Melt processed antimicrobial composition.
Abstract
A method for forming a composition that includes mixing an antimicrobially active botanical oil (e.g., thymol, carvacrol, etc.) and a modified starch polymer within a melt blending device (e.g., extruder) is provided. Unlike the problems associated with proteins, the use of starch polymers allows for a greater degree of flexibility in the processing conditions and is still able to achieve good properties in the resulting composition. The present inventors have also discovered that a plasticizer may be employed to facilitate melt processing of the starch, as well as to enhance the ability of the botanical oil to flow into the internal structure of the starch where it can be retained in a stable manner. The composition is also typically generally free of solvents. In this manner, the starch will not generally disperse before use and prematurely release the botanical oil. Due to the water sensitivity of the modified starch, however, it may be subsequently dispersed by moisture when it is desired to release the botanical oil.

Term
5.1 yearsleft in the term
Expires 31 October 2031.
- Priority
- Filed
- Granted
- Today
- Expires
14 claims: 9 independent, 5 dependent
- 1REIVINDICACIONES 1. Un método para formar una composición antimicrobiana que comprende mezclar dispersivamente un aceite esencial, almidón modificado, y un plastificante dentro de un dispositivo de mezclado de derretido, en donde los aceites esenciales constituyen de 0.01% en peso a 25% en peso de la composición, los almidones modificados constituyen de 30% en peso a 95% en peso de la composición y los plastif icantes constituyen de 0.1% en peso a 40% en peso de la composición, en donde la composición está en la forma de partículas, y en donde las partículas tienen un tamaño promedio de 100 a 600 micrómetros.
- 2El método de conformidad con la reivindicación 1, en donde el aceite esencial incluye un fenol monoterpeno.
- 3El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el almidón modificado es un almidón de hidroxialquilo.
- 4El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el plastificante es un alcohol polihídrico o en donde el plastificante es un ácido carboxílico alifático. IMPI
- 55 5 tNsrmrro m uucano DS LA rROMIDAP INDUSTRIAL 5 . El método de conformidad con ai ia.l giiίHp i as e reivindicaciones anteriores, caracterizado porque los aceites esenciales constituyen de 0.1% en peso a 20% en peso de la composición, los almidones modificados constituyen de 40% en peso a 90% en peso de la composición, y los plastificantes constituyen de 1% en peso a 35% en peso de la composición.
- 6El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el aceite esencial, el almidón modificado y el plastificante son mezclados de3ntro del dispositivo de mezclado de derretido a una temperatura de 50°C a 250°C.
- 7El método de conformidad con cualquiera de las reivindicaciones anteriores, caracterizado porque el dispositivo de mezclado de derretido es un extrusor que comprende además extrudir la composición antimicrobiana sobre una superficie para formar una película.
- 8Una composición antimicrobiana procesada con derretido que comprende un aceite esencial, almidón modificado, y un plastificante, en donde los aceites esenciales constituyen de 0.01% en peso a 25% en peso de la composición, los almidones modificados constituyen de 30% en peso a 95% en peso de la composición y los plastificantes constituyen de 0.1% en peso a 40% en peso de la composición, en donde la composición está en la IMPI 5 6 INSTITUTO MIXIQj· DS Ut PftOÑI&AD JNDVSTfcW· forma de partículas, y en donde las partículas·-tienen-tm-tamaño* promedio de 100 a 600 micróraetros.
- 9un paño limpiador que comprende una composición antimicrobiana que comprende un aceite esencial, almidón modificado, y un plastificante, en donde los aceites esenciales constituyen de 0.01% en peso a 25% en peso de la composición, los almidones modificados constituyen de 30% en peso a 95% en peso de la composición y los plastificantes constituyen de 0.1% en peso a 40% en peso de la composición, en donde la composición está en la forma de partículas, y en donde las partículas tienen un tamaño promedio de 100 a 600 micrómetros.
- 10El paño limpiador de conformidad con la reivindicación 9, caracterizado porque el paño limpiador comprende un tejido fibroso que contiene fibras absorbentes.
- 11Un método no terapéutico para remover bacterias de una superficie, el método comprende poner en contacto la superficie con el paño limpiador de cualquiera de las reivindicaciones 9 a 10.
- 12El método de conformidad con la reivindicación 11, caracterizado porque el aceite esencial del paño limpiador incluye fenol monoterpeno y antes de poner en contacto la Γ !< ví γ ! I INSTITUTO MEXICANO Ot .'.A PROPIEDAD INDUSTRIAL superficie con el paño limpiador, se aplica nna-goiiirión acuosa a la composición para liberar el fenol monoterpeno.
- 13El método de conformidad con la reivindicación 12, 5 caracterizado porque la concentración del fenol monoterpeno liberado en la solución acuosa es mayor que 0.1$ en peso.
- 14El método de conformidad con la reivindicación 12, caracterizada porque la solución acuosa contiene un ácido. LO L5
Independent claims14
324 paragraphs in 26 sections, as filed
(54) Title: ANTIMICROBIAL COMPOSITION PROCESSED WITH MELT. (54) Title: MELT PROCESSED ANTIMICROBIAL COMPOSITION.
(57) Summary
A method of forming a composition is provided which includes mixing an antimicrobially active botanical oil (eg, thymol, carvacrol, etc.) and a modified starch polymer within a melt mixing device (eg, an extruder). Unlike the problems associated with proteins, the use of starch polymers allows a greater degree of flexibility under processing conditions and is still capable of achieving good properties in the resulting composition. The present inventors have also discovered that a plasticizer can be used to facilitate melt processing of the starch, as well as improve the ability of botanical fluid oil within the internal structure of the starch where it can be stopped in a stable manner. The composition is also typically typically solvent free. In this way, the starch will not generally disperse before use and there will be no premature release of the botanical oil. Due to the sensitivity of the water of said modified starch, however, it can be subsequently dispersed by humidity when it is desired to release the botanical oil.
(57) Abstract
A method for forming a composition that ineludes mixing an antimicrobially active botanical oil (eg, thymol, carvacrol, etc.) and a modified starch polymer within a melt blending device (eg, extruder) is provided. Unlike the problems associated with proteins, the use of starch polymers allows for a greater degree of flexibility in the Processing conditions and is still able to achieve good properties in the resulting composition. The present inventors have also discovered that a plasticizer may be employed to facilítate melt Processing of the starch, as well as to enhance the ability of the botanical oil to flow into the internal structure of the starch where it can be retained in a stable manner. The composition is also typically generally free of solvents. In this manner, the starch will not generally disperse before use and prematurely release the botanical oil. Due to the water sensitivity of the modified starch, however, it may be subsequently dispersed by moisture when it is desired to release the botanical oil.
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<img file="MX356246B_D0001.tif" />
PATENT TITLE No. 356246
Headlines): KIMBERLY-CLARK WORLDWIDE, INCORPORATED
Address: 2300 Winchester Road, Neenah, Wisconsin, 54956, USA
Denomination: ANTIMICROBIAL COMPOSITION PROCESSED WITH MELTING.
Classification:
Inventor (s):
CIP: A01N43 / 04; A01N65 / 00; A01P1 / 00; A61K31 / 70
CPC: A01N31 / 08; AG1N65M fl29C47 / 0Q; B29C47 / 6087; B29B7 / 10; B29B7 / 38;
B29B9 / 06; B29B9 / 42; B29é9 / 16
JAMES H. WANG; BO SHI; JAEHONG LEE; VA8ÍLY A. TOPOLKARAEV; NEIL T. SCHOLL; YOUNGSOOK KIM ~
<img file="MX356246B_D0002.tif" />
Number:
MX / a / 2013/006449
Pafs:
US: F> ^ i International:
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Number:
12/961,638
Validity: Twenty years
Expiration Date »October 31, 2031 Issue Date: deβ de fhayo 2018,
The patent of reference ^ eíp ^ ga with fundárftepto en los afffpílos 1 °, y 5§kíje la Lja # de la PTopedád Industrial.
, ------ afj p ^ e ^ g tiedib. óne ^ gem "of twenty ^ (festufxórrogables, told
In accordance with the aftejkS of the Law of the Proffcd ^ from the filing date of the soliSsilirrtefjaciájjJ
Who subscribes to the present title is Mee based on the provisions of (Official Gazette of the Federation {p.ü.FÓ * 06/27/1991, amended <sup>;</sup>0f 25/01/2006. 06/05 / 2009.06 / 01/2010, 18/00 / 28.10. 06/28/2010/27/01/2012 and Regulations of the Mexican Institute d * :: HL /<sup>,</sup>rapi «(ted ti $ & tírt5f» (li | .QiF. 1 <1 articles 1st, 3rd, 4th, 5th fraction V subsection aJ,<sup>3</sup>® fractions I and '30 * 8ek 12/27/1999, amended on 10/10/2002, 29 / O77JB043 (WÍfll | (p ^ ¡Slg / jg (itS ^) Deputy Generals, Coordinator, Directors *
Departmental and other subordinates of the MáxicpftO Institute 08/04/2004 and 09/13/2007).
t Ó payment dejjjj | ín8m¡ar * marjMfier in force t ^ t ^ echos.
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Ales.
