The present invention relates to skin care compositions and, in particular, pigmented skin care compositions that are useful in improving the visible appearance of skin.
A variety of products are available to consumers to aid in improving skin appearance, and in particular minimizing the visibility of discontinuities in skin appearance. One way to accomplish this is through the use of compositions including colored pigments. For example, cosmetic foundations (either in powdered or lotion form) contain colored pigments that are intended to mimic the skin's natural color. A problem with foundations of this type is that if such foundations are applied in a localized manner (e.g. only in a selected area of redness) the difference between the foundation color and the surrounding natural skin color may be readily apparent resulting in an irregular skin appearance. Alternatively, if such foundations are applied in a continuous manner over a larger area of skin, to thereby provide a more uniform skin appearance, an artificial “mask-like” appearance may result. It is further noted that in order to effectively conceal skin discontinuities, foundations of the type described above require relatively high pigment contents, which further contributes to the undesirable “mask-like” qualities of such compositions.
Certain colored lotions known in the art are specifically intended to reduce “redness”, that is reduce the red appearance of certain skin discontinuities. These redness reduction lotions typically rely upon classic pigments or dyes that appear green (the complementary color of red) to thereby deliver the redness reduction effect. The problem with such redness reduction lotions is that they can impart an unnatural green color to the healthy skin surrounding the skin discontinuity.
Efforts have been made to overcome the shortcomings of the products described above by way of personal care compositions that utilize interference pigments, in lieu of conventional pigments. Interference pigments typically are thin plate-like, colorless, particles including two or more layers. The layers of the interference pigment have different refractive indices, and reflect a color resulting from the constructive or destructive interference of reflections of light from the different layers.
A specific skin care composition including interference pigments is disclosed in US Patent Publication 2007065381A to Elsbrock, et al. Elsbrock discloses a skin care composition that includes a first pigment that reflects a first color and a second pigment that reflects a second complementary color.
The inventors of the present invention have discovered that one drawback of the composition disclosed in Elsbrock et al. is that a formulator making a composition in accordance with the teachings of Elsbrock et al. is limited in the selection of interference pigments that may be employed. Specifically, since the composition of Elsbrock et al. requires the use of a combination of a first and second pigment that reflect complementary colors, a formulator is thus limited in the selection of interference pigments that may be employed. In addition, the inventors of the present invention have discovered that if redness reduction is desired, using a composition of the type disclosed in Elsbrock et al., may require the use of relatively high total pigment concentrations. Finally, the inventors of the present invention have discovered that since the composition of Elsbrock et al. requires the use of a combination of a first and a second pigment that are complementary colors, if the chroma of the composition is to be minimized the first and second pigments must be employed in a 1:1 ratio or substantially similar ratio.
In view of the above, the inventors have recognized that further improvements in skin care compositions including interference pigments are required. More specifically, the inventors of the present invention have recognized the need for compositions that minimize the red appearance of certain skin discontinuities with minimal impact on the appearance of the healthy skin surrounding the skin discontinuity. The inventors of present invention have also recognized the need for skin care compositions including interference pigments that can effectively reduce the red appearance of certain skin discontinuities at low total pigment concentrations. Finally, the inventors of the present invention have recognized the need for skin care compositions including at least a first and second interference pigment that have a relatively low chroma over a wide range of first and second pigment ratios.
In view the of the foregoing, the present invention provides a skin care composition including a dermatologically acceptable carrier, at least a first and a second interference pigment, wherein the composition has a redness reduction index (RRI) of less than −9.5, and wherein the composition has a healthy skin color change value (HSCCV) of less than 3.
All percentages listed in the specification are percentages by weight, unless otherwise specifically mentioned.
As used herein, the term “skin care” means the treatment of the human body, in certain embodiments preferably topical treatment, including, but not limited to application of composition to mammalian skin to improve the appearance of the skin, including the self-perception of one's skin. While the term “skin,” is meant broadly, to include all keratinacious parts of the body (including hair and nails), in certain preferred embodiments “skin” is meant to be exclusive of hair and nails.
The present inventors have surprisingly found that it is possible to minimize the visibility of discontinuities in mammalian skin and improve the overall skin appearance by using skin care compositions according to the present invention. Skin care compositions according to the present invention include at least a first and second interference pigment. Skin care compositions according to the present invention may optionally include more than two interference pigments.
Herein, “minimize the appearance of visible discontinuities in mammalian skin” means improving the appearance of mammalian skin such that positive change in skin appearance after topically applying the composition of the present invention to the skin is observed at a distance of two feet from the user, relative to the appearance of the skin prior to application of the composition. “Visible discontinuities” include, but are not limited to, discoloration due to hyper-pigmentation, age spots, freckles, acne, scar tissue, wound, abrasion, under-eye circles, and uneven skin tone.
Applicants have also surprisingly found that it is possible to reduce the red appearance of certain skin discontinuities with minimal impact on the appearance of the healthy skin surrounding said skin discontinuity by using skin care compositions according to the present invention.
The compositions of the present invention include “interference pigments.” Interference pigments typically are thin plate-like, colorless, particles including two or more layers. The layers of the interference pigment have different refractive indices, and reflect a color resulting from the constructive or destructive interference of reflections of light from the different layers. Certain interference pigments that are useful in the present invention are those that are formed from mica or borosilicate flakes coated with thin films of TiO2 or Fe2O3.
