimicrobial composition is between about 10 wt. % and about 60 wt. % of the total composition.
  • Preferred embodiments utilize between about 20 wt. % to about 50 wt. % alkyl phenol and about 1 wt. % to about 10 wt. % styrenated phenol.
  • the quantity of anti- foaming agent needed for successful practice of the invention will range between about 0 wt. % to about 20 wt. %.
  • the remainder of the antimicrobial composition comprises water.
  • the quantity of water present in the claimed composition will be between about 5 wt. % and about 30 wt. %, more preferably between about 10 wt. % and about 20 wt. %. Again, the exact quantity of water will depend upon the particular application and those skilled in the art a capable of making the necessary adjustments.
  • the invention also encompasses a method of making the antimicrobial composition. Although this method is contained in priority documents US Provisional Applications 60/525,910 and 60/551,485, it is provided herein as an aid to the reader. [0067] In broad terms, the method comprises the steps of blending a phenol with a quaternary ammonium antimicrobial agent, heating the blended phenol and quaternary ammonium antimicrobial agent if necessary (some combinations of phenol/quaternary agent may not require heat), and admixing a quantity of water.
  • the phenol e.g., TRTIONTM X-207
  • the quaternary ammonium antimicrobial agent e.g., ONYXIDETM
  • the heat is applied because in many instances the quaternary ammonium antimicrobial agent is a solid at room temperature. Care should be taken not to heat the admixture of phenol and antimicrobial agent to a point where there is unacceptable volatilization of either.
  • ONYXIDETM is the antimicrobial agent
  • a mixing temperature of between about 65° C and about 75° C is recommended. At this temperature the ONYXIDETM melts into the phenol to form a liquid.
  • Anti-foaming agents and anti-freezing agents such as those discussed previously can be added at this point if needed or desired.
  • the heat may be removed. As the admixture cools to room temperature water is added with stirring.
  • antimicrobial agent phenol, and water utilized in the method are the same as those discussed in relation to the composition.
  • anti-foaming agents, anti- freezing agents, and additional antimicrobial agents, if used are the same as those discussed in relation to the composition.
  • Antimicrobial Composition #3 is the same as those discussed in relation to the composition.
  • the invention comprises insulation paper treated with a microemulsion of a quaternary ammonium antimicrobial agent and two different types of antimicrobial agents.
  • the microemulsion can come in two forms. One is an aqueous microemulsion well suited for aqueous systems. The other is a non-aqueous microemulsion well suited for non- aqueous or organic solvent type systems. In the context of insulation it is expected that the aqueous microemulsion will be the more frequently used form.
  • this embodiment is an aqueous antimicrobial composition that can impart antimicrobial characteristics to paper.
  • this embodiment of the invention comprises an aqueous microemulsion.
  • the microemulsion comprises at least three (3) antimicrobial agents and water.
  • the first antimicrobial agent comprises a quaternary ammonium antimicrobial agent.
  • the second and third antimicrobial agents are different from the quaternary ammonium antimicrobial agent.
  • Quaternary ammonium antimicrobial agents utilized in this composition include those listed in the previous embodiments of the antimicrobial composition.
  • the quaternary ammonium antimicrobial agent comprises a dimethylbenzyl ammonium compound such as N-alkyl dimethylbenzyl ammonium saccharinate.
  • N-alkyl dimethylbenzyl ammonium saccharinate is commercially available from Stepan Chemical Company of Northfield, Illinois, under the tradename ONYXCIDETM 3300. This particular form of ONYXIDETM is approximately 95% active and is a solid at room temperature but will form a liquid at elevated temperature. It is light yellow-orange in color and is insoluble in water.
  • the phenol utilized in the practice of this embodiment of the invention may comprise an alkyl phenol having at least one an alkyl group selected from the group consisting of C 7 alkyls, C 8 alkyls, C 9 alkyls, o alkyls, and Cn alkyls.
  • the alkyl phenol comprises an alkyl phenol having a C alkyl group.
  • Alkyl phenols suitable for use in the practice of the claimed invention are available commercially from a number of sources.
  • a particularly preferred commercially available alkyl phenol is sold by Dow Chemical Company under the tradename TRITONTM X-207.
  • the phenol utilized in the practice of the invention can comprise a styrenated phenol.