.E, <49712/1999 ij Jtieuldfe 6th fractions III and 7th, bls 2déla Industrial Property Law Ϊ1994, 10/30/1996, 12/26/199X047 ^ 95/1999, 01/26/2004, 06/16 / 2005, »/ 2012 $ artÍOTe? .D °. 3rd fraction ytqoise a). 4th and 12th fractions I and III of / 1599, íjfofiredb * l 01 »7 / 2ΒΤ 16 ^ / 2004, 28/07/2004 and 7/09/2007): ijW9s © rgániCttjdet Institúja ^ naxltaflb of Industrial Property ( DO F.
«Mo that delegates powers to the Directors, Divisional Deputy Directors, Coordinators amended on 02/04/2000, 07/29/2004,
This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 fraction III, 2 fraction V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.
<img file="MX356246B_D0004.tif" />
DIVISIONAL DIRECTOR OF PATENTS NAHANNY CANAL REYES
Original string:
NAHANNY MARISOL CANAL REYES | 00001000000403252793 | Tax Administration Service | 1695 || MX / 2018/42319 | MX / a / 2013/006449, Patent title PCT | 1223 | GAGV | Page (s) | D9LFMZt3 + X / 8LPhE5tJmlgnSie4 =
Digital stamp:
Ny + HtE5 / tJis3xh6jakDHQtx6fgjZAG2RyQZbtxg3BODEOC / BA + rV¡WRhTOuVhP4vxlpwBMSgYYUOKR15BNmvmUCmW
WmvKbzo9mCxl8rMWE6rlBhsYluymePIBGW6PJOjdqios5qCq4v9M8x9EWyx7qGE1TtO3RgqJ / vtK8W2zu2w2gFR5j fL7aCyG0nucoic9tRZrhbaroHuuelX / yVNrl / 33Jfl + Azze + pPfPp8yZuDg5CargVTf8pVJfX¡Uxv / 7yaf¡HV4sq50 fzTbUs9IFrNPf / QOyQ7GS4p5d7TtR + Exays28yXJ / 2Y5lhrgrgX8z5Vh4k / cj5ueX0Q + Huia ==
Sand; No. 550. Floor 1. Santa María Tepepan Town. Xochímilco, 16020, Mexico City.
(55) 53340700 vyww.gob.rnx / impi
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MX / 2018/42319
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IMPI
ANTIMICROBIAL COMPOSITION PROCESSED WITH DERRETÍffÓ<sup>1</sup>
BACKGROUND OF THE INVENTION
Certain types of botanical oils such as thymol and carvacrol are known because they are environmentally friendly and effective in fighting microorganisms. Unfortunately, however, the use of such oils has been limited in many commercial applications (for example cleaning cloths) due to their high volatility and instability in the presence of oxygen. Attempts to overcome this problem frequently involve the use of larger amounts of botanical oils to prolong antimicrobial activity. Unfortunately, this only leads to another problem, which is the high concentrations of essential oils that can cause damage to certain types of food products, such as fruits. Other attempts have involved encapsulating the oil component with certain types of polymers, such as proteins. For example, an article entitled Encapsulation of Essential Oils in Nanospherical Zein Particles (Parris, et al. J. Agrie. Food Chem 2005, 53, 4788-4792) extensively describes encapsulating thymol in zein nanospheres by mixing the oil with Zein particles in the presence of a solvent (for example ethanol). The particles are said to be useful for either oral administration or injectable administration of biological materials in
<img file="MX356246B_D0007.tif" />
IMPI ¡Krmiro miucano 'Ot THE IND PROPERTY'. 'STSLAL of the body. Another article titled Zein-Based Film Thymol Controlled Release (Matromateo, and other Journal of Emerging Technologies and Innovative Foods 2009, 10,
222-227) broadly describes films formed by dissolving corn zein and glycerol from methanol, and then adding thymol to form a solution. The solution is poured into a Petri dish and dried to form the film.
One problem with the techniques described above is that they generally rely on solvents (eg ethanol ·) to help dissolve botanical oil in a solution. A disadvantage of the use of solvents is that both botanical oil and protein must be soluble in a common solvent system, which limits what type of components can be used in the composition. Solvent-based solutions require a substantial amount of time, energy, and material for processing. Still further, some of the botanical oil can escape from the solution when the solvent is evaporated, which requires the use of a larger amount of the oil than would normally be required. Notwithstanding the foregoing, the ability to use a solvent-free process is complicated by the tendency of proteins to lose their flow properties when exposed to intense shear and at an elevated temperature normally associated with melt processing. For example, proteins can undergo a conformational change (denaturation) that causes the bisulfide linkages in the polypeptide to become IMPI
J IKTTTVie MEXICANO
OF THE «OMÉDAD. <sub>w </sub>INDUSTRIAL dissociate into sulfhydryl groups or thiyl radicals. The
<img file="MX356246B_D0008.tif" />
Sulfhydryl groups form when the disulfide bonds are chemically reduced while the mechanical division of the disulfide bonds causes the thiyl radicals to form. Once the free sulfhydryl groups are disassociated, they are again randomly associated with other sulfhydryl groups to form new disulfide bonds between the polypeptides. The thiyl radicals can again randomly associate with other thiyl radicals by forming new disulfide linkages or thiyl radicals that can react with other amino acid functionality creating new forms of cross-launch between the polypeptides. Because a polypeptide contains multiple thiol groups, random cross-launch between polypeptides leads to the formation of an aggregated polypeptide network, which is relatively brittle and leads to a loss of flow properties.
As such, there is currently a need for a solvent-free process to form a stable composition containing an antimicrobial active botanical oil.
SYNTHESIS OF THE INVENTION
In accordance with an embodiment of the present invention, a method for forming an antimicrobial composition is described comprising dispersively mixing a botanical oil, a modified starch, and a plasticizer
<img file="MX356246B_D0009.tif" />
within a mixing device with derrefe¿dcu-.JJ. botanical oils make up from about 0.01 weight percent to about 25 weight percent of the composition, modified starches make up from about 30 percent by weight to about 95 percent by weight of the composition, and plasticizers constitute from about 0.1 percent by weight to about 40 percent by weight of the composition.
In accordance with another embodiment of the present invention, a melt processed antimicrobial composition is disclosed which comprises at least one monoterpene phenol in an amount of from about 0.01 weight percent to about 25 weight percent, by at least one hydroxyalkyl starch in an amount of from about 30 percent by weight to about 95 percent by weight, and at least one plasticizer in an amount of from about 0.1 percent by weight to about 40 percent by weight. In yet another embodiment, a method of removing bacteria from a surface is described which comprises contacting the surface with a cleaning cloth comprising a fibrous material containing the melt processed antimicrobial composition.
Other aspect features of the present invention are discussed in greater detail below.
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DETAILED DESCRIPTION OF REPRESOlifíHítVA INCORPORATIONS ^ Reference will now be made in detail to various embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of explanation of the invention and not by limitation of said invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For example, the features illustrated or described as part of one embodiment may be used on another embodiment to give yet another embodiment. Therefore, the present invention is intended to cover such modifications and variations as fall within the scope of the appended claims and their equivalents.
Generally speaking, the present invention is directed to a method of forming a composition that includes mixing an antimicrobially active botanical oil (for example thymol, carvacrol, etc.) and a modified starch polymer within a melt mixing device (for example an extruder). Unlike the problems associated with proteins, the use of starch polymers allows for a greater degree of flexibility under processing conditions and is still capable of achieving good properties in the resulting composition. The present inventors have also discovered that a plasticizer can be used to
<img file="MX356246B_D0010.tif" />
IMMPL facilitate melt processing of the starch, as well as to enhance the ability of botanical oil to flow into the internal structure of the starch where it is and can be retained in a stable manner. The composition is typically generally solvent free. In this way, the starch will not generally disperse before use and the botanical oil will not be released prematurely. Due to the water sensitivity of the modified starch, however, it can be subsequently dispersed by moisture when it is desired to release the botanical oil.
Various embodiments of the present invention will now be described in greater detail below.
I. Components.
A. Botanical Oil
Botanical oils are used in the composition of the present invention as antimicrobial actives. Oil can be an essential oil that is extracted from a plant. Similarly botanical oil can also be isolated or purified from an essential oil, or it can simply be made synthetically to mimic a plant-derived compound (eg, thymol made synthetically). Botanical oils are generally soluble in liquids and are believed to exhibit antimicrobial efficacy due to their ability to cause damage to the
<img file="MX356246B_D0011.tif" />
cell membrane in the
....... I. '^ 11' I both proliferate. Those of herbs, flowers, trees, and present as small droplets, component of the liquid of the microorganisms, inhibiting by essential oils, other plants are derived and are typically among the cells of the plants and can be extracted by methods known by those skilled in the art. art (for example by steam distillation, enfleurage (for example extraction using fat or grease, maceration, solvent extraction or mechanical pressing). Examples of oils suitable for use in the present invention may include, for example, anise oil, lemon oil, orange oil, oregano, rosemary oil, gauteria oil, thyme oil, lavender oil, Clove, Hops, Tea Tree Oil, Citronella Oil, Wheat Oil, Barley Oil, Lemon Grass Oil, Cedar Leaf Oil, Cedar Wood Oil, Cinnamon Oil, Flea Grass Oil, geranium, sandalwood oil, violet oil, cranberry oil, eucalyptus oil, verbena oil, peppermint oil, benzoin gum, basil oil, fennel oil, fir oil, balsam oil, menthol, ocmea origano, hydastis carradensis oil, berberi da ceae daceae oil, Ratanhíae and Turmeric longa oil, sesame oil, macadamia nut oil, evening primrose oil, Spanish salt oil, Spanish rosemary oil , coriander oil, thyme oil, pepper berry oil, rose oil, vergamot oil, rosewood oil, chamomile oil, sage oil, oil
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of light sage, cypress oil, sea fennel oil, frankincense oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lime oil, tangerine oil, marjoram oil, myrrh oil, Neroli Oil, Patchouli Oil, Pepper Oil, Black Pepper Oil, Small Grain Oil, Pine Oil, Oto Rose Oil, Peppermint Oil, Tuberose Oil, Vetiver Oil, or Ylang Ylang. Still other essential oils known to those of skill in the art are also contemplated as being useful within the context of the present invention (for example International Cosmetic Ingredients Dictionary, Tenth Edition and Eleventh Edition, 2004 and 2008 respectively, which are incorporated by reference).
