Patent Application
20080008676
All percentages, ratios and proportions herein are by weight of the composition, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise specified.
As used herein, the term “comprising” and its derivatives means are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other, unstated features, elements, components, groups, integers, and/or steps.
As used herein, the term “deodorant product” means a deodorant product for sale and use. The deodorant product comprises a plurality of individual bodies of the deodorant composition of the present invention packed together in a package.
As used herein, the term “amine type malodors” means malodors which are caused by a compound comprising an amine group. Typical compounds in the living environment giving out amine type malodors include, but are not limited to ammonia, trimethyl amine, triethylamine, etc.
As used herein, the term “acid type malodors” means malodors which are caused by a compound comprising a carboxylic acid group. Typical compounds in the living environment giving out acid type malodors include, but are not limited to isovaric acid, butyric acid, propionic acid, etc.
As used herein, the term “sulfur type malodors” means malodors which are caused by a compound comprising sulfur. Typical compounds in the living environment giving out sulfur type malodors include, but are not limited to hydrogen sulfide, methylmercpatan, methyl sulfide, dimethyl sulfide, etc.
As used herein, the term “average particle diameter” means the average particle diameter measured along the longest axis of a given particle material as determined by conventional analytical techniques such as, microscopic determination utilizing a scanning electron microscope (SEM).
As used herein, the term “surface area” means the summation of the areas of exposed surfaces of a three-dimensional shape. For example, when the three-dimensional shape is a cuboid having a length, breadth and a height of a, b and c, then, the surface area of the cuboid is 2(ab+ac+bc), when the three-dimensional shape is a sphere shape having a radius of r, the surface area of the sphere is 4 πr2, etc. For irregular shapes, there are several methods which can be employed for measuring the surface area described in the literature. For example, three dimensional digital imaging by digital optical microscopic is one of the methods widely used for measuring surface area of irregular shaped three dimensional structures with great accuracy.
The deodorant composition herein comprises a metallic deodorizing agent, a carboxylic group-containing gelling polymer and a liquid media. The deodorant composition herein may further comprise a deodorant polymer, a preservative, a solubilizer, a UV absorbent, a perfume, a dye and a mixture thereof.
The deodorant composition herein comprises from about 0.005% to about 2%, or from about 0.01% to about 1%, or from about 0.05% to about 0.5% by weight of a metallic deodorizing agent selected from copper, zinc, silver, platinum, nickel, iron, cobalt, a copper compound, a zinc compound, a silver compound, a platinum compound, a nickel compound, an iron compound, a cobalt compound and a mixture thereof. Metal or metal compound is known to be effective in deodorizing sulfur type malodors which are common in living environment, especially toilet room, by reacting with the sulfur-containing chemicals. However, as discussed hereinabove, while it is desirable to formulate a high level of metal or metal compound in a deodorant composition to improve the deodorant performance, where the level of a metal compound in a gel deodorant composition is higher than 2%, the gel deodorant composition will have an unappealing color, such as dark blue and also a poor color integrity. On the other hand, where the level of a metal or metal compound in the gel deodorant composition is lower than 0.005%, the deodorant composition will not give satisfactory deodorant performance.
Metal compound useful herein can be a metal oxide or an organic or inorganic salt of a metal. Where a metal or water-insoluble metal compound is used, a water-insoluble oxides or salts of a metal, the metal or water-insoluble metal compound are preferably added into the deodorant composition in a fine powder form having an average particle diameter of from about 20 nm to about 20 microns. Suitable water-insoluble metal compound useful herein include copper monoxide, copper suboxide, zinc oxide, nickel oxide, etc.
Suitable metal salt useful herein include chloride, sulfate and carbonate of copper, zinc, silver, platinum, nickel, iron and cobalt, as well as a complex of copper, zinc, platinum, silver, iron, cobalt with carboxylic acids or carboxylic acid-containing polymers.
Copper chloride, copper sulfate, copper carbonate, zinc chloride, zinc sulfate, silver and a mixture thereof are the most preferred metallic deodorizing agent useful herein.