Interference pigments suitable for use in compositions of the present invention have a particle size range wherein fifty percent of the particles fall within the size range (D50) of about 2 μm and about 75 μm. Particle size may be determined using a Malvern Mastersizer S particle size analyzer, commercially available from Malvern Instruments Ltd., Worcestershire, United Kingdom. When the term “particle size” is used herein this term is meant to refer to the D50 particle size.
Commercially available interference pigments suitable for use in the present invention are available from BASF Corporation, Florham Park, N.J. (select pigments from those sold under the Flamenco®, Lumina® and Reflecks® tradenames), from Impact Colors, Inc., Newark, Del. (select pigments from those sold under the Gemini™ tradename), and from Kobo Products, Inc., South Plainfield, N.J. (select pigments from those sold under the KTZ™ tradename).
In certain embodiments of the present invention, the composition includes at least a first and second interference pigment wherein the first interference pigment has a hue angle (h°) between 180°-224° and wherein the second interference pigment has a hue angle (h°) between 45°-135°. In certain embodiments of the present invention the second interference pigment has a hue angle (h°) between 80°-95°. Hue angle (h°) was measured using an X-Rite MA98 Multi-Angle Spectrophotometer, commercially available from X-Rite, Inc., Grand Rapids, Mich. To determine the hue angle (h°) of each of the pigments used in the inventive compositions described in detail herein, a 3% pigment in lacquer (clear nail lacquer Sally Hansen, Hard as Nails, Nail Color 4860-01 Invisible, commercially available from Coty, Inc., New York, N.Y.) suspension was formulated. The suspension was drawn down onto the black portion of a Laneta Test Opacity Chart 2A, using an Elcometer 4340 Motorized Applicator machine (the Elcometer 4340 is commercially available from Elcometer Ltd of Manchester, UK; Leneta test charts are commercially available from The Leneta Company, Mahwah, N.J.). The drawdown was performed onto the test card at a speed setting of 1 with the bird applicator, resulting in a 8 mil application in a 3″ wide area. After coating the test card, the card was then allowed to dry overnight prior to taking measurements. Measurements were taken of the test card using the 45as15 and 45as45 settings on the X-Rite MA98 Multi-Angle Spectrophotometer to measure the hue angle (h°).
In order for a pigment to be useful in compositions according to the present invention, and therefore considered within the scope of the present invention, the measured hue angle (h°) at both settings must fall within the specified range of between 180°-224° for the first interference pigment or between 45°-135° for the second interference pigment. In certain embodiments of the invention the second interference has a hue angle (h°) between 80°-95°. If the measured hue angle (h°) for a pigment is outside the specified range at either setting (i.e. at 45as15 and 45as45) then the pigment is considered outside the scope of the present invention.
Herein, “chroma,” describes color and color intensity. For the purposes of the present invention, color is defined according to a value on the CIELAB color system, which is based on the XYZ color system, defined by the Commission Internationale de l'Eclairage (CIE system) to provide a manner of objectively representing perceived color and color differences. X, Y and Z can be expressed in a variety of manners, or “scales,” one of which is the Hunter scale. The Hunter scale has three variables, L, a, and b, which correlate mathematically to X, Y and Z, and is described by Robertson, A. R. in “The nCIE 1976 Color Difference Formulas,” Color Research Applications, vol. 2, pp. 7-11 (1977). The compositions of the present invention may be analyzed with a Konica Minolta CR-400 Chroma Meter (commercially available from Konica Minolta Sensing Americas, Inc., Ramsey, N.J.), which generates values for L, a, and b. The value for “a” correlates to a value along the red-green (horizontal) axis, and the value for “b” correlates to a value along the blue-yellow (vertical) axis. For example, a blue-colored sample will have a negative b-value, whereas a red-colored sample will have a positive a-value. A more positive or negative value represents a more intense color. The value for “L” is an indicator of lightness and/or darkness, and correlates to a value along the z-axis, which is perpendicular to both the horizontal and vertical axes. “Chroma” is measured by a vector having its origin at the intersection of the red-green and blue-yellow axes and extending outward into the color space defined by the horizontal and vertical axes of the CIELAB color system. The length of the vector represents the chroma, and the direction of the vector represents the shade, or hue. The shorter the vector, the less colored is the composition, and the lower the chroma.
The inventors of the present invention have discovered that skin care compositions of the present invention can be effectively employed to reduce the red appearance of skin discontinuities with minimal impact on the appearance of the surrounding healthy skin. As noted above, skin care compositions according to the present invention include at least a first and second interference pigment. Surprisingly, the inventors of the present invention have discovered that the redness reduction benefit can be delivered by way of the skin care compositions of the present invention over a relatively wide range of first and second interference pigment ratios. In particular, in certain embodiments, skin care compositions of the present invention can deliver the redness reduction benefit over a first interference pigment to second interference pigment ratio range between 20:80 and 80:20.
The inventors of the present invention have discovered that the interference pigments used in the inventive compositions have unique properties when used in combination. Specifically, the interference pigments of certain embodiments of the present invention when used in combination provide a relatively low chroma over a wide range of pigment ratios. In particular, in certain embodiments of the invention, the first and second interference pigments may be employed over the entire 20:80 to 80:20 ratio range and all of such compositions will have a chroma of less than 8.5 when formulated using a substantially colorless carrier of the type described in Table 4 herein. Accordingly, when the language “wherein chroma of said composition over the entire range is less than 8.5” is used herein it means that when a plurality of different compositions are formulated using the first and second interference pigments employed in the inventive composition, and a substantially colorless carrier of the type set for in Table 4, all of such compositions will have a chroma less than 8.5. For example, if a plurality of compositions are formulated using first and second interference pigments according to certain embodiments and the carrier set forth in Table 4 at the pigment ratios of 20:80; 30:70; 40:60; 50:50; 60:40; 70:30; and 80:20 all of such compositions will have a chroma of less than 8.5. The above properties provide the formulator significantly more flexibility than the compositions disclosed in the prior art in that the formulator can provide a relatively low chroma composition over a wide range of first to second pigment ratios.