In one embodiment, the carvacrol and thymol containing oils are purified from the Origanum vulgare species of the hirtum variety. Ideally this is a hybrid strain that produces high quality oils, but is not limited to this genus, species, or strain. The oil extract can also be obtained from a plant of the Nepeta genus including but not limited to spices Nepeta racemosa (cat's meta), Nepeta citriodora, Nepeta elliptic, Nepeta hindostoma, Nepeta lanceolada, Nepeta leucofila, Nepeta longiobracteata, Nepeta mussinii, Nepeta nepetela, Nepeta sibotorfii, Nepeta subsessilis, Nepeta tuberosa, Timus grandulosus, Timus hyemalis, Timus vulgaris and Timus zygis.
<img file="MX356246B_D0013.tif" />
As indicated above, isolates and / or derivatives of essential oils can also be used in the present invention. For example, monoterpene phenols are particularly suitable for use in the present invention, which can be isolated and purified from plant oil extracts, or can be made synthetically by known methods. Suitable monoterpene phenols can include, for example, thymol, carvacrol, eucalyptol, etc. Thymol (isopropyl-cresol) is a particularly suitable monoterpene phenol which is a crystalline substance that has a boiling point of around 238 degrees Celsius at atmospheric pressure. Carvacrol (isopropylcresol) a thymol isomer, is another suitable compound, carvacrol is a liquid with a boiling point of around 233 degrees Celsius at atmospheric pressure. Thymol and carvacrol, as well as isomers thereof, can be derived from plant oil extracts or can be synthesized. For example, carvacrol can be synthesized by reacting nitrous acid with l-methyl-2-amino-4propyl benzene. In addition to being employed in an isolated or pre-synthesized form, essential oils containing monoterpene phenols as a major constituent may be employed, with the final concentrations of monoterpene phenols being within the ranges provided herein. The term main constituent generally refers to those essential oils having monoterpene phenols in an amount of more than 50 percent by weight. Is well known
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<img file="MX356246B_D0015.tif" />
ΙΝΓΠΤϋΤΟ MEXICAN Üt U FRCPiÉDAD
INWSTRIAL in the art that such essential oils may also contain minor amounts of other constituents such as non-aromatic terpene compounds. Essential oils with organic phenolic compounds as the main constituent include, for example, anise oil, bay oil, sinterpino, clove blossom, clove leaf, clove oil, clove stem, origanum oil, balsam of Peru, pepper oil, eucalyptus oil and thyme oil.
Due to the stability achieved by the antimicrobial composition of the present invention, a relatively small amount of botanical oils can be employed and still achieve the desired antimicrobial efficacy. More particularly, the composition may employ botanical oils in an amount of from about 0.01 percent by weight to about 25 percent by weight, in some additions from about 0.1 percent by weight to about 20 percent by weight, and in some additions, from about 0.2 percent by weight to about 10 percent by weight.
B. Modified starch
The antimicrobial composition of the present invention also contains a modified starch. Because botanical oil tends to leak out during storage and before it is used in the application
<img file="MX356246B_D0016.tif" />
'' MEXICAN site úí
ΙΈ LA PXOFItVAÜ .j
INl'UJTRIAl hjhy- / to improve the desired, modified starch polymer ayudty long-term stability of the oil and, in turn, antimicrobial efficacy. Without trying to be bound by theory, it is believed that the physical structure of starch can effectively encapsulate botanical oil and inhibit its premature release. Notwithstanding this, when it is desired to release the botanical oil prior to use and / or during use, the modified starch may disperse (eg disintegrate, dissolve, physically change etc.) when placed in an aqueous environment. The amount of time required for dispersion of such polymers so that they release the desired antimicrobial active will depend at least in part on that particular end-use design criteria. In most additions, the modified starch will begin to disperse and release the antimicrobial active within about 5 minutes, suitably within about 1 minute, more suitably within about 30 seconds, and more suitably within about 10 seconds.
Even though cotton polymers are produced in many plants, typical sources include the seeds of cereal grains, such as corn, waxy maize, wheat, sorghum, rice, and waxy rice; tubers such as potatoes; roots, such as tapioca (for example marvioca and manioca), sweet potato and arrowroot; and the soul heart of sago. Regardless of its source, the starch is modified so that it has a higher degree of sensitivity to water, which helps facilitate the
<img file="MX356246B_D0017.tif" />
degradation on contact with water. Such modified starches can be obtained through typical processes known in the art (for example esterification, oxidation, acid hydrolysis, and enzymatic hydrolysis, etc.).
Starch ethers and / or starch ethers are particularly desirable, such as hydroxyalkyl starches. Without attempting to be bound by theory, such modified sources are believed to possess polar (eg hydroxy) and nonpolar (eg alkyl) groups that are capable of interacting with polar (eg phenolic hydroxyl) and nonpolar groups. (eg isopropyl) respectively, found in phenolic monoterpene botanical oils. This improves the ability of the starch polymer to trap and stop botanical oil before use. Furthermore, modification of the starch polymer provides improved chain flexibility, which further improves its trapping efficiency. The hydroxyalkyl group of hydroxyalkyl starches may contain, for example, from 2 carbon atoms to 10 carbon atoms, in some additions of carbon atoms to 6 carbon atoms and in some additions, from 2 carbon atoms to 4 carbon atoms. Representative hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxybutyl starch, and derivatives thereof. Starch esters, for example, can be prepared using a wide variety of anhydrides (for example
MFI
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WSTri uto mwicano,.-Y.
DElAMOfflM)
INÜIWTRIAI, acetic, propionic, butyl, and others), organic acids, acid chlorides, or other esterification reagents Έ1 degree of esterification may vary as desired, such as from one ester group per glycosidic unit of starch or three ester groups per unit glycosidic of the starch.
The starch polymer can contain different weight percentages of amylose and amylopectin, different polymer molecular weights, etc. High amylose starches contain more than about 50 weight percent amylose and low amylose starches contain less than about 50 weight percent amylose. When not required, low amylose starches have an amylose content of from about 10 percent to about 40 percent by weight, and in some additions, from about 15 percent by weight to about 35 percent. percent by weight and are particularly suitable for use in the present invention. Examples of such amylose starches include cornstarch and potato starch, both of which have an amylose content of approximately 20 weight percent. Low amylose starches are particularly suitable as those having a number average molecular weight (Mn) ranging from about 75,000 grams per mole to about 800,000 grams per mole, and in some additions, from about 10,000 grams per mole. mole at about 600,000 grams per mole, and / or a molecular weight per weight (Mw) ranging from about
<img file="MX356246B_D0019.tif" />
IMPÍ of 5,000,000 million grams per mole to around 25,000,000 million grams per mole, in some additions from about 5,500,000 grams per mole to about 15,000,000 million grams per mole, and in some additions, from about 6,000,000 from grams per mole to about 12,000,000 million grams per mole. The ratio of weight average molecular weight to number average molecular weight (Mw / Mn), for example, the polydispersity index is relatively high. For example, the polydispersity index can range from about 10 to about 100, and in some additions, from about 20 to about 80. The weight average molecular weight and number average molecular weight can be determined. by methods known to those skilled in the art. The antimicrobial composition of the present invention typically employs modified starch polymers in an amount of from about 30 percent by weight to about 95 percent by weight, in some additions from about 40 percent by weight to about 90 percent. percent by weight, in some additions from about 50 percent by weight to about 80 percent by weight.
C. Pastifying
A plasticizer can also be employed in the antimicrobial composition to help make the starch more flowable under the melt processing conditions (for example making the thermoplastic starch) and which goes on to receive the botanical oil within the internal structure. For example, the plasticizer typically softens and penetrates into the outer membrane of the starch and causes the starch chains to absorb water and swell. This swelling will, at some point, evoke the outer shell breaking and resulting in irreversible destructurization of the starch grain. Once de-structured, the starch polymer chains, which are initially compressed within the granules, can stretch outward and form a generally disordered intermix of the polymer chains. With resolidification, however, the chains can reorient themselves to form amorphous solids or crystalline solids having varying strengths depending on the orientation of the starch polymer chains.