As used herein, “carboxylic group-containing gelling polymer” means a polymer comprising a unit of carboxylate or carboxylic acid and the polymer swells upon absorbing a liquid media, such as water and/or other solvent and forms a gel. Gel is typically considered to be a colloid in which the dispersed phase has combined with the dispersion medium to produce a semisolid material, such as a jelly. As a consumer preferred deodorant product form, gel is used as a carrier of the other components of the deodorant product. Furthermore, the carboxylic group-containing gelling polymer herein may also play the function of a deodorant active agent since the carboxylic group contained therein reacts with the amine groups in a chemical compounds responsible for the amine type malodors.
Suitable carboxylic group-containing gelling polymers herein include homepolymers and copolymers comprising a monomer of olefinically unsaturated carboxylic acid or anhydrides that contain at least one carbon-to-carbon olefinic double bond. Examples of such monomers include acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, β-methylacrylic acid (crotonic acid), α-phenylacrylic acid, β-acryloxypropionic acid, sorbic acid, α-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, β-sterylacrylic acid, itaconic acid, citroconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, maleic acid anhydride, alkali metal salt of acrylic acid or methacrylic acid, butyl(meth)acrylate, ethyl(meth)acrylate, methyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and a mixture thereof. The carboxylic group-containing gelling polymer can be a cross-linked or non cross-linked polymer. There are no specific limits on the way of cross-linking the polymers or the cross-linking agent can be used. Examples of cross-linking agent useful herein include tetraallyl ethoxyethane, 1,1,1-trimethylopropanetricrylate, methylene bisacrylamide, diethylene glycaol diacrylate, triallylamine, allyl methacrylate, tetraallyloxyethane. Typically, the cross-linking agent is used in amounts ranging from 0.0005 to 5 parts by weight per 100 parts by weight of monomers (including any possible co-monomers) used. These polymers can be used either solely or in the form of a mixture of two or more different polymers. Examples of these polymer materials are disclosed in U.S. Pat. No. 3,661,875, U.S. Pat. No. 4,076,663, U.S. Pat. No. 4,093,776, U.S. Pat. No. 4,666,983, and U.S. Pat. No. 4,734,478.
Preferably, the carboxylic group-containing gelling polymers is a partially neutralized cross-linked polyacrylic acid, such as poly (sodium acrylate/acrylic acid) and cross-linked isobutylene-maleic acid anhydride copolymer. Commercially available gelling polymers herein include Aqualic™ from Nihon Shokubai (Tokyo, Japan), Aquakeep™ from Sumitomo Seika (Osaka, Japan), Aquabeads™ from Kuraray (Osaka, Japan) and Hysorb™ from BASF (Germany). More examples of carboxylic group-containing gelling polymers can be found in the book entitled Modem Superabsorbent Polymer Technology, Ed by Fredric L. Bucholz and Andrew T. Graham, published by John Wiley & Sons, Inc., 1998.
The deodorant composition herein comprises from about 0.5% to about 40%, or from about 1% to about 20%, or from about 4% to about 10% by weight of a carboxylic group-containing gelling polymer.
The liquid media useful herein is typically selected from water, oil, an organic solvent, such as an alcohol, and a mixture thereof. In an embodiment herein, the liquid media is water.
Typically, the deodorant composition herein comprises from about 50% to about 95%, or from about 80% to about 90% by weight of a liquid media.
According to one embodiment, the deodorant composition herein further comprises a deodorant polymer comprising both “cationically dissociating groups” and “anionically dissociating groups”.
The term “cationically dissociating groups” as used herein means those ion-exchange groups whose counter ion is a cation. A typical cationically dissociating group is an acid group. Cationically dissociating groups have the ability to adsorb polar substances and are capable of releasing a proton (hydrogen ion) to enter into neutralizing reaction with basic substances, such as ammonia or amines. As a result, the basic substances can be removed. One or more cationically dissociating groups may be introduced into the polymer. Examples of such cationically dissociating groups include a carboxyl group, a sulfate group, a phosphate group, a sulfoethyl group, a phosphomethyl group and a carbomethyl group, etc. Preferred cationically dissociating groups include a sulfate group and a carboxyl group. Monomers that have such cationically dissociating groups and that are useful herein include, for example, acrylic acid, methacrylic acid, allylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid and salts thereof, and 2-acrylamido-2-methylpropanesulfonic acid.