  • styrenated phenols acceptable for use with the invention are CHROMASIST WEZ and STANDAPOL HS. Both are available from Cognis Corporation of Cincinnati, Ohio. Both are identified by CAS # 3217120.
  • Technical data sheets indicate that the primary difference between the two is the level of ethoxylation.
  • the second and third antimicrobial agents used in this embodiment of the invention are preferably selected from the azole family of antimicrobial agents.
  • azoles comprise a large class of compounds characterized by a fivemembered ring which contains an atom of nitrogen and at least one other noncarbon atom (e.g., nitrogen, oxygen, and sulphur). Certain azoles exhibit antimicrobial (i.e., antifungal) properties. Triazoles are a subclass of azoles that are often used as antimicrobial agents.
  • propiconazole and tebuconazole Two of the more well known antimicrobial triazoles are propiconazole and tebuconazole.
  • the chemical name for propiconazole (CAS No. 50207-90-1) is l [[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2- yl]methyl]-l H-l,2,4-triazole.
  • tebuconazole (CAS No. 107534-96-3) is ⁇ -[2-(4-chloropheny l)ethy l]- ⁇ -( 1 , 1 -dimethy lethyl)- 1 H- 1 ,2,4- triazole-1-ethanol.
  • Tebuconazole is commercially available from a number of sources.
  • a particularly preferred form of tebuconazole is available from Bayer Corporation under the tradename PREVENTOLTM A8.
  • propiconazole is available from a number of sources.
  • a particularly preferred form of propiconazole is available from Janssen Pharmaceutica under the tradename WOCOSENTM TECHNICAL.
  • the second and third antimicrobial agents are propiconazole and tebuconazole.
  • Either agent can be the second or third; the particular designation does not matter.
  • tebuconazole will generally be referred to as the second antimicrobial agent and propiconazole will be the third antimicrobial agent.
  • a small quantity of a glycol may be present in this embodiment of the antimicrobial composition if desired.
  • Glycols can add to the stability of the emulsion and provide other benefits such as retarding foam.
  • Preferred glycols include alkyl glycols with polyethylene glycol, polypropylene glycol, and dipropylene glycol being preferred.
  • Water makes up the other primary component of the recited antimicrobial composition.
  • the antimicrobial composition according to the invention may contain other additives. Two such additives are anti-foaming agents and anti- freezing agents. [0089] Some phenols used in the practice of the invention can be susceptible to foaming depending upon the particular application. Therefore, it is envisioned that many commercial embodiments of the invention will contain anti-foaming agents.
  • this composition is used to treat insulation paper.
  • One method of treating this type of paper is to add the antimicrobial composition to the water box, a device toward the end of the paper process that returns a certain quantity of water to the paper after the paper has undergone heat based drying.
  • the water box is often agitated due to the continuous movement of paper through it. This agitation can cause foaming upon the addition of the claimed antimicrobial composition. Generally, the presence of foam is detrimental to the water box portion of a paper process. Therefore an anti- foaming agent is added to the composition according to the invention when the invention is used to treat paper at the water box.
  • the paper can also be treated using a spraybar. Foam buildup in the spraybar can be detrimental to a process so an antifoaming agent can be used there as well.
  • Preferred anti-foaming agents are ethoxylated co-polymers of polyethylene glycol.
  • the commercial formulations of phenols may contain a quantity of an antifoaming agent.
  • TRITONTM X-207 contains a small quantity of polyethylene glycol. Accordingly, if TRITONTM X-207 is one source of the phenol additional antifoaming agent may not be needed.
  • anti-freezing agents may be added to the composition according to the invention. They are used to keep the composition from freezing or becoming too viscous during transport in cold weather. In most instances a glycol will serve the function of an anti-freezing agent.
  • a preferred anti-freezing agent is dipropylene glycol.
  • One of the benefits of the present composition is that it provides a novel and improved platform for taking advantage of the antimicrobial properties of various azoles and tebuconazole and propiconazole in particular.
  • tebuconazole and propiconazole in combination, one can achieve a greater antimicrobial effect for a given amount of antimicrobial agent.
  • Tebuconazole and propiconazole are also well known for their hydrophobicity and difficulty of use in an aqueous environment. They resist forming aqueous emulsions and to the extent they can be forced into some type of aqueous emulsion the emulsions tend to be delicate and are easily destabilized (e.g., the actives form crystals in water and precipitate out or they form distinct phases with water).