Suitable plasticizers can include, for example, polyhydric alcohol plasticizers, such as sugars (for example glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose and erythrose), sugar alcohols (for eg erythritol, xylitol, malitol, mannitol, and sorbitol), polyols (eg, ethylene glycol, glycerol, propylene glycol, dipropylene glycol, butylene glycol, and hexane Tirol), etc. Organic hydrogen bonding compounds which do not have a hydroxyl group are also suitable, including urea and urea derivatives; sugar alcohol anhydrides such as
<img file="MX356246B_D0020.tif" />
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INDUSTRIAL ____ sorbitol; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soy bean protein, cottonseed protein; and mix them. Suitable plasticizers can include phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol tracetate, glycerol mono acetate and diacetate, glycerol mono propionate, dipropionate and tripropionate, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, steric acid esters, oleic acid esters, and other acid esters. Aliphatic acids can also be used, such as copolymers of ethylene and acrylic acid, maleic acid grafted polyethylene, polybutadiene-acrylic acid, polybutadiene-maleic acid, propylene-acrylic acid, polypropylene-co- maleic acid, and other hydrocarbon-based acids. A low molecular weight plasticizer is preferred, such as at less than 20,000 grams per mole, preferably less than 5,000 grams per mole and more preferably less than about less than 1,000 grams per mole.
The plasticizer can be incorporated into the antimicrobial composition using any of a variety of known techniques. For example, the starch polymers can be pre-plasticized prior to incorporation into the composition to form what is frequently referred to as thermoplastic starch. The relative amount of starch and
<img file="MX356246B_D0021.tif" />
The plasticizer used in the thermoplastic starch can vary depending on a variety of factors, such as the desired molecular weight, the type of starch, the affinity of the plasticizer for the starch, etc. Typically, however, the starch polymer constitutes from about 40 percent by weight to about 98 percent by weight, in some additions, and from about 50 percent by weight to about 97 percent by weight, and in some additions from about 60 percent by weight to about 90 percent by weight of the thermoplastic starch. Similarly, the plasticizer typically constitutes from about 2 percent by weight to about 60 percent by weight, in some additions from about 5 percent by weight to about 50 percent by weight, and in some incorporations, from about 10 percent to about 40 percent by weight of the thermoplastic starch. Plasticizers may similarly comprise from about 0.1 percent by weight to about 40 percent by weight, in some additions from about 1 percent by weight to about 35 percent by weight, in some additions of from about 5 percent by weight to about 30 percent by weight of the antimicrobial composition.
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D. Other components -. ___
In addition to those previously noted, still other additives are also incorporated into the composition. For example, in addition to the modified starch, the composition may also contain other natural biopolymers such as native starches, cellulose obtained from various plant sources, algae materials from various sources which are a mixture of carbohydrates, proteins and oils. natural, hemicelluloses, modified cellulose (hydroxyalkylcellulose, cellulose ethers, cellulose esters, etc.) and others. When cooled, the amount of such additional natural biopolymers can range from about 0.1 percent by weight to about 50 percent by weight, in some additions from about 0.5 percent by weight to about 40 percent by weight, in some additions from about 1 percent by weight to about 30 percent by weight.
Dispersion aids can also be employed to help create a uniform dispersion of the oil / starch / plasticizer and to retard or prevent the separation of the antimicrobial composition within the constituent phases. When used, the dispersing aid or dispersing aids typically constitute from about 0.01 percent by weight to about 10 percent by weight, in some additions from about 0.1
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INDUSTRIAL weight percent to about 5 weight percent, and in some additions, from about 0.5 weight percent to about 4 weight percent of the antimicrobial composition. Even though any dispersing aid can generally be employed in the present invention, surfactants having certain hydrophilic / lipophilic balances can improve the long-term stability of the composition. As known in the art, the relative hydrophilicity or lipophilicity of an emulsifier can be characterized by the hydrophilic / lipophilic balance scale (HLB), which measures the balance between the hydrophilic and lipophilic solution trends of a compound. The hydrophilic / lipophilic balance scale ranges from approximately 0.5 to 20, with the lowest numbers representing the highest hydrophilic trends and the highest numbers representing the highest hydrophilic trends. In some embodiments of the present invention, the hydrophilic / lipophilic balance value of the surfactants is from about 1 to about 15, in some additions from about 1 to about 12 in some additions, from about 2 to around 10. If desired, 2 or more surfactants can be employed which have hydrophilic / lipophilic balance values either below or above the desired value, but together they have an average hydrophilic / lipophilic balance value within the desired range.
<img file="MX356246B_D0022.tif" />
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Another particularly suitable class of surfactants for use in the present invention are nonionic surfactants, which typically have a hydrophobic base (for example a long chain alkyl group or an alkylated aryl group) and a hydrophilic chain (for example a chain containing epoxy and / or propoxy halves). For example, some suitable nonionic surfactants that may be used include, but are not limited to, alkylphenols, ethoxylates, ethoxylated and propoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, block copolymers of ethylene propylene oxide. , ethoxylated ethers of fatty acids (C8-C18), condensation products of ethylene oxide with long-chain amines or amides, condensation products of ethylene oxide with alcohols, fatty acid esters, monoglyceride or diglycerides of long-chain alcohols and mixtures thereof. In a particular embodiment, the nonionic surfactant can be a fatty acid ester, such as a sucrose fatty acid ester, a glycerol fatty acid ester, a propylene glycol fatty acid ester, a sorbitan acid ester, a pentaerythritol fatty acid ester, a sorbitol fatty acid ester, and others. The fatty acid used to form such esters can be saturated or unsaturated, substituted or unsubstituted, and can contain from 6 carbon atoms to
<td>22 carbon atoms,</td><td>in</td><td>some</td><td>incorporations</td><td>from from 8</td>
<td>carbon atoms a</td><td> 18</td><td>atoms</td><td>carbon and</td><td>in some</td>
<td>incorporations, from</td><td> 12</td><td>atoms</td><td>carbon to 14</td><td>atoms of</td>
<img file="MX356246B_D0023.tif" />
carbon. In a particular embodiment, the monoglycerides and the di-glycerides of the fatty acids can be used in the present invention.
<td></td><td>The</td><td>composition</td><td>also can</td><td>contain a</td>
<td>preservative</td><td>or</td><td>a system</td><td>condom for</td><td>inhibit the</td>
<td>increase</td><td>of</td><td colspan="3">microorganisms over a period of time</td>
<td colspan="2">extended. The</td><td>condoms</td><td>suitable can</td><td>include, for</td>
<td>example the</td><td colspan="2">alcandés, the</td><td>Disodium EDTA</td><td>(ethylenediamine</td>
<td>tetracetate),</td><td colspan="3">ethylenediamine tetraacetate salts,</td><td>conjugates of</td>
ethylenediamine tetracetate fatty acid, isothiazolidone, benzoic esters (parabens) (for example, methylparaben, propylparaben, butylparaben, ethylparaben, isopropylparaben, isobutylparaben, benzylparaben, methylparaben sodium, and propylparaben sodium), benzoic acid, propylene glycols, urea (eg, urea diazolidinyl), and others. Other suitable preservatives include those sold by Sutton Labns, such as Germall 115 (urea amidazolidinyl), Germall II (urea diazolidinyl), and Germanll Plus (urea diazolidinyl and iodopropylnyl butylcarbonate). Another suitable preservative is Kathon CG®, which is a mixture of methyl chloroisothiazolinone and methylisothiazolinone available from Rohm & Haas; Mackstat H 66 (available from Mclntyre Group of Chicago Illionis). Still another suitable preservative system is a combination of 56% propylene glycol, 30% diazolidinyl urea, 11% methylparaben, and 3% propylparaben available under the
I
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GERMABEN® II name of International Specialilty Products of Wayne, New Jersey, United States of America.
To further enhance consumer benefits, other optional ingredients may also be used. For example, some classes of ingredients that can be used include, but are not limited to: antioxidants (product integrity); anti-redness agents, such as aloe extract; astringent-cosmetics (induce tightness or tingling sensation on the skin); colorants (imparts color to the product); deodorants (reduce or eliminate unpleasant odor and protect against the formation of bad odor on body surfaces); fragrances (consumer appeal); or pacifying (reduce clarity with the transparent appearance of the product); skin conditioning agents, skin exfoliating agents (ingredients that increase the rate of skin cell change such as hydroxyalpha acids and hydroxy betata acids); skin protectors (it is a drug product which protects injured or exposed skin or mucous membrane surface from harmful or bothersome stimuli); and thickeners (to increase viscosity).
Even though a wide variety of different components can be employed it is typically desired that the antimicrobial composition be formed without the use of solvents, particularly organic solvents, such as alcohols.
<img file="MX356246B_D0025.tif" />
organic (for example ethanol). Not only this - ». JiigÍ.S £ a__Manufacturing efficiency, but also limits evaporation of botanical oil that may otherwise be encountered during solvent removal. Although the composition may be generally free of such solvents, it should of course be understood that a small amount may still be present in the resulting composition. Notwithstanding this the composition typically contains solvents in an amount of less than about 20 weight percent, in some additions of less than about 10 weight percent and in some additions of from about 0.01 weight percent to about 5 percent by weight.