The term “anionically dissociating groups” as used herein means those ion-exchange groups whose counter ion is an anion. Anionically dissociating groups have the ability to absorb polar substances and are capable of entering into neutralizing reaction with acidic substances, such as, hydrogen sulfide or mercaptans. As a result, the acidic substances can be removed. One or more kinds of anionically dissociating groups may be introduced into the polymer. Examples of anionically dissociating groups include quaternary ammonium group and primary, secondary, and tertiary amino or amido groups, such as amino group, methylamino group, dimethylamino group, and diethylamino group. Monomers having such anionically dissociating groups and that are useful in the present invention include, for example, vinylbenzyltrimethyl ammonium salt, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminomethyl methacrylate, tertiary-butylaminoethyl acrylate, tertiary-butylaminoethyl methacrylate, dimethylaminopropylacrylamide, acrylamide, allylamine, N,N-dimethylacrylamide, N,N-dimethylaminoethylacrylate and N,N-dimethylaminopropyl acrylamide.
Specifically preferred deodorant polymers are those comprising both carboxyl group and amino group, such as copolymers of acrylic acid with diethylamino ethyl methacrylate, dimethylamino ethyl acrylate, dimethylamino ethyl methacrylate, diethylamino ethyl acrylate, diethylamino methyl methacrylate, tert-butylamino ethyl acrylate, tert-butylamino ethyl methacrylate, dimethylaminopropyl acrylamide, acrylamide, allylamine, N,N-dimethylacrylamide, N,N-dimethylaminoethyl acrylate, or N,N-dimethylaminopropyl acrylamide.
According to another embodiment herein, the deodorant polymer is grafted onto a substrate. By grafting, it means that the polymer is bonded to the substrate at specific sites. Substrates useful herein are not limited in any particular way and can be any materials able to link with the polymer. Illustrative substrates useful for grafting the deodorant polymers include aldohexose, glucose, starch and cellulose. Without intending to be bound by theory, it is believed that the substrate herein is used to support the deodorant polymers containing functional groups. By grafting the deodorant polymers onto the substrate, the contact of the functional groups in the deodorant polymers with the chemical compounds to be absorbed is increased, and thus a better deodorizing performance is obtained.
The deodorant polymer can be grafted onto the substrate by any known polymerization method, such as a reaction initiator polymerization method, a thermal polymerization method, or an ionizing radiation polymerization method. According to one embodiment herein, the graft deodorant polymer is obtained by mixing the monomers and substrate to give a mixture which is then subjected to γ-ray radiation, as described in Japanese Patent No. Publication Kokai No. 2003-887551.
The deodorant composition herein comprises from about 1% to about 40%, or from about 3% to about 15%, or from about 5% to about 10% by weight of a deodorant polymer, if present.
The deodorant composition herein may further comprise adjunct ingredients selected among a perfume, a dye, a stabilizer, a UV absorbent, a preservative and a mixture thereof.
A perfume may further added into the deodorant composition herein at an amount of from about 0.1% to about 5% by weight.
A highly preferred ingredient in the present invention is a UV protector which is used herein to describe a material which absorbs, blocks and/or reflects UV light so as to reduce UV damage. Specifically, polymer molecules in the deodorant composition may degrade and/or break when exposed to light energy. Many light wavelengths, especially in the UV spectrum are known to affect polymer molecules by breaking and/or weakening the internal chemical bonds between monomers. This may cause the shape of the gel deodorant composition herein to become deformed or make the gel appear to be melting over time. In an extreme case, the shape may be destroyed if excessive breaking of molecules occurs because of exposure to light during manufacture, shipping, storage, and/or use.
Useful UV protectors include the UV absorber SEESORB™ 101, available from Shipro Kasei Kaisha (Osaka, Japan), which can be absorbed or otherwise incorporated into the gel. SEESORB™ 101 is a benzophenone based UV absorber. Also useful herein are benzo triazole based UV absorbers such as SEESORB™ 701, also available from Shipro.