The inventors of the present invention have discovered that skin care compositions of the present invention can be effectively employed to reduce the red appearance of certain skin discontinuities with minimal impact on the appearance of the surrounding healthy skin. Surprisingly, the inventors of the present invention have discovered that this benefit can be delivered by way skin care compositions according to the present invention having relatively low total pigment concentrations. In particular, the compositions of the present invention may comprise a total amount of interference pigments of from 0.1% to 5% by weight, and in certain embodiments from 1.0% to 4%.
The inventors of the present invention have discovered that skin care compositions of the present invention can be effectively employed to reduce the red appearance of certain skin discontinuities with minimal impact on the appearance of the surrounding healthy skin. Surprisingly, the inventors of the present invention have discovered that this benefit can be delivered despite the skin care compositions not having a chroma that approaches zero. In particular, compositions according to certain embodiments of the present invention have a chroma greater than 3.5, and certain embodiments between 4.0 and 15.0.
Compositions of the present invention include a carrier useful for delivering the pigment to the human body. In certain embodiments the composition includes a cosmetically-acceptable carrier that is useful for distributing the pigment evenly across an expanse of skin. As used herein, the term “cosmetically-acceptable carrier” means a carrier that is suitable for use in contact with the skin without undue toxicity, incompatibility, instability, irritation, allergic response, and the like. This term is not intended to limit the carrier for use solely as a cosmetic (e.g., the ingredient/product can be used as a pharmaceutical).
The cosmetically-acceptable topical carrier generally includes one or more of the following fluids: water, hydrophobic compounds (e.g., hydrocarbons suitable for use in cosmetic products, such as those having carbon chains from about C6 to about C50, more preferably from about C8 to about C22, such as oils, fatty esters, fatty alcohols, fatty esters; as well as silicone fluids/oils) such as ones suitable to provide emolliency, spreadability, or phase stability; glycols such as ones suitable to provide humectancy such as glycerol, or diols such as propylene glycol or butylene glycol; or lower alcohols such as those suitable to provide solvency or spreadability such as ethanol or isopropanol.
In certain embodiments the carrier may include one or more solid, semi-solid, paste-like, or powder materials useful in helping to distribute the pigment across the skin. Examples include hydrophobic compounds, including waxes and other hydrophobic compounds that melt above ambient temperature; powders such as starch, talc, corn starch and the like.
In a preferred embodiment, the embodiment, the cosmetically acceptable topical carrier is present in a concentration that is from about 20% to about 99.9%, preferably form about 50% to about 99.8%, more preferably from about 75% to about 99.5%. In another embodiment, the cosmetically-acceptable topical carrier includes a substrate useful for wiping the composition onto the skin. In yet another embodiment, the cosmetically-acceptable topical carrier includes a bandage for applying the composition to the skin and/or maintaining the composition in contact with the skin.
Preferably the cosmetically acceptable topical carrier is substantially colorless. That is, the carrier does not impart any substantial color to the overall composition independent of the interference pigments employed in the composition. A suitable substantially colorless carrier is disclosed in the Table 4 although other substantially colorless carriers will be readily apparent to those of skill in the art.
The interference pigments may be distributed into the composition via techniques known to those skilled in the art. For example, the pigment may be suspended or dispersed into an oil phase and/or a water phase that is present in the composition. In order to facilitate distribution of the pigment within the composition, the composition may include a stabilizing agent (e.g., a rheology modifier, a thickening agent, a dispersing agent, or similar materials). Any of a variety of commercially available stabilizing agents which are capable of imparting the appropriate viscosity to the compositions are suitable for use in this invention. If used, the thickener may, for example, be present in an amount sufficient to raise the Brookfield viscosity of the composition to a value of between about 500 to about 10,000 centipoise. Examples of suitable thickening agents nonexclusively include: crosslinked polyacrylic acids (e.g., CARBOPOL ULTREZ 10 from Noveon, Inc. of Cleveland, Ohio); mono or diesters of 1) polyethylene glycol of formula: HO—(CH2CH2O)zH, wherein z is an integer from about 3 to about 200; and 2) fatty acids containing from about 16 to about 22 carbon atoms; fatty acid esters of ethoxylated polyols; ethoxylated derivatives of mono and diesters of fatty acids and glycerine; hydroxyalkyl cellulose; alkyl cellulose; hydroxyalkyl alkyl cellulose; hydrophobically-modified alkali swellable emulsions (HASEs); hydrophobically-modified ethoxylated urethanes (HEURs); xanthan and guar gums; and mixtures thereof.