II. Melt Processing Technique
As indicated above, the antimicrobial composition of the present invention is formed by processing the components together in a melt mixing device (eg, an extruder). The heat and mechanical shear provided by the device allows the components to be mixed together in a highly efficient manner without the use of a solvent. Continuous charge and / or melt mixing techniques can be employed in the present invention. For example, a mixer / kneader, a Banbury mixer, a Farrel continuous mixer, a single screw extruder, a twin screw extruder, a roller mill, etc. can be used. A device
<img file="MX356246B_D0026.tif" />
Mixed with particularly suitable melt is a co-rotating twin screw extruder (for example, the USALAB twin screw extruder available from Thermo Electron Corporation of Stone, United Kingdom of Great Britain or an extruder available from Werner-Pfleiderer of Coperion Ramsey of New Jersey, United States of America). Raw materials for example botanical oil, starch, plasticizer, etc., can be supplied to the mixing device with melt separately and / or as a mixture. For example, starch and / or botanical oil may initially be fed through a twin screw extrusion supply port. Thereafter, a plasticizer can be injected into the downstream extruder from the botanical oil and starch. Alternatively, the components can be fed simultaneously to the extruder feed throat or separately at a different point along its length.
However, the materials can be dispersively mixed at sufficient cut / pressure and temperatures to ensure adequate mixing (for example at or above the softening point of the starch polymer), but without adversely impacting the physical properties of the starch. For example, mixing with melt typically occurs at a temperature of from about 50 degrees Celsius to about 250 degrees Celsius, in some additions from about 70 degrees Celsius to about 200
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degrees Celsius, in some additions - from about 80 degrees Celsius to around 250 degrees Celsius, and in some additions, from around 80 degrees Celsius to around 125 degrees Celsius. Lower processing temperature can reduce evaporation of botanical oil and potential loss during processing. Similarly, the apparent shear rate during melt mixing can range from about 100 seconds.<sup>-1</sup> at about 5,000 seconds<sup>-1</sup>, in some additions from around 200 seconds<sup>-1</sup> at about 2,000 seconds<sup>-1</sup>, and in some additions, from about 400 seconds' to about 1,200 seconds<sup>-1</sup>. The apparent cut rate is equal to 4Q / TTR<sup>3</sup>, where Q is the volumetric flow rate (m<sup>3</sup>/ s) the polymer melt and R is the radius (m) of the capillary vessel (for example extruder matrix) through which the melted polymer flows. The apparent melt viscosity of the resulting antimicrobial composition can be relatively low, such as from about 1 Pascal seconds to about 100 Pascal seconds (Pa »s), in some additions from about 5 Pascal seconds to about 60 Pascal seconds and in some additions from about 20 Pascal seconds to about 50 Pascal seconds, as a temperature of 160 degrees Celsius and a cut rate of 1000 sec were determined<sup>-1</sup>. The melt flow rate (190 degrees Celsius, 2.16 kilograms) of the composition can also range from about 0.05 grams per 10 minutes to
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about 50 grams per 10 minutes, in some additions from about 0.1 grams per 10 minutes to about 15 grams per 10 minutes, in some additions from about 0.5 grams per 10 minutes to about 5 grams per 10 minutes.
Once formed, the antimicrobial composition of the present invention can be used in a variety of ways such as particles, lotions, creams, gel, liniment, ointment, sage, oil, foam, gel, film, wash, coating, liquid, capsule , tablet, concentrate, etc. In a particular embodiment, for example, the antimicrobial composition can be formed into a film, either alone or in conjunction with an additional film-forming material. The film can be used in a wide variety of applications, such as in the packaging of articles (for example food products, medical products, garments, garbage, absorbent articles (for example diapers) etc. The film can have a monolayer structure or a multilayer structure Multilayer films usually contain at least one base layer and at least one skin layer, but can contain any number of desired layers. The base layer and / or the skin layer may contain the antimicrobial composition of the present invention. Any known technique can be used to form a film of the combined material, including blowing, setting, flat die extrusion, etc. In a particular embodiment, the film may
<img file="MX356246B_D0029.tif" />
INSTITUTO MtXlCAI *) DS INDUSTRIAL PROPERTY to be formed by a blowing process in the ....... gpial- a (for example air) is used to expand a bubble of the extruded polymer mixture through an annular matrix . The bubble is then collapsed and collected in a flat film form. Processes for producing blown films are described, for example, in US Patent No. 3,354,506 issued to Raley; in US Patent No. 3,650,649 issued to Schippers; and in the United States of America Patent No. 3,801,429 issued to Schrenk et al., as well as in the publication of the United States of America Patent Application No. 2005/0245162 by McCormack et al. and in the patent application of the United States of America No. 2003/0068951 to Boggs et al., All of which are incorporated herein by reference in their entirety for all purposes. In yet another embodiment, however, the film is formed using a setting technique.
In addition to being formed into a film, the antimicrobial composition of the present invention can also be particulate and applied to other types of articles. Powder reduction can be accomplished using any of a variety of known techniques. Suitable powder reduction techniques may include, for example, the hammer mill or cryogenic disc mill, solid state cutting spray using cold extrusion technology, dual stream mills (for example type mills
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PSKM or PPSM available from Pallmann Industries), · -and other methods .......
known spray nozzles. Cryogenic depletion techniques or cold extrusion spray techniques may be particularly suitable since such techniques limit the degree to which volatile botanical oil is heated and lost during powder formation. Examples of such techniques are described in greater detail, for example, in US Patent No. 5,395,055 issued to Shutov et al. Which is incorporated herein by reference in its entirety for all purposes.
The shape of the particles can vary as desired, such as spherical, nodule, flake, etc. The average particle size can also be selected to utilize the ability of botanical oil to be released during use. More particularly, the present inventors have discovered that smaller particle sizes can generally result in a higher oil release rate when dispersed in an aqueous solution due to their high surface area to volume ratio. However, at a very small size, botanical oil can become unstable during storage and currently begin to filter out of the particles before use. In this regard, the present inventors have found that an average size of from about 10 microns to about 3,000 microns, in some incorporations from about 50 microns to about 800 microns, and in some incorporations from about 100 microns around
<img file="MX356246B_D0031.tif" />
600 micrometers can help achieve a good balance between stability and release.
Regardless of their particular shape, antimicrobial particles can be applied to a wide variety of different articles to impart antimicrobial efficacy. In a particular embodiment, the composition is applied to a cleaning cloth. Such cleaning cloths can be used to reduce microbial or viral populations on a hard surface (eg, a sink, table, or counter, sign, and others) or a surface on a user / patient (eg, skin , the mucous membrane such as the mouth, nasal passage, stomach, vagina, etc., as a living site, a surgical site, and others). The cleaning cloth can provide an increased surface area to facilitate contact of the composition with microorganisms. In addition, the cleaning cloth can also serve other purposes, such as providing barrier properties with water absorption. The cleaning cloth can also remove microorganisms again from frictional forces imparted to the surface.