Other examples of UV protectors which can be used alone or as a mixture with another UV protectors or with an anti-oxidant include the CYASORB™ UV series from American Cyanamid Co. (Wayne, N.J., USA) and the Tinogard™ TL series from Ciba Specialty Cehmicals Co. (Basel, Switzerland). Such UV protectors may be incorporated into any relevant portion of the product, for example, in to the packaging, into or onto the gel, etc.
Preservatives known in the art may also be useful herein. An example of a preservative is phenoxyethanol.
Anti-oxidants known in the art may also be useful herein to prevent degradation and/or damage to the gelling polymer, perfume, and/or other ingredients in the deodorant composition. While such anti-oxidants are well-known in the art, an example of a preferred anti-oxidant is SEENOX-BCS™ available from Shipro.
The deodorant composition herein has a three-dimensional shape selected from a block shape, a sphere shape, an ellipsoid shape, a cone shape and a cylinder shape, the three-dimensional shape has a surface area of from about 24 mm2 to about 2400 mm2, or from about 150 mm2 to about 600 mm2. As used herein, “block shape” means a polyhedron with no curved surfaces or edges. All sides of a block shape are polygons and all edges of a block shape are line segments. Notwithstanding the above definition, it should be understood that polyhedrons having slightly curved surfaces or edges due to the actual manufacturing capability are not intended to be excluded from the range of block shape herein. Preferably, the deodorant composition herein has a block shape selected from the group consisting of a cube, a cuboid, a parallelepiped and an oblique rectangular prism. By “oblique rectangular prism”, it means a voluminous body having six sides, wherein three pairs of parallel and equally shaped and sized sides exist and wherein one pair of sides are in the shape of a parallelogram and the remaining two pairs of sides are of rectangular shape.
The three-dimensional shape described hereinabove is preferred since a deodorant product for sale and use comprises a plurality of individual bodies of the deodorant composition packed in a package, spaces in-between the individual bodies of the deodorant composition herein facilitate flow of air and allow the air to penetrate into such spaces, thus, contact of the deodorant actives with the malodorous compounds to be removed from the environment is increased. Without intending to be bound by theory, it is believed that where the three-dimensional shape has a surface area of lower than 24 mm2, the individual gel body of the deodorant composition tends to be packed closely in a deodorant product because the gel is soft and in a small size. As a result, flow of air in-between the individual gel bodies is blocked. On the other hand, where the three-dimensional shape has a surface area of larger than 2400 mm2, the total surface area of the deodorant composition per unit amount is decreased due to the large size of a single body. As a result, contact of malodorous compound with the metallic deodorizing agent in a deodorant product is limited.
The gel deodorant composition in the three-dimensional shape herein can be prepared by any known process, such as by mixing all the ingredients and forming a gel deodorant composition, then cutting the gel into a desired shape and size. Preferably, the gel deodorant composition having the three-dimensional shape and surface area described herein is prepared by using a gelling polymer having a preformed three-dimensional shape selected from a block shape, a sphere shape, an ellipsoid shape, a cone shape and a cylinder shape. Specifically, this preferred process comprises steps of preparing a gelling polymer having a preformed 3-dimensional shape; premixing and homogenizing other ingredients of the deodorant composition in a mixer to form a premix; and adding the premix into the gelling polymer and allowing the gelling polymer to adsorb the premix to form a gel deodorant composition, wherein the preformed shape of the gelling polymer is selected from a block shape, a sphere shape, an ellipsoid shape, a cone shape and a cylinder shape, and wherein the weight ratio of the gelling polymer to the premix is from about 1:200 to 1:1, or from about 1:30 to about 1:10. One of the methods for preparing a gelling polymer having a desired three-dimensional shape is suspension polymerization which is described in detail in the book entitled Modem Superabsorbent Polymer Technology, Ed by Fredric L. Bucholz and Andrew T. Graham, published by John Wiley & Sons, Inc., 1998. Gelling polymers having a preformed sphere shape are commercially available as Aquabeads™ from Kuraray (Osaka, Japan).