  • the composition according to the invention provides a stable aqueous microemulsion of a quaternary ammonium antimicrobial agent and azoles, particularly tebuconazole and propiconazole.
  • This composition can be as dilute as about 0.02 wt. % of combined azole (e.g., 100 ppm of tebuconazole and 100 ppm of propiconazole) or as concentrated as about 50 wt. % combined azole. This characteristic provides great flexibility in how the composition may be used.
  • each of the listed components may vary to accommodate particular process requirements. Accordingly, each of the listed components may be present in different amounts depending upon the particular needs of the user. Again, those skilled in the art are fully capable of making these adjustments without undue experimentation.
  • the quaternary ammonium antimicrobial agent is present in the overall composition in an amount between about 0.33 wt. % and 20 wt. %. In particularly preferred embodiments the quaternary ammonium antimicrobial agent is present between about 2 wt. % and 16 wt. % of the overall composition, most preferably between about 3 wt. % and 9 wt. %.
  • the phenol i.e., alkyl phenol, styrenated phenol, or combinations of them
  • the phenol is preferably present in the overall composition in an amount between about 30 wt. % and about 80 wt. % of the total composition.
  • the phenol is present in the composition between about 40 wt. % and about 70 wt. %, most preferably between about 45 wt. % and 65 wt. %.
  • the second antimicrobial agent is preferably present in the overall composition in an amount between about 5 wt. % and about 45 wt. %, more preferably between about 12 wt. % and about 30 wt. %. As noted prevbusly, the second antimicrobial agent is preferably tebuconazole.
  • the third antimicrobial agent is preferably present in the overall composition in an amount between about 5 wt. % and about 45 wt. %, more preferably between about 12 wt. % and about 30 wt.%. As noted previously, the third antimicrobial agent is preferably propiconazole.
  • a small quantity of a glycol may be present in the composition according to the invention.
  • Preferred glycols include alkyl glycols with polyethylene glycol, polypropylene glycol, and dipropylene glycol being preferred. Dipropylene glycol is particularly preferred. It is anticipated that in most applications the quantity of glycol will be between about 0 wt. % and about 4 wt. %. of the total composition.
  • an anti-foaming agent can be added.
  • the anti-foaming agents suitable for use with the invention include those compounds commonly used as anti-foaming agents.
  • an additional amount of a glycol can be added as an antifoaming agent.
  • the glycol used as an anti-foaming agent can be more of the same glycol discussed previously or a different glycol.
  • a preferred anti-foaming agent is an ethoxylated co-polymer such as polyethylene glycol which is commercially available from Cognis Corporation. It is anticipated that in most applications the quantity of antifoaming agent needed for successful practice of the invention will range between about 0 wt. % to about 3 wt. %, more preferably between about 0.5 wt. % and 1.5 wt. %. The quantity of antifoaming agent can be adjusted upwards or downwards depending upon the particular application. Those skilled in the art can readily determine the appropriate quantity of antifoaming agent to use without undue experimentation.
  • the remainder of the composition according to the invention comprises water.
  • the quantity of water present in the claimed composition will be between about 0 wt. % and about 15 wt. %, more preferably between about 3 wt. % and about 9 wt. %. Again, the exact quantity of water will depend upon the particular application and those skilled in the art are capable of making the necessary adjustments.
  • the invention also encompasses a method of making this antimicrobial composition.
  • the method according to the invention comprises the steps of blending a phenol with a quaternary ammonium antimicrobial agent. Heat may be necessary during this blending step and particularly if the phenol is an alkyl phenol and the quaternary agent is an N-alkyl dimethylbenzyl ammonium compound.
  • a quantity of a first non-metallic antimicrobial agent then a quantity of a second non-metallic antimicrobial agent.
  • the first and second non-metallic agents can also be mixed together prior to mixing with the phenol/quaternary mixture.
  • the alkyl phenol e.g., TRTIONTM X-207
  • the quaternary ammonium antimicrobial agent e.g., ONYXIDETM 3300