The cleaning cloth can be formed from any of a variety of materials as is well known in the art, typically, however, the cleaning cloth includes a fibrous fabric containing absorbent fibers. For example, the cleaning cloth may be a paper product that contains a fabric
<img file="MX356246B_D0032.tif" />
ΙΜΡϊ of paper or more tissue paper, such as facial tissue, a bathroom tissue, paper towels, napkins, and others. The paper product can be single layer in which the fabric that forms the product includes a single layer or is layered (eg it has multiple layers), or can be multi-layer in which the fabrics that make up the product can in themselves being either a single layer or multiple layers. Typically the basis weight of such a paper product is less than about 120 grams per square meter (gsm), in some additions less than about 80 grams per square meter, in some additions less than about 60 grams per square meter, and in some additions, from about 10 grams per square meter to about 60 grams per square meter. Any of a variety of materials can also be used to form the paper fabric or fabrics of the product. For example, the material used to make the paper product can include absorbent fibers formed from a variety of pulping processes, such as kraft pulp, sulphite pulp, thermomechanical pulp, etc. The pulp fibers can include soft wood fibers having an average fiber length of more than one millimeter and particularly from about 2 millimeters to 5 millimeters based on the average heavy length. Such softwood fibers may include, but are not limited to northern softwood, southern softwood, redwood, red cedar, hemlock, pine (eg southern pine) spruce (black spruce) combinations thereof, and others. . The fibers of 'nítwt »mexican IZ & v'S & Jl ·
DE IA proprietary UX .IX «Tg <3 Nr, l>« TRIAl TJ · -? 'S' formed from polypropylene, pulp commercially available from suitable examples .. for the present invention include those available from Kimberly Clark Corporation under the Longlac trade designations19. Hardwood fibers such as eucalyptus, maple, birch, aspen, and others can also be used. In certain cases the eucalyptus fibers may be particularly desired to increase the softness of the fabric. Eucalyptus fibers can also improve brilliance, increase opacity, change the pore structure of the fabric to increase its transmission capacity. In addition, if desired, secondary fibers obtained from recycled materials can be used, such as pulp fiber from sources, such as newspaper, reclaimed paper, and office waste. In addition, other natural fibers can also be used in the present invention, such as abaca, sabai grass, milkweed silk, pineapple leaf, bamboo, seaweed, and others. In addition, in some cases synthetic fibers can also be used. If desired, absorbent fibers (for example t
pulp fibers) can be integrated with the synthetic fibers to form a composite. Thermoplastic fibers can also be used in non-woven fabric such as those of polyolefins, polybutylene, etc .;
polyesters, for example polyethylene terephthalate and others; polyvinyl acetate, polyvinyl chloride acetate, polyvinyl butyral; acrylic resins, for example polyacrylate, polymethylacrylate, polymethylmethacrylate and others; polyamides, for example, polyethylene, poly tetrafluorobut Hay,
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ΙΚϋ! '«Π» ΙΑ! -i '' · * example nylon, polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; polyurethane; polylactic acid; polyhydroxyalkanoate; copolymers thereof, and others. Because many synthetic thermoplastic fibers are inherently hydrophobic (eg non-wettable) such fibers can optionally be made more hydrophilic (eg wettable) by treatment with a surfactant solution prior to tissue formation, during formation and / or after tissue formation. Other known methods of increasing wettability may also be employed, as described in U.S. Patent No. 5,057,361 issued to Sayovitz, et al. Which is incorporated herein in its entirety by reference thereto for all purposes. The relative percentages of such fibers can vary over a wide range depending on the desired characteristics of the compound. For example, the compound may contain from about 1 percent by weight to about 60 percent by weight, in some additions from 5 percent by weight to about 50 percent by weight, and in some additions, from from about 10 percent by weight to about 40 percent by weight of synthetic polymeric fibers. The similar compound may contain from about 40 weight percent to about 99 weight percent, in some additions from 50 weight percent to about weight percent, and in some additions, from
<img file="MX356246B_D0033.tif" />
<img file="MX356246B_D0034.tif" />
INSTITUTO MEXICANO DE LA PROFLEOAl INOI 'STKIAL about 60 percent by weight to about 90 percent by weight of absorbent fibers. ~~
Compounds as described above can be formed using a variety of known techniques. For example, a nonwoven composite can be formed which is a coform material containing a stabilized matrix blend of thermoplastic fibers and a second non-thermoplastic material. As an example, coform materials can be made by a process in which at least one meltblown die head is arranged near a conduit through which other materials are added to the tissue as it is being formed. Such other materials may include, but are not limited to fibrous organic materials such as woody pulps or non-woody pulps such as cotton, rayon, recycled paper, pulp fluff and also super absorbent particles, inorganic absorbent materials and / or materials. organic absorbents, treated polymeric short fibers and others. Some examples of such coform materials are described in United States Patent No. 4,100,324 to Anderson et al .; in United States Patent No. 5,284,703 issued to Everhart, et al .; and in the United States Patent of Améric to No. 5,350,624 issued to Georger, et al .; which are incorporated in their entirety by reference to them for all purposes. Alternatively, the nonwoven compound can be formed by short length fibers
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DF IA PROWEDAl. , - ·· ^ · hydraulically entangled and / or filaments with current<sup>F</sup>to<sup>, l</sup>’<sup>s</sup>a ^ 'agida— jet high pressure. Various techniques »-« gora · winding ------- hydraulically the fibers are generally described, for example, in the patent of the United States of America No. 3,494,821 issued to Evans and in the patent of the United States of America No. 4,144,370 issued to Bouolton, which are incorporated herein in their entirety by reference to them for all purposes. Hydraulically entangled continuous filament nonwoven compounds (eg, spunbond fabric) and natural fibers (eg, pulp) are described, for example, in U.S. Patent No. 5,284,703 to Everhart, et al. And in the patent United States of America No. 6,315,864 issued to Anderson et al. which are incorporated herein in their entirety by reference to them for all purposes. The hydraulically entangled nonwoven compound of the blends of short fiber (eg, polyester and rayon) and natural fibers (eg, pulp) also known as yarn-tied fabrics are described, for example, in US Patent 5,240,764. awarded to Haid and others; which is incorporated herein in its entirety by reference to them for all purposes.
Regardless of the materials are processes used to form the cleaning cloth, the basis weight of the cleaning cloth is typically from about 20 grams per square meter to about 200 grams per square meter.
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The cleaning cloth can take a variety of shapes, including but not limited to the generally circular, oval, square, rectangular, or irregularly shaped shape. Each individual cleaning cloth can be arranged in a folded configuration and stacked one on top of the other to provide a stack of wet cleaning cloths. Such folded configurations are recognized by those of skill in the art and include the C-fold, Z-fold, and quarter-fold and other configurations. For example, the cleaning cloth may have an unfolded length of from about 2.0 centimeters to about
80.0 centimeters and in some additions from around 10.0 centimeters to around 25.0 centimeters. Cleaning cloths may similarly have an unfolded width of from about 2.0 centimeters to about 80.0 centimeters and in some additions, from about 10.0 centimeters to about 25.0 centimeters. The stack of folded cleaning cloths can be placed inside a container, such as a plastic tube to provide a package of cleaning cloths for eventual sale to the
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consumer. Alternatively, cleaning cloths can
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include a continuous strip of material in the box. Perforations between each cleaning cloth and 1 arranged in a pile or rolled on a roll for the assortment, Various suitable dispensers, containers and systems for the delivery of the cleaning cloths are described in United States Patent No. 5,785,179 issued to Buczwinski et al .; in United States Patent No. 5,964,351 issued to Zander; in the patent of the United States of America No. 6,030,331 issued to Zander; in United States Patent No. 6,158,614 to Haynes, et al .; in United States Patent No. 6,269,969 to Huang et al .; in United States Patent No. 6,269,970 issued to Huang, et al .; and in United States Patent No. 6,273,359 to Newman, et al., all of which are incorporated herein by reference in their entirety for all purposes.
The composition can be incorporated into the cleaning cloth in a variety of different ways. For example the composition can be applied to a surface of the cleaning cloth using known techniques such as printing, embedding, spraying, melt extrusion, coating (eg solvent coating, powder coating, brush coating , etc.), foaming and others. If desired, the composition can be applied in a pattern that
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INDUSTIAL covers from about 5 percent to about 95 percent, in some additions from about 10 percent to about 90 percent, in some additions from about 10 percent to about 90 percent, and in some additions of from about 20 percent to about 75 percent of a cleaning cloth surface. Such patterned application can have several benefits, including improved aesthetic traction, improved absorbency, etc. The particular type or style of the pattern is not a limiting factor of the invention, and may include, for example, any arrangement of strips, bands, dots, or other geometric shape. The pattern can include clues (eg marks, texts and logos) floral designs, abstract designs, any art work settings etc. It will truly be appreciated that the pattern can take on virtually any desired appearance. The composition can also be mixed with the fibers used to form the cleaning cloth. This can be particularly useful when the composition is in the form of particles. For example, such particles may be mixed with known absorbents (eg, pulp fibers, short fibers, etc.) during hydraulic entanglement, shaping, etc. The particles can also be incorporated into the thermoplastic material of the cleaning cloth (for example meltblown fabric) using techniques
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known.
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The amount of the antimicrobial composition on the cleaning cloth may vary depending on the nature of the substrate and its intended application. For example, the aggregate level of composition may be from about 5 percent to about 100 percent, in some additions from about 10 percent to about 80 percent, in some additions from about 20 percent to about 70 percent. The aggregate level is determined by subtracting the weight of the untreated substrate from the weight of the treated substrate, dividing this calculated weight by the weight of the untreated substrate and then multiplying by 100 percent. Lower aggregate levels can provide optimal substrate personality, while higher aggregate levels can provide optimal antimicrobial efficacy.
To use the composition, an aqueous solution can simply be added, thereby dispersing the starch and releasing the botanical oil. The aqueous solution may contain only water or it may contain water in combination with other components. For example, a weak acid can be used to help disperse the starch and facilitate oil release on contact with the aqueous solution. Acids suitable for this purpose may include, for example, organic carboxylic acids such as citric acid, oxalic acid, lactic acid, acetic acid, etc. Regardless of this, the present inventors have discovered
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surprisingly, the amount of botanical oil released into the aqueous solution may be even greater than the limit of its normal oil solubility in water. Without attempting to be bound by theory, it is believed that this can be accomplished due to the physical structure of the starch that is capable of effectively carrying the volatile into the released solution. For example, the solubility limit of thymol in water (at 25 degrees Celsius) is typically around 0.1 percent by weight. When released from the composition of the present invention, however, the concentration of thymol in the released solution may be greater than 0.1 weight percent, in some incorporations greater than about 0.15 weight percent, and in some incorporations of from about 0.2 percent by weight to about 10 percent by weight, and in some additions, from about 0.2 percent by weight to about 4 percent by weight.