The composition may include any of various surfactants, wetting agents, or emulsifiers commonly used in personal care formulations. These materials may be ionic, non-ionic, as may be selected for their ability to provide wetting, emulsification, low irritation, foam (or lack thereof), or other desired properties. Examples of suitable surfactants, wetting agents, or emulsifiers include anionics such as surfactants include those selected from the following classes of surfactants: alkyl sulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates, alkyl carboxylates, alkyl amidoethercarboxylates, alkyl succinates, fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates, fatty alkyl sulfoacetates, alkyl phosphates; nonionic surfactants such as polyoxyethylene derivatives of polyol esters, wherein the polyoxyethylene derivative of polyol ester (1) is derived from (a) a fatty acid containing from about 8 to about 22, and preferably from about 10 to about 14 carbon atoms, and (b) a polyol selected from sorbitol, sorbitan, glucose, α-methyl glucoside, polyglucose having an average of about 1 to about 3 glucose residues per molecule, glycerine, pentaerythritol and mixtures thereof, (2) contains an average of from about 10 to about 120, and preferably about 20 to about 80 oxyethylene units; and (3) has an average of about 1 to about 3 fatty acid residues per mole of polyoxyethylene derivative of polyol ester; amphoterics such as amphocarboxylates such as alkylamphoacetates (mono or di); alkyl betaines; amidoalkyl betaines; amidoalkyl sultaines; amphophosphates; phosphorylated imidazolines such as phosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines; alkylimino-dipropionates; alkylamphoglycinates (mono or di); alkylamphoproprionates (mono or di); N-alkyl β-aminoproprionic acids; alkylpolyamino carboxylates; and cationics such as alkyl quaternaries (mono, di, or tri), benzyl quaternaries, ester quaternaries, ethoxylated quaternaries, alkyl amines.
The compositions may include any of various other functional ingredients such as chelating agents (e.g., EDTA); pH adjusters (citric acid, sodium hydroxides, and the like); preservatives; and the like.
Furthermore, compositions of the present invention may also include a skin benefit agent. A skin benefit agent is any element, an ion, a compound (e.g., a synthetic compound or a compound isolated from a natural source) or other chemical moiety in solid (e.g. particulate), liquid, or gaseous state and compound that has a cosmetic or therapeutic effect on the skin. As used herein, the term “benefit agent” includes any active ingredient such as a cosmetic or pharmaceutical, that is to be delivered into and/or onto the skin, hair, mucosa, or teeth at a desired location.
Examples of suitable benefit agents include those that provide benefits such as, but not limited to: de-pigmentation agents; amino acids and their derivatives; antimicrobial agents; allergy inhibitors; anti-acne agents; anti-aging agents including anti-wrinkling agents and benefit agents suitable for treating loss of skin elasticity, uneven skin, blotchiness, and skin tone; tropoelasin promoters and tropoelastin crosslinkers; antiseptics; analgesics; antipruritics; local anesthetics; anti-hair loss agents; hair growth promoting agents; hair growth inhibitor agents, antihistamines; antiinfectives; anti-inflammatory agents; anticholinergics; vasoconstrictors; vasodilators; wound healing promoters; peptides, polypeptides and proteins; deodorants and anti-perspirants; medicament agents; skin firming agents, vitamins; skin lightening agents; skin darkening agents; antifungals; depilating agents; counterirritants; enzymes for exfoliation or other functional benefits; enzyme inhibitors; NFκB-inhibitors; herbal extracts; flavenoids; sensates and stress-reducing agents; anti-oxidants; hair lighteners; sunscreens; anti-edema agents, neo-collagen enhancers, anti-dandruff/sebhorreic dermatitis/psoriasis agents; keratolytics; and mixtures thereof.
Particularly suitable benefit agents include depigmentation agents and skin-lightening agents such as hydroquinone and extracts of soy; keratolytic agents and/or anti-acne agents such as alpha and beta hydroxyacids such as salicylic acid; anti-aging actives such as retinoids including retinol, amines such as N,N,N′,N′-Tetrakis(2-hydroxypropyl)ethylenediamine (THPED), N,N,N′,N′-Tetrakis(2-hydroxyethyl)ethylene diamine (THEED), N,N,N′,N′-tetramethylethylene diamine (TEMED), substituted resorcinols such as 4-hexyl resorcinol, anti-inflammatories such as extracts of feverfew, tropoelastin promoters such as extracts of blackberry, tropoelastin crosslinkers such as extracts of dill, among other skin benefit agents.
The amount of the benefit agent that may be used may vary depending upon, for example, the ability of the benefit agent to penetrate through the skin, nail, mucosa, or teeth; the specific benefit agent chosen, the particular benefit desired, the sensitivity of the user to the benefit agent, the health condition, age, and skin and/or nail condition of the user, and the like. In sum, the benefit agent is used in a “safe and effective amount,” which is an amount that is high enough to deliver a desired skin or nail benefit or to modify a certain condition to be treated, but is low enough to avoid serious side effects, at a reasonable risk to benefit ratio within the scope of sound medical judgment.
The compositions may be made into a wide variety of product types that include but are not limited to cleansing liquid washes, gels, sticks, sprays, solid bars, shampoos, pastes, foams, powders, mousses, wipes, patches, hydrogels, and films. These product types may comprise several types of cosmetically-acceptable carriers including, but not limited to solutions, emulsions (including for example, oil-in-water, water-in-oil, microemulsions and nanoemulsions, and the like), gels, and solids. The following are non-limitative examples of such carriers. Other carriers can be formulated by those of ordinary skill in the art.