A plurality of individual bodies of the deodorant composition herein is packed together as a deodorant product for sale and use. Preferably, the deodorant product is provided in a sealed package to prevent the loss of moisture and thus the deformation of the three-dimensional shape of the individual bodies during shipment and storage. Packaging materials providing such function are known in the art.
An air stock with desired concentration of a malodorous compound can be prepared by the following method.
A single cock 25 liter Tedlar™ bag (Shibao Shoten, Osaka, Japan) fitted with an open/close valve through which gas can be injected and released is filled with about 20 to 25 liters of clean air using an air-pump.
Standard malodorous compound, such as hydrogen sulfide or ammonia is fed into the Tedlar bag through the valve. After adding a small volume of a malodorous compound, check the concentration of the compound with Gastec's standard detector tube system comprising a gas tube (Model 4H, 4HM, 4M, 4L, 4LL, 4LK, 4LB, 4LT for hydrogen sulfide and Model 3HM, 3M, 3LA and 3L for ammonia, the appropriate model is selected according to the target concentration of the compound and the instruction in the Gastec Handbook: Environmental Analysis Technology published by Gastec Corporation, March 2003, 4th Edition.) and a gas sampling pump (GV-100 gas sampling pump), supplied by Gastec Corporation (Kanagawa, Japan). Adjust the concentration of the malodorous compound to an appropriate level using the Gastec detector tube, for the bag containing hydrogen sulfide, adjust the concentration of hydrogen sulfide to be 100 ppm, and for the bag containing ammonia, adjust the concentration of ammonia to be 200 ppm. After that, shake the bag well and leave it for 5 minutes and detect the concentration again using the detector to confirm the desired concentration.
Deodorant performance of the deodorant composition herein against a malodorous compound is measured as follows.
A 5 liter Tedlar™ bag is prepared with one corner of the bag being cut. 3.0 grams of a deodorant composition is prepared and put on a small glass Petri dish which is then placed inside the Tedlar bag. After completely pressing the air inside the Tedlar bag out, the cut-opened corner of the bag is sealed completely without any substantial leakage using a heat sealer.
Fill the 5 liter Tedlar™ bag having the deodorant composition sample inside with the air stock comprising a predetermined concentration of a malodorous compound through a connection tube having a valve. After the filling, remove the connection and immediately seal the 5 liter Tedlar™ bag by closing the valve.
Measure the concentration of a malodorous compound after a certain period of time using the standard detector system mentioned above. For the bag comprising hydrogen sulfide, measure the concentration of hydrogen sulfide after 24 hours, for the bag comprising ammonia, measure the concentration of ammonia after 3 hours. Repeat the test three times and take an average of these tests as the deodorant performance.
Examples of the invention are set forth hereinafter by way of illustration and are not intended to be in any way limiting of the invention. The examples are not to be construed as limitations of the present invention since many variations thereof are possible without departing from its spirit and scope.
Prepare 5 grams of a crosslinked sodium salt of polyacrylic acid gelling polymer having a preformed cuboid shape of 4 mm×4 mm×5 mm in a container. Premix ingredients described in Table 1 by stirring and homogenizing with a high-shear mixer to obtain a premix. Add the premix into the container comprising the gelling polymer and allow the gelling polymer to absorb the premix by keeping the mixture overnight. A deodorant composition having a cuboid shape and a surface area of 600 mm2 to 680 mm2 is then obtained. The deodorant composition has a light blue color.
Deodorant performance of the deodorant composition prepared in Examples 1-3 is measured by the test method described hereinabove. The initial concentration of hydrogen sulfide is 100 ppm and concentration of the hydrogen sulfide after 24 hours is measured and recorded in the below Table 2. The initial concentration of ammonia is 200 ppm and the concentration of ammonia after 3 hours is measured and recorded in the below Table 3.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
This application claims the benefit of U.S. Provisional Application No. 60/818,924, filed Jul. 6, 2006.
| Number | Date | Country | |
|---|---|---|---|
| 60818924 | Jul 2006 | US |