The present inventors have discovered that the composition of the present invention can inhibit (for example reduce by a measurable amount or completely prevent) the growth of one or more microorganisms when exposed to them. Examples of microorganisms that can be inhibited include bacteria, protozoa, algae, and fungi (eg, molds and yeasts). In addition, it is possible to use this invention to inactivate viruses, prions, and other infectious particles. For example, the composition can inhibit the growth of various groups of significant bacteria
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0 INDUSTHIAL medically, such as rods gram ne ga tj vaapo-i ·· exemplary l-er Entereobacteria); gram negative arched rods (eg Helicobacter, Campylobacter, etc.); gram negative cocci (for example Neiseria); gram positive rods (for example Bacillus, Clostridium, etc.), gram positive cocci (for example Staphylococcus, Streptococcus, etc.); obligate intracellular parasites (eg Ricyckettsia and Chlamydia); acid fast rods (eg Myobacterium, Nocardia, etc.); spirochetes (for example Treponema, Borellia, etc.); and microplasms (for example small bacteria that lack a cell wall). Particularly the species of bacteria that can be inhibited with the composition of the present invention include Escherichia coli (gram negative rod), klebsiella pneumonia (gram negative rod), Streptococci (gram positive), Salmonella coleraesuis (gram negative rod), Staphylococcus aureus (cocus gram positives) and P. aeruginosa (gram negative rod). In addition to bacteria, other microorganisms of interest include fungi (eg Aspergillus niger) and yeast (eg Candida albicans).
With exposure for a certain period of time, the composition can provide a reduction of at least about 2, in some additions of at least about 3, in some additions of at least about 4, and in some additions of at least around 5 (for example around 6). In the reduction
<img file="MX356246B_D0039.tif" />
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Log, for example can be determined from it. percent of population killed by composition according to the following correlations;
% Reduction
99.9
99.99
99.999
99.9999
Log reduction
Such a log reduction can be achieved according to the present invention after only a relatively short exposure time. For example, the desired log reduction can be achieved after exposure for as little as 30 minutes, in some additions for 15 minutes, in some additions for 10 minutes, in some additions for 5 minutes, in some additions for 1 minute, and in some incorporations for 30 seconds.
The present invention may be better understood with reference to the following examples.
<img file="MX356246B_D0040.tif" />
Materials employed
Thymol (99.5 percent purity) was obtained from SigmaAldrich.
Native corn starch, Cargill Gum ™ 03460, was obtained from Cargill Inc. (of Minneapolis, Minnesota, United States of America).
Hydroxypropylated starch, Glucosol® 800, was obtained from Chemstar Product Company (Minneapolis, Minnesota, United States of America).
Glycerin (or Glycerol) was obtained from Cognis Corporation.
Excel P-40S (mono-diglyceride dispersion aid) was obtained from Kao Corporation.
Test Methods
Timol stability
The samples were placed in an oven at 40 degrees centigrade, 50 degrees centigrade or 55 degrees centigrade for a certain number of days. The residual thymol level was determined through an analysis of
High Performance Liquid Chromatography (HPLC). More particularly, the thymol level in each sample was determined by generating a thymol calibration curve by the following method. Approximately 70 milligrams of thymol were weighed in a 100 milliliter volumetric bottle.
<img file="MX356246B_D0041.tif" />
Approximately 50 milliliters of a 0.1 percent acetic acid: IPA (50:50) mixture was added to the bottle and the contents were rotated to promote dissolution. The volume was diluted with a 0.1 percent mixture of acetic acid: IPA (50:50) and subsequent dilutions were carried out to generate a calibration curve with a concentration range of approximately 700 pg / milliliter to 70 pg /milliliter. The samples were prepared as follows. Approximately 100 milligrams of sample were used for each code, where each code was analyzed in duplicate at each pull point. The measured material was cut into small pieces and placed in a 40 milliliter container. To each container, 10.0 milliliters of 0.1 percent acetic acid were added and the contents were shaken and sonicated over 30 minute periods until the sample was dispersed. To each container, 10.0 milliliters of IPA were added and the contents were sonicated for 10 minutes to promote mixing and extraction of thymol. The resulting solutions were filtered through nylon filters before injection. Thymol levels were calculated using the thymol calibration curve described above.
Equipment and HPLC Conditions
Column: Phenomenex NH2
Column temperature: Ambient
Mobile phase:
50:50 (IPA: 0.1% acetic acid)
<img file="MX356246B_D0042.tif" />
Flow rate:
Injection volume: 15 microliters
ELS detection:
280 nm
Concentrations of Red 1 in Extractions
An aliquot of a sample was spun at approximately 5,000 revolutions per minute until visible settling occurred (approximately 30 minutes). The solution was filtered using two different types of syringe filters: (1) Pall Life Acrodisc 0.2 micron 13mm nylon panty and (2) Whatman Puradisc 0.2 micron polyethersulfone membrane with a polypropylene enclosure. 1.0 milliliters of the centrifuged solution was pipetted into a 10 milliliter bottle. The contents were dissolved and diluted with a 0.1 percent AA: IPA (50:50) solution by volume. The solution was then filtered with a 0.45 micron Pall Acrodisc nylon membrane. Thymol concentration was determined through High Performance Liquid Chromatography (HPLC) analysis according to the following conditions:
Equipment and HPLC Conditions
HPLC: Agilent 1100 HPLC System.
Column: Environment Phenomenex Luna NH2 (5 pm,250
Mm x 4.6 mm).
Detector:
Mobile phases:
Flow rate:
Injection volume Run time:
Inhibition Zone
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5 PE PROPERTY
INDUSTRIAL
UV / Vis at 280 nm ___ (75:25) (IPA: 0.1% acetic acid) approximately 0.6 milliliters per minute.
about 15 pL minutes
<img file="MX356246B_D0043.tif" />
To determine antimicrobial efficacy, an inhibition test was carried out. More specifically, a 0.05 gram sample was placed on a freshly spread meadow of test microorganism on TSA (Soybean Tripicasa Agar). Two microorganisms were used, Staphylococcus aureus (ATTC # 27660) as a gram positive bacterium and Escherichia coli as a gram negative bacterium (ATCC # 25922). After 24 hours, incubation at 37 degrees Celsius, the plates were measured for clear zones of inhibition surrounding each sample (clear zone (millimeters) = diameter of sample area (cleaning cloth) diameter).
Microplate Assay
To determine the germicidal efficacy of an extracted thymol solution, a microplate germicidal assay was carried out. In this method, the test solution was put
<img file="MX356246B_D0044.tif" />
in contact with 60 wells of rip microorganisms, pr 11 pha, _ (q * 1_0 <sup>6</sup>Cj <sup>1</sup> j ,. . (forming units (colony) / well) coated on the bottom of flat plates of 96 wells for 4½ minutes. At the end of the contact time, 200pL of a neutralizing Lettheen broth (included 0.5 percent Tween 80) was added to each well to deactivate the active ingredients. After the addition of the neutralizer, 50 L of TSB (Tryptic Soy Broth) were added and then the microplate was incubated to allow survivors to grow. After incubation, the number of wells was recorded showing growth of the target microorganism. If the medium in the well was cloudy, then the well was counted as a disinfecting failure. If the well was not cloudy after incubation, then the well was recorded as achieving disinfection. All the tests were carried out against two different microorganisms, Staphylococcus aureus (ATCC # 6538) as gram positive bacteria and Pseudomonas ¿eruginosa (ATCC # 15442) as negative bacteria.
EXAMPLE 1
The TermoPrism USALabl6 extruder (from Thermo
Electron Corporation, Stone, United Kingdom of Great Britain) was employed to form the antimicrobial composition. The extruder is a joint and continuous rotary twin screw micro extruder, with a screw diameter of 16 <r
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millimeters and a screw length of 64 0 wtilimctrri »& r - The · extruder had 10 barrels. An A-K-Tron supplier (K-Tron America, Pitman New Jersey) was used to feed a mixture of 74 weight percent Glucosol 800, 1 weight percent Excel P-40S, and 25 weight percent of glycerol. The thymol was then added so that it constituted 5 percent by weight of the mixture. Material supply rate was maintained at two pounds per hour. Processing temperatures were 100 degrees Celsius, 110 degrees Celsius, 120 degrees Celsius, 130 degrees Celsius, 135 degrees Celsius, 135 degrees Celsius, '130 degrees Celsius, 125 degrees Celsius, 120 degrees Celsius, and 115 degrees Celsius for areas 1 to 10, respectively. The torsion force was around 40% to 42%, the screw rotation speed was 150 revolutions per minute, and the pressure in the die was from 8 bars to 10 bars. The resulting wire was cooled down through a cooling rod (Bondine, Electric Co. Chicago, Illinois, United States of America). A pelletizer (from Emerson Industrial Controls, Gran Island, New York) was used to cut the yarn from the extruder die and the resulting pellets were collected in a plastic bag for subsequent testing.
<img file="MX356246B_D0045.tif" />
An extruded antimicrobial composition was carried out as described in Example 1, except that the native corn starch was used, the twisting force was around 50% to 53%, and the pressure in the matrix was from 13 bars to 14 bars. The resulting wire was cooled through a cooling strip (Bondine Electric Co. of Chicago, Illinois). A pelletizer (Emerson Industrial Control, Grand Island, New York) was used to cut the yarn from the extruder material and the resulting pellets were collected in a plastic bag for subsequent testing.
Once formed, the pellets of Examples 1 and 2 (approximately 3 millimeters in size) were placed in an oven at 40 degrees Celsius and subjected to the thymol stability test described above. The results set forth below in Table 1.