The compositions useful in the present invention can be formulated as solutions. Solutions typically include an aqueous or organic solvent (e.g., from about 50% to about 99.99% or from about 90% to about 99% of a cosmetically acceptable aqueous or organic solvent). Examples of suitable organic solvents include: polyglycerols, propylene glycol, polyethylene glycol (200, 600), polypropylene glycol (425, 2025), glycerol, 1,2,4-butanetriol, sorbitol esters, 1,2,6-hexanetriol, ethanol, and mixtures thereof. In certain preferred embodiments, the compositions of the present invention are aqueous solutions comprising from about 50% to about 99% by weight of water.
According to certain embodiments, compositions useful in the subject invention may be formulated as a solution comprising an emollient. Such compositions preferably contain from about 2% to about 50% of an emollient(s). As used herein, “emollients” refer to materials used for the prevention or relief of dryness, as well as for the protection of the skin. A wide variety of suitable emollients are known and may be used herein. Sagarin, Cosmetics, Science and Technology, 2nd Edition, Vol. 1, pp. 32 43 (1972) and the International Cosmetic Ingredient Dictionary and Handbook, eds. Wenninger and McEwen, pp. 1656 61, 1626, and 1654 55 (The Cosmetic, Toiletry, and Fragrance Assoc., Washington, D.C., 7.sup.th Edition, 1997) (hereinafter “ICI Handbook”) contains numerous examples of suitable materials. A lotion can be made from such a solution. Lotions typically comprise from about 1% to about 20% (e.g., from about 5% to about 10%) of an emollient(s) and from about 50% to about 90% (e.g., from about 60% to about 80%) of water.
The present compositions may be of varying phase compositions, including those having an exterior aqueous phase (e.g., aqueous phase is the most exterior phase of the composition). As such, compositions of the present invention may be formulated to be oil-in-water emulsions that are shelf-stable in that the emulsion does not lose phase stability or “break” when kept at standard conditions (22 degrees Celsius, 50% relative humidity) for a week or more after it is made.
For those compositions that include an aqueous phase, the pH of the present compositions is not critical, but may be in a range that does not facilitate irritation to the skin, such as from about 4 to about 7. The viscosity of the personal care composition is not critical, although it may be a spreadable cream or lotion or gel.
The pigment, carrier and optional other components of the composition may be combined according to the present invention via any conventional methods of combining two or more fluids or solids. For example, one or more compositions comprising, consisting essentially of, or consisting of at least one pigment and one or more compositions comprising, consisting essentially of, or consisting of water or suitable ingredients may be combined by pouring, mixing, adding dropwise, pipetting, pumping, and the like, one of the compositions comprising the polymerized surfactant into or with the other in any order using any conventional equipment such as a mechanically stirred propeller, paddle, and the like.
In certain embodiments, the composition may be impregnated within a substrate (e.g., non-woven fibrous material, a film material, or combinations thereof). The substrate material may be selected to facilitate depositing the pigment on the skin.
The methods of the present invention may further comprise any of a variety of steps for mixing or introducing one or more of the optional components described hereinabove with or into a composition comprising the pigment, either before, after, or simultaneously with the combining step described above.
In certain embodiments, the compositions produced via the present invention are preferably used as or in personal care products for treating at least a portion of a mammalian body, for example, the human body. Examples of certain preferred personal care products include various products suitable for application to the skin or hair. Particularly preferred products are those that are designed to be applied to the skin and not immediately rinsed off. Examples of these “leave-on” products particularly for use on the face, but also including those for the body, hands, feet, and the like.
As discussed above, the inventors of the present invention have surprisingly found that it is possible to reduce the red appearance of skin discontinuities with minimal impact on the appearance of the healthy skin surrounding said skin discontinuity by using skin care compositions according to the present invention. The Redness Reduction Index (RRI) Test set forth in detail below was used to illustrate the inventive skin care compositions ability to reduce the red appearance of skin discontinuities. The Healthy Skin Color Change Value (HSCCV) Test set forth in detail below was used to illustrate inventive skin care compositions ability to deliver redness reduction with minimal impact on the appearance of the healthy skin surrounding the skin discontinuity. The inventors of the present invention have further discovered that in order for a skin care composition to preserve the natural tone of healthy skin it cannot impart a “green” tone to the healthy skin. Furthermore, any such green tone must not be visible when the skin is viewed from multiple angles since the human eye simultaneously views a surface from multiple angles. The Multi-Angle Δa* (MADA) Test set forth below was used to illustrate the inventive skin care compositions ability to preserve the natural tone of healthy skin without imparting a “green” tone thereto when the skin is viewed from multiple angles.
Redness Reduction Index (RRI) Test
A test card including a first portion that is representative of a healthy Caucasian skin color and a second portion that is representative of an inflamed skin discontinuity was prepared as follows. The test card had dimensions of 4″×6″ and was formed from Olympus P100 photo paper. The photo paper was printed using an Olympus P-10 printer which was loaded with the bundled ink ribbon. The first and second portions, each measuring 1.3″×6″, were created by entering the RGB values, set forth in Table 1 below, into MATLAB R2011a software (commercially available from Mathworks, Inc., Natick, Mass.) and then printing the test card.
A mimic stratum corneum overlay was prepared as follows. A stratum corneum mimic layer formed from VITRO-CORNEUM® (commercially available from IMS, Inc., Portland, Me.) was attached in a non-hydrated state to a cellulose acetate slide measuring 5″×7″ (PP2500 Transparency Film for Plain Paper Copiers, commercially available from 3M, St. Paul, Minn.) using collagen glue (Resine ou Pigment Pur, concentration 8% in water, commercially available from Sennlier, Paris, France) such that it covered the entire slide, with the rough surface of the VITRO-CORNEUM® facing outward. After setting, the prepared substrate was cut into strips measuring 1.5 cm×6.0 cm, each strip constituting one mimic stratum corneum overlay.