  • the heat is applied because in many instances the quaternary ammonium antimicrobial agent is a solid at room temperature. If the quaternary ammonium antimicrobial agent is a liquid or available as a flowable composition heat may still be used to aid in the mixing. Care should be taken not to heat the admixture of alkyl phenol and quaternary antimicrobial agent to a point where there is unacceptable volatilization of either.
  • the temperature is kept below about 200 °C.
  • TRITONTM X-207 is the alkyl phenol and ONYXIDETM 3300 is the antimicrobial agent, a mixing temperature of between about 65° C and about 75° C is recommended. At this temperature the ONYXIDETM 3300 melts into the TRITONTM X-207 to form a liquid.
  • the steps of admixing a second antimicrobial agent and admixing a third antimicrobial agent may occur separately.
  • the second and third antimicrobial agents can be admixed together then added to the quaternary ammonium antimicrobial agent. It has been observed that propiconazole and tebuconazole exhibit little to no compatibility outside of the presence of the quaternary ammonium antimicrobial agent.
  • the admixing of the second and third antimicrobial agents can be accomplished in the presence of heat, if needed.
  • WOCOSENTM TECHNICAL i.e., propiconazole
  • PREVENTOLTM A8 i.e., tebuconazole
  • the tebuconazole and propiconazole are mixed together in the presence of heat to form a less viscous solution that can then be added to the quaternary ammonium/alkyl phenol mixture.
  • the tebuconazole and propiconazole mixture is heated to between about 65 °C and 75 °C with stirring. [00113] Heating can continue during the admixture of the second and third antimicrobial agents and the quaternary ammonium antimicrobial agents if needed. Glycols and any anti-foaming agents or anti-freezing agents such as those discussed previously can be added at this point.
  • an alternative embodiment of the invention is particularly well suited for use in non-aqueous systems.
  • the invention comprises a non-aqueous microemulsion.
  • the microemulsion comprises a quaternary ammonium antimicrobial agent, a first non-metallic antimicrobial agent, a second non-metallic antimicrobial agent, and a glycol.
  • the preferred quaternary ammonium antimicrobial agent, first non-metallic antimicrobial agent, and second non-metallic antimicrobial agent are the same as in the previous embodiment.
  • Almost any glycol can be used in the practice of the invention but dipropylene glycol is a preferred glycol.
  • each element in the composition according to the invention is as follows: quaternary ammonium antimicrobial agent- about 0.33 wt. % to about 17 wt. %; second antimicrobial agent- about 10 wt. % to about 33 wt. %; third antimicrobial agent- about 10 wt. % to about 33 wt. %; glycol- about 17 wt. % to about 80 wt. %.
  • the ratio of tebuconazole:propiconazole:quaternary ammonium agent is about 4:4: 1.
  • the method of making this embodiment of the invention is generally similar to the method of making the aqueous embodiment.
  • the various components are mixed together in the appropriate quantities in the presence of heat, if needed.
  • several samples of the composition according to the invention were made in the following manner.
  • the second antimicrobial agent e.g., WOCOSEN TECHNICAL
  • dipropylene glycol under heat (approximately 65°C) in the desired relative amounts.
  • the quaternary ammonium compound e.g., ONYXIDE 3300
  • the third antimicrobial agent e.g., PREVENTOL A8 was then added with heat and mixing. The entire mixture was then stirred under heat until a clear microemulsion was formed.
  • the above non-aqueous embodiment of the invention is well suited for imparting antimicrobial characteristics to products produced in a non- aqueous environment.
  • Both the aqueous and non-aqueous embodiments of this antimicrobial composition should be applied to the paper in a manner that transfers a level of active agent sufficient to provide the paper a commercially acceptable level of efficacy against microbes.
  • the composition is applied in a manner (e.g., spray bar, water box) to impart at least 100 ppm combined antimicrobial agent, preferably between about 200 ppm and about 20,000 ppm.
  • the amount of antimicrobial agent picked up by the paper can be adjusted by several methods known to those skilled in the art such as adjusting the speed of the paper under a spray bar. Such adjustments will likely have to be made in each papermaking process.
  • Antimicrobial composition number 4 is very similar to composition number 3. Both contain the same combination of three different antimicrobial agents with the first, second and third agents being the same in both compositions at a ratio of about 4:4: 1. The concentration range of all three antimicrobial agents is the same as well. The primary difference between composition number 3 and composition number 4 is the aqueous portion of the microemulsion.
  • composition number 3 relies heavily upon the use of phenols in the aqueous phase