TABLE 1: Thymol levels after aging at 40 ° C
<td rowspan="2">EXAMPLE</td><td rowspan="2">% POST EXTRUSION THYMOL</td><td colspan="5">Thymol% levels after aging for specified number of days</td>
<td colspan="5">1 DAY 5 DAYS 9 DAYS 20 DAYS 61 DAYS</td>
<td>EXAMPLE 1 (MODIFIED STARCH)</td><td> 5.2</td><td> 5.3</td><td> 5.2</td><td> 5.3</td><td> 5.5</td><td> 5.0</td>
<td>EXAMPLE 2 (NATIVE STARCH)</td><td> 4 . 4</td><td> 3.9</td><td> 3.4</td><td> 2.9</td><td> 1.7</td><td> 1.6</td>
<img file="MX356246B_D0046.tif" />
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As indicated, the composition example 1 was surprisingly very effective Timol, even after 61 days of high aging. The composition of Example 2 was not in trapping Timol.
The pellets from Examples 1 and 2 were also subjected to the zone of inhibition test (ZOI), as described above. The results are set forth below in Table 2.
to store the at the temperature almost as effective
Table 2: Inhibition Zone Test Results after aging at 40 ° C
<td rowspan="3"></td><td colspan="12">INHIBITION AREA AREA (millimeters)</td>
<td colspan="2"> 0</td><td colspan="2">1 DAY</td><td colspan="2">4 DAYS</td><td colspan="2">12 DAYS</td><td colspan="2">20 DAYS</td><td colspan="2">60 DAYS</td>
<td>AND. col i</td><td>s. Aureu-s</td><td>AND. coi i</td><td>s. Aureus</td><td>AND. col i</td><td>s. Aureua</td><td>AND. col i</td><td>s. Aureua</td><td>AND. col i</td><td>3. aureus</td><td>AND. col i</td><td>s. Aureus</td>
<td>one (starch modify fallen</td><td> 11</td><td> 9</td><td> 8</td><td> 7</td><td> 8</td><td> 8</td><td>Ί</td><td> 8</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>
<td>2 (starch native</td><td> 11</td><td> 10</td><td> 9</td><td> 9</td><td> Ί</td><td> 6</td><td> 5</td><td> 6</td><td> 3</td><td> 2</td><td> 1</td><td> 1</td>
As indicated, the antimicrobial composition of Example 1 was surprisingly effective in inhibiting the growth of the bacteria. For example, even after 60 days at an elevated temperature of 40 degrees Celsius, the zone of inhibition values were 6 for both species of bacteria. However, the composition of Example 2 was not as
<img file="MX356246B_D0047.tif" />
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E TEMPLE 3
A composition of 70 percent Glucosol® 800, 24 percent glycerol, 5 percent thymol, and 1 percent Excel P-40S was prepared by extrusion, it was palletized, the material was put in a plastic bag , and was placed at a temperature of minus 32 degrees Celsius for a minimum of 24 hours. The resulting chilled material was downsized through a Bríckmann / Retsch laboratory scale grinding mill (set speed = 1) and a size of <250 micron was collected. The resulting sample was tested for thymol stability at 55 degrees Celsius using the test method described above. The results are established in Table 3.
Table 3: Thymol levels after aging
<td rowspan="3">EXAMPLE 3</td><td colspan="3">Thymol level (percent by weight)</td>
<td>0 days</td><td>7 days</td><td>19 days</td>
<td> 5.3</td><td> 1.2</td><td> 1</td>
In addition, 100 milliliters of deionized water was added to 20 grams of the unaged particles. The concentration of thymol in the solution was determined after
<img file="MX356246B_D0048.tif" />
2, 10, 60 minutes by the method thymol concentrations by weight 0.128% respectively.
described above giving 0.107%, 0.118%,
EXAMPLE 4
A composition of 80% Glucosol® 800, 14% glycerol, 5% thymol, and 1% Excel P-40S was prepared as written in Example 3. The resulting cooling material was downsized through from a Brickmann / Restsch lab scale grinding mill (set speed = l) and collected at a size of 250-425 microns per screen. The resulting sample was tested for thymol stability at 50 degrees centigrade using the test method described above. The results are established in Table 4.
Table 4: Thymol levels after aging
<td rowspan="3">EXAMPLE 4</td><td colspan="7">Thymol level (percent by weight)</td>
<td>0 days</td><td>1 day</td><td>4 days</td><td>5 days</td><td>7 days</td><td>28 Days</td><td>48 Days</td>
<td> 5.09</td><td> 4.81</td><td> 4.65</td><td> 4.6</td><td> 4.47</td><td> 4.5</td><td> 4.46</td>
A series of thymol extractions were carried out from the particles prepared in Example 4 involving various amounts of modified starch particles / thymol various amounts of water, addition of citric acid particles, and extraction time. The method
<img file="MX356246B_D0049.tif" />
extraction involved adding a quantity ..speat?,! f .i. nothing - of. water to the starch / thymol particles and to the citric acid particles, wait a specified amount of time while stirring, and centrifugation to collect the supernatant. In addition, the water was cooled to pure thymol as a control, stirred for a specified amount of time, and centrifuged to collect the supernatant. Thymol concentration in supernatant was determined by the method described above. The composition of the solutions and the resulting thymol concentration are set forth in Table 5 below.
Table 5: Thymol Extractions from Particles
<td colspan="9">PARTICLE COMPOSITION</td><td></td>
<td>Starch</td><td>Plasti- spicy</td><td>% Thymol</td><td>Size Of Particle (Microns)</td><td>Quantity (grams)</td><td>Acid Citric (grams)</td><td>Water deioni- zada (milli- liters)</td><td>Weather of extraction (min.)</td><td>% Tim (% p weight) solution extract</td><td>ol or in or</td>
<td rowspan="2">80% Glucos ol 800</td><td rowspan="2">14% glycer ol</td><td rowspan="2"> 5</td><td rowspan="2"> 250-425</td><td> 0.75</td><td> 0.38</td><td> 12.4</td><td> 30</td><td> 0.15!</td><td></td>
<td> 1.5</td><td> 0.38</td><td> 12.4</td><td> 30</td><td>0.24C</td><td></td>
<td rowspan="2">n / a</td><td rowspan="2">n / a</td><td rowspan="2">100 (with- troll)</td><td rowspan="2"> <250</td><td> 2</td><td> 1.14</td><td> 97</td><td> 30</td><td> 0.081</td><td></td>
<td> 2</td><td> 0</td><td> 100</td><td> 30</td><td> 0.084</td><td></td>
The reported solubility limit of thymol with water is normally 0.1 grams x 100 grams of water (0.1%) at 25 degrees Celsius. As shown above, however, thymol concentrations in solutions of this extract were up to 2.4 times greater than the reported limited solubility. Two of the solutions given above (0.159% thymol and
<img file="MX356246B_D0050.tif" />
0.240% thymol) were also tested for antimicrobial efficacy according to the microplate assay described above. The results are set forth below in Table 6.
Table 6: Efficacy of Thymol Extractions
As indicated, both extracts are shown as obtaining antimicrobial efficacy. Surprisingly, Example 6 had very strong antimicrobial efficacy, showing zero microbial growth.
<td>Example</td><td>Starch</td><td>Plasti- spicy</td><td>& Thymol</td><td>Particle Measure s (microns )</td><td>Quantity d (grams )</td><td># of wells showing growth after the S. aureus test</td><td># of wells showing growth after. test for P. aeruijinosa</td>
<td>Example 5</td><td>80% Glucose 1 800</td><td rowspan="2">14% glycerol</td><td> 5</td><td> 250-425</td><td> 0.75</td><td> 9</td><td> 2</td>
<td>Example 6</td><td></td><td></td><td></td><td> 1.5</td><td> 0</td><td> 0</td>
Even though the invention has been described in detail with respect to specific embodiments thereof, it will be appreciated by those of skill in the art to achieve an understanding of the foregoing, that equivalent variations of these embodiments can be readily conceived. Therefore, the scope of the present invention should be evaluated as that of the appended claims and any equivalent thereof.
<img file="MX356246B_D0051.tif" />
Contents26
51 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51
56 members in 10 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 12961638 | United States of America | – | |
| 96163810 | United States of America | A | |
| 2011054828 | International Bureau of the World Intellectual Property Organization (WIPO) | W |
Members56
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| MX2013006449A | Mexico | A | |
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| EP2648522A2 | European Patent Office (EPO) | A2 | |
| EP2648523A2 | European Patent Office (EPO) | A2 | |
| KR20140017500A | Republic of Korea | A | |
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| EP2648522A4 | European Patent Office (EPO) | A4 | |
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| AU2012356251A1 | Australia | A1 | |
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| AU2011340217B2 | Australia | B2 | |
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1 legal event, as the office reported them to INPADOC
Events
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|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 356246
- Application
- 6449
Titles2
- Spanish
- COMPOSICION ANTIMICROBIANA PROCESADA CON DERRETIDO.
- English
- MELT PROCESSED ANTIMICROBIAL COMPOSITION.
Classification
- CPC, 13
- A01N65/00
- A01N31/08
- B29B7/10
- B29B7/38
- B29B9/06
- B29B9/12
- B29B9/16
- B29C48/00
- B29C48/625
- B29C48/405
- B29C48/40
- A61P31/02
- A01N43/04
- IPC, 8
- A01N43 04
- A01N65 00
- A01P1 00
- A61K31 70
- B29C48 00
- B29C48 40
- B29C48 405
- B29C48 625