After printing of the test card, the color of the test card was assessed using a Hunter UltraMax Colorimeter (commercially available from Hunter Associates Laboratory, Inc., Reston, Va.), both with and without the mimic stratum corneum overlay. The readings for the test card alone are set forth in Table 2 below and the readings for the test card measured through the mimic stratum corneum overlay (i.e. with the stratum corneum overlay on top of the test card, with the VITRO-CORNEUM® surface facing towards the measurement device) are set forth in Table 3 below.
The pigmented skin care composition to be assessed was finger applied on the mimic stratum corneum overlay in an amount of 2.5 mg/cm2 and smoothed until a consistent layer was attained and then allowed to dry at room temperature overnight. To assess the pigmented skin care composition's impact on the inflamed and healthy skin color targets, the treated mimic stratum corneum overlay was placed over the two color targets on the test card and using a Hunter UltraMax colorimeter, L*, a* and b* values were measured over both portions of the test card, that is separate L*, a* and b* measurements were conducted over the “Healthy Skin” portion of the test card through the treated mimic stratum corneum overlay and separately over the “Inflamed Skin” portion of the test card through the treated mimic stratum corneum overlay.
Using the measured values for a* over the “Inflamed Skin” portion, and the original a* value of the test card over the “Inflamed Skin” portion of the test card set forth in Table 3 above, Δa* was calculated according to the equation Δa*=a*2−a*1, where a*2 is the a* value measured through the treated mimic stratum corneum overlay over the “Inflamed Skin” portion of the test card and a*1 is the original a* value set forth in Table 3 above for the “Inflamed Skin” portion of the test card measured through the non-treated mimic stratum corneum overlay. This measured value of Δa* indicates the ability of the test composition to reduce the “red” appearance of a skin discontinuity, the more “negative” the Δa* value the greater the redness reduction capabilities of the test composition.
The above described test was repeated four (n=4) times for each test composition. An average was taken of each of the four calculated Δa* values to provide an average Δa* value. This average Δa* is referred to herein as the Redness Reduction Index (RRI).
Compositions according to the present invention have a redness reduction index (RRI) of less than −7, in some embodiments less than −7.5, in some embodiments less than −9.5, in some embodiments between −7.5 and −16.0, and in some embodiments between −10.0 and −16.0.
Healthy Skin Color Change Value (HSCCV) Test
Using the values for L*, a* and b* measured through the treated mimic stratum corneum overlay over the “Healthy Skin” portion of the test card, and the original L*, a* and b* values of the “Healthy Skin” of the test card measured through the non-treated mimic over the “Healthy Skin” portion of the test card (set forth in Table 3 above), the ΔE of the “Healthy Skin” portion of the test card was determined according to the formula set forth below.
ΔE=√((L*2−L*1)2+(a*2−a*1)2+(b*2+b*1)); where
The calculated ΔE value indicates the degree to which the test composition changed the appearance of healthy skin, the smaller the ΔE value the less the test composition altered the appearance of healthy skin.
The above described test was repeated four (n=4) times for each test composition. An average was taken of each of the four calculated ΔE values to provide an average ΔE value. This average ΔE is referred to herein as the Healthy Skin Color Change Value (HSCCV). Compositions according to the present invention have an HSCCV of less than 3 and in certain embodiments between 0 and 2.5. In this regard, it is noted that the human eye can barely detect a ΔE≈2.3. (Gaurav Sharma (2003). Digital Color Imaging Handbook (1.7.2 ed.). CRC Press. ISBN 0-8493-0900-X)
Compositions of the present invention simultaneously provide a negative RRI and a small HSCCV. The combination of a negative RRI and a small HSCCV indicates that the inventive compositions are both effective at reducing the red appearance of skin discontinuities while at the same time have minimal impact on the appearance of the surrounding healthy skin.
Chroma Measurement Test
For each of the test compositions tested above, the chroma of such composition was determined as follows.
Three grams (3 g) of the test composition was drawn down onto an AF4300 Write-On Transparency Film (commercially available from 3M, St. Paul, Minn.). The drawdown was conducted by hand using the 6 mil side of a 2-path, 5 inch applicator, part #663479, Precision Gage and Tools Co., Dayton, Ohio. After coating the transparency was allowed to dry overnight prior to taking measurements. After drying, the transparency was placed over the black portion of Laneta Test Opacity Chart 2A (commercially available from The Leneta Company, Mahwah, N.J.).
Using a Konica Minolta CR-400 Chroma Meter (commercially available from Konica Minolta Sensing Americas, Inc., Ramsey, N.J.), L*, a* and b* values were measured over the black portion of the test card. Using these values, chroma for the test composition was calculated according to the following equation.
Chroma=√(a*2+b*2)
The above described test was repeated three (n=3) times for each test composition. An average Chroma value was taken from the four calculated Chroma values to provide an average Chroma value. Compositions according to certain embodiments of the present invention have an average chroma greater than 3.5, and in certain embodiments between 4.0 and 15.0.