  • composition number 4 relies upon glycols and alcohol ethoxylates.
  • composition number 4 comprises between about 0 and 20 wt. % phenol (preferably a styrenated phenol) and more preferably between 1 wt. % and 5 wt. %.
  • Composition number 4 also comprises between about 20 wt. % and 40 wt. % glycol, preferably between about 25 wt % and 35 wt. %. Almost any glycol is suitable for use in the composition but dipropylene glycol is preferred.
  • Alcohol ethoxylate and water make up the remainder of composition 4.
  • Preferred alcohol ethoxylates include secondary alcohol ethoxylates such as Tergitol 15-S-15 which is commercially available from Dow Chemical Company.
  • the alcohol ethoxylate is preferably present in the composition in an amount between about 8 wt % and 30 wt. %. Water makes up the remainder of the composition and is present between about 5 wt. % and 40 wt. %.
  • composition number 4 may be made by mixing the following components in the following manner. Note that the ratio oftebuconazole:propiconazole:quaternary agent is around 4:4:1. The percentages are weight percent. The products should be mixed at 65C (150F):
  • Adhesive The adhesive that attaches the fiberglass batting to the non ⁇ voven covering may also serve as a carrier for antimicrobial compositions. Several types of adhesives may be used depending upon the physical and chemical characteristics of the insulation and the non-woven covering. In preferred embodiments, however, the adhesive is an asphalt or tar-like compound such as those that are commonly used in the manufacture of insulation.
  • the antimicrobial compositions can be added to the adhesive prior to application of the adhesive to the non-woven covering. Simple mixing or blending of the antimicrobial agent with the adhesive will probably be the most effective method of addition inmost instances. Other methods of combining the antimicrobial composition with adhesives will be readily apparent to those skilled in the art.
  • the antimicrobial compositions that can be used in combination with the adhesive include all of those discussed previously, including the preferred antimicrobial compositions.
  • Preferred embodiments utilize an antimicrobial composition that includes agents selected from the group consisting of triclosan, propiconazole, sodium pyrithione, tolyl diiodomethyl sulfone; tebuconazole; thiabendazole; 3-iodo-2-propynyl butylcarbamate, metal ions, n-octyl-isothiazolinone, quaternary ammonium compounds, and mixtures thereof.
  • N-octyl-isothiazolinone (OIT) and silver ions or silver zeolites are particularly preferred.
  • the weight percent of antimicrobial composition in the adhesive may vary from very little (e.g., less than 100 ppm) to very great (e.g., over 5000 ppm). The exact amount will depend upon the particular use of the insulation and the amount of antimicrobial composition used in conjunction with the non-woven covering.
  • the invention also encompasses a method of manufacturing insulation which exhibits antimicrobial properties.
  • the various examples set forth above discuss several methods of manufacture (e.g., spraying the non- woven covering). The above discussed methods are exemplary only and should not be interpreted as limiting the scope of the invention.
  • the method according to the invention comprises the steps of applying an antimicrobial composition to the non- woven covering and contacting a non-woven covering to an insulating material.
  • the order of these steps may be reversed if such reversal is better suited to the overall process.
  • the step of contacting the non-woven covering to the insulating material includes any contacting step currently used in the industry. Such steps could include melt pressing synthetic polymer non-woven coverings to insulation or coating a non-woven covering with an adhesive then contacting the non-woven covering to the insulation.
  • tar like adhesives to contact paper coverings to fiberglass batting is probably the most commonly used method in the industry.
  • the step of applying an antimicrobial composition to the non-woven covering comprises any of the methods discussed above including spraying, coating, dipping, etc. or otherwise contacting the antimicrobial composition to the non-woven covering. Adding the antimicrobial composition to an adhesive prior to or concurrent with contacting the non- woven covering to the adhesive is also included in the scope of this step.
  • the antimicrobial compositions utilized in the method according to the invention include all of those antimicrobial compositions capable of providing a commercially acceptable level of efficacy against the microbe of concern.
  • Particularly preferred embodiments of the method include the specific antimicrobial compositions discussed above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paper (AREA)