Multi-Angle Δa*Test (MADA)
For each of the test compositions tested above, the MADA of such composition was determined as follows. Using the same test card and mimic stratum corneum overlay described above in the Redness Reduction Index (RRI) Test, an a* reading was measured for the Healthy Skin portion of the test card through the mimic stratum corneum overlay using an X-Rite MA98 Multi-Angle Spectrophotometer, commercially available from X-Rite, Inc., Grand Rapids, Mich. It is noted that for purposes of the MADA test the mimic stratum corneum was cut to have dimensions of 3.81 cm×3.81 cm. The a* reading was measured at eight different angles and each of these values was averaged to provide an average a* reading for the Healthy Skin portion of the test card through the mimic stratum corneum overlay. The eight different angles comprised the following angle settings on the test apparatus 45 as-15, 45as15, 45as25, 45as45, 45as75, 45as110, 15 as-15, and 15as15.
The pigmented skin care composition to be assessed was finger applied on the mimic stratum corneum overlay in an amount of 2.5 mg/cm2 and smoothed until a consistent layer was attained and then allowed to dry at room temperature overnight.
An a* reading was measured for the Healthy Skin portion of the test card through the test composition. The a* reading was measured at eight different angles and each of these values was averaged to provide an average a* reading for the Healthy Skin portion of the test card measured through test composition. The eight different angles comprised the following angle settings on the test apparatus 45 as-15, 45as15, 45as25, 45as45, 45as75, 45as110, 15 as-15, and 15as15.
Using the measured a* values an average Δa* value, or MADA value, was calculated according to the following formula:
Δa*=a*2−a*1; where
The above described test was repeated four (n=4) times for each test composition. An average MADA value was taken from the four calculated MADA values to provide an average MADA value. Compositions according to the present invention have an average MADA value of greater than −4.0, and in certain embodiments between −3.5 and 0.3.
Pigmented skin care compositions according to the present invention were formulated to include an oil in water cream carrier and the selected interference pigments. The amount of water in the formulation was adjusted according to the amount of pigment employed in the specific inventive example. The base oil in water cream carrier was selected due to its low optical impact to the L*a*b* measurements conducted according to the test methods set forth above herein. The inventive formulations are summarized in Table 4 below. The pigments employed in each inventive formulation are summarized in Table 5 below. The hue angle (h°) as measured at 45as15 and 45as45 is specified for each pigment used in each of the inventive compositions.
In a clean beaker, combine all oil phase ingredients then began agitation and heat to 55-60° C. until the oil phase is homogeneous. In a separate clean beaker, combine water and other water phase ingredients and began agitation and heat to 55-60° C. until the water phase is homogeneous. Add the oil phase to water phase with increased agitation, mixing at a high speed for 8 minutes at 55-60° C. Cool the mixture to 50° C. and then add the Dimethicone. At 40° C., add the Phenonip, and continue mixing until uniform. Continue cooling until a temperature of 30° C. is reached, check the pH and adjust with Sodium Hydroxide solution to a target pH of 5.4 or in a range from 5.2 to 5.7
Disperse the pigment in thirty percent of the deionized water to be contained in the final composition to suspend the particles and mix thoroughly with propeller blade (or spatula depending on batch size) inside a beaker. Combine pigment premix with oil in water cream carrier prepared above in main beaker and mix thoroughly until uniform.
A total of eight commercial skin care products were evaluated using the test methods described above. The eight commercial products evaluated are listed below.
Eucerin Redness Relief Daily Perfecting Lotion
Dermalogica Sheer Tint Redness Relief
Clearasil ULTRA Overnight Face Lotion
Eucerin Redness Relief Soothing Anti-Aging Serum
Neutrogena Oil Free Acne Stress Control
Clinique Redness Solutions Daily Relief Cream
Estee Lauder Idealist Even Skintone Illuminator
Clinique Redness Solutions Urgent Relief Cream
Additional comparative examples were formulated using the oil in water carrier described above in Table 4 in combination with the pigments set forth below in Table 6.
The Inventive Examples and Comparative Examples described above were tested according to the Redness Reduction Index (RRI) Test, Healthy Skin Color Change Value (HSCCV) Test, Chroma Measurement Test and the Multi-Angle Δa* (MADA) Test set forth herein. The results of such test are summarized in the Table of Results set forth below.
While particular embodiments of the present 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 department 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.
Number | Name | Date | Kind |
---|---|---|---|
3692768 | Takata | Sep 1972 | A |
3978207 | Fotiu | Aug 1976 | A |
4456486 | Bernhard | Jun 1984 | A |
4457784 | Bernhard | Jul 1984 | A |
4494993 | Bernhard | Jan 1985 | A |
4552593 | Ostertag | Nov 1985 | A |
4565581 | Bernhard | Jan 1986 | A |
4623396 | Kimura | Nov 1986 | A |
4648908 | Takasuka | Mar 1987 | A |
4710375 | Takasuka | Dec 1987 | A |
4828826 | Franz | May 1989 | A |
4952245 | Iwano | Aug 1990 | A |
5116664 | Kimura | May 1992 | A |
5156678 | Glausch | Oct 1992 | A |
5169442 | Noguchi | Dec 1992 | A |
5302199 | Prengel | Apr 1994 | A |
5326392 | Miller | Jul 1994 | A |
5364467 | Schmid | Nov 1994 | A |
5496543 | Lagrange | Mar 1996 | A |
5607504 | Schmid | Mar 1997 | A |
5618342 | Herget | Apr 1997 | A |
5624486 | Schmid | Apr 1997 | A |
5624487 | Schmidt | Apr 1997 | A |
5624731 | Desjardins | Apr 1997 | A |
5662738 | Schmid | Sep 1997 | A |
5690916 | Kimura | Nov 1997 | A |
5733658 | Schmid | Mar 1998 | A |
5741355 | Yamamoto | Apr 1998 | A |
5753026 | Kuntz | May 1998 | A |
5776497 | Lagrange | Jul 1998 | A |
5807497 | Gailberger | Sep 1998 | A |
5851277 | Muller Rees | Dec 1998 | A |
5958125 | Schmid | Sep 1999 | A |
5972098 | Andes | Oct 1999 | A |
6001373 | Igo Kemenes | Dec 1999 | A |
6113683 | Herren | Sep 2000 | A |
6117435 | Painter | Sep 2000 | A |
6132504 | Kuntz | Oct 2000 | A |
6132873 | Dietz | Oct 2000 | A |
6156115 | Pfaff | Dec 2000 | A |
6187298 | Kurz | Feb 2001 | B1 |
6190445 | Noguchi | Feb 2001 | B1 |
6190648 | Kouzu | Feb 2001 | B1 |
6238471 | Vogt | May 2001 | B1 |
6238472 | Andes | May 2001 | B1 |
6267810 | Pfaff | Jul 2001 | B1 |
6280520 | Andes | Aug 2001 | B1 |
6306409 | Ogawa | Oct 2001 | B1 |
6428773 | Oko | Aug 2002 | B1 |
6451294 | Simon | Sep 2002 | B1 |
6475500 | Vatter | Nov 2002 | B2 |
6485556 | DeLuca, Jr. | Nov 2002 | B1 |
6500251 | Andes | Dec 2002 | B1 |
6508876 | Bernhardt | Jan 2003 | B1 |
6511672 | Tan | Jan 2003 | B2 |
6517628 | Pfaff | Feb 2003 | B1 |
6524598 | Sunkel | Feb 2003 | B2 |
6531221 | Schuhmacher | Mar 2003 | B1 |
6545809 | Phillips | Apr 2003 | B1 |
6579355 | Schmidt | Jun 2003 | B1 |
6596070 | Schmidt | Jul 2003 | B1 |
6599355 | Schmidt | Jul 2003 | B1 |
6630018 | Bauer | Oct 2003 | B2 |
6632275 | Schoen | Oct 2003 | B1 |
6641823 | Piot | Nov 2003 | B2 |
6641874 | Kuntz | Nov 2003 | B2 |
6648957 | Andes | Nov 2003 | B1 |
6656259 | Pfaff | Dec 2003 | B2 |
6663852 | Simon | Dec 2003 | B2 |
6689205 | Brückner | Feb 2004 | B1 |
6692561 | Schoen | Feb 2004 | B1 |
6696049 | Vatter | Feb 2004 | B2 |
6706109 | DeLuca, Jr. | Mar 2004 | B2 |
6719837 | Bertaux | Apr 2004 | B2 |
6719838 | Heider | Apr 2004 | B2 |
6743285 | Anselmann | Jun 2004 | B1 |
6744559 | Phillips | Jun 2004 | B2 |
6747073 | Pfaff | Jun 2004 | B1 |
6749936 | Argoitia | Jun 2004 | B2 |
6751022 | Phillips | Jun 2004 | B2 |
6773499 | Schoen | Aug 2004 | B2 |
6783584 | Takahashi | Aug 2004 | B2 |
6794037 | Zimmermann | Sep 2004 | B2 |
6800125 | Zimmermann | Oct 2004 | B2 |
6821333 | Zimmermann | Nov 2004 | B2 |
6831785 | Phillips | Dec 2004 | B2 |
6833959 | Phillips | Dec 2004 | B2 |
6837925 | Kubo | Jan 2005 | B2 |
6840993 | Schmidt | Jan 2005 | B2 |
6875264 | Zimmermann | Apr 2005 | B2 |
6884289 | Schoen | Apr 2005 | B2 |
6906015 | Shiloach | Jun 2005 | B1 |
7014700 | DeLuca, Jr. | Mar 2006 | B2 |
7045007 | Bagala, Sr. | May 2006 | B2 |
7060126 | Andes | Jun 2006 | B2 |
7077897 | Brueckner | Jul 2006 | B2 |
7169223 | Pfaff | Jan 2007 | B1 |
7202199 | Shiloach | Apr 2007 | B2 |
7226503 | Anselmann | Jun 2007 | B2 |
7241503 | Noguchi | Jul 2007 | B2 |
7255736 | Pfaff | Aug 2007 | B2 |
7264670 | Rüger | Sep 2007 | B2 |
7300510 | Seeger | Nov 2007 | B2 |
7303622 | Loch | Dec 2007 | B2 |
7318861 | Bagala, Sr. | Jan 2008 | B2 |
7326671 | Shiloach | Feb 2008 | B2 |
7344590 | Schmidt | Mar 2008 | B2 |
7365109 | Rathschlag | Apr 2008 | B2 |
7387669 | Mronga | Jun 2008 | B2 |
7396401 | Jungnitz | Jul 2008 | B2 |
7452597 | Bujard | Nov 2008 | B2 |
7455726 | Schoenefeld | Nov 2008 | B2 |
7479323 | Rathschlag | Jan 2009 | B2 |
7485183 | Hochstein | Feb 2009 | B2 |
7517404 | Bujard | Apr 2009 | B2 |
7531184 | Horino | May 2009 | B2 |
7578879 | Huber | Aug 2009 | B2 |
7579079 | Huber | Aug 2009 | B2 |
7604862 | Ambrosius | Oct 2009 | B2 |
7621966 | Brun