Abstract

L'invention concerne une isolation présentant des caractéristiques antimicrobiennes, un procédé pour fabriquer ladite isolation ainsi que des agents antimicrobiens appropriés, pouvant être appliqués à cette isolation ou à tout constituant de cette dernière et parmi lesquels figurent le propiconazole, le pyrithione de sodium, le tolyl diiodométhyl sulfone, le tébuconazole, le thiabendazole, le 3-iodo-2-propynyl butylcarbamate, le triclosan, des composés d'ammonium quaternaires, des métaux et mélanges de ces derniers.
PCT/US2004/019360 2003-12-01 2004-06-16 Isolation antimicrobienne Ceased WO2005061228A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
MXPA06014847A MXPA06014847A (es) 2004-06-16 2005-05-04 Aislamiento antimicrobiano.
AU2005262841A AU2005262841A1 (en) 2004-06-16 2005-05-04 Antimicrobial insulation
PCT/US2005/015506 WO2006007044A1 (fr) 2004-06-16 2005-05-04 Isolation antimicrobienne
CNA2005800196497A CN1989005A (zh) 2004-06-16 2005-05-04 抗微生物绝热体
BRPI0512072-1A BRPI0512072A (pt) 2004-06-16 2005-05-04 isolamento antimicrobiano
EP05742871A EP1755887A4 (fr) 2004-06-16 2005-05-04 Isolation antimicrobienne
CA2569871A CA2569871C (fr) 2004-06-16 2005-05-04 Isolation antimicrobienne

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US52591003P 2003-12-01 2003-12-01
US60/525,910 2003-12-01
US52916403P 2003-12-12 2003-12-12
US60/529,164 2003-12-12
US55148504P 2004-03-09 2004-03-09
US55142604P 2004-03-09 2004-03-09
US60/551,485 2004-03-09
US60/551,426 2004-03-09
US56882104P 2004-05-06 2004-05-06
US60/568,821 2004-05-06
US56896104P 2004-05-07 2004-05-07
US60/568,961 2004-05-07

Publications (1)

Publication Number Publication Date
WO2005061228A1 true WO2005061228A1 (fr) 2005-07-07

Family

ID=34714706

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/019360 Ceased WO2005061228A1 (fr) 2003-12-01 2004-06-16 Isolation antimicrobienne

Country Status (1)

Country Link
WO (1) WO2005061228A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1755887A4 (fr) * 2004-06-16 2011-07-06 Microban Products Isolation antimicrobienne
EP2536557A4 (fr) * 2010-02-17 2014-08-20 Henry Co Llc Barrières architecturales atténuant les microbes, compositions pour former de telles barrières et procédés apparentés

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030035981A1 (en) * 2001-08-03 2003-02-20 Charles Capps Antifungal gypsum board

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030035981A1 (en) * 2001-08-03 2003-02-20 Charles Capps Antifungal gypsum board

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1755887A4 (fr) * 2004-06-16 2011-07-06 Microban Products Isolation antimicrobienne
EP2536557A4 (fr) * 2010-02-17 2014-08-20 Henry Co Llc Barrières architecturales atténuant les microbes, compositions pour former de telles barrières et procédés apparentés
US9758679B2 (en) 2010-02-17 2017-09-12 Henry Company, Llc Microbe mitigating architectural barriers, compositions for forming such barriers and related methods

Similar Documents

Publication Publication Date Title
EP1511905B1 (fr) Cloison seche antimicrobienne
JP5841171B2 (ja) 殺生物性サイジング乳化物
CA2569871C (fr) Isolation antimicrobienne
EP1859103B1 (fr) Efficacité accrue de fongicides dans le papier et le carton
US20050154030A1 (en) Antimicrobial composition
US7507281B2 (en) Antimicrobial cementitious composition, method and article
AU2011352988A1 (en) Antimicrobial size emulsion and gypsum panel made therewith
US20050182140A1 (en) Antimicrobial compositions
KR101647856B1 (ko) 살생물 조성물
WO2005061228A1 (fr) Isolation antimicrobienne
AU2011213715A1 (en) Antimicrobial Insulation
CZ20011906A3 (cs) Konzervační prostředek
HK1103691A (en) Antimicrobial insulation
US7179773B2 (en) Fungicidal composition
KR101609783B1 (ko) 석고보드용 수분산 방균제 조성물
US7306811B2 (en) Fungicide composition based on halosulphone in particular for packaging
JPH04356404A (ja) 工業用防カビ剤
HK1075924B (en) Antimicrobial wallboard
WO2008147411A1 (fr) Composition cimentaire antimicrobienne, procédé et article
US20090047533A1 (en) Composition and method for treating fibrous materials
JPS59144680A (ja) 柔軟剤組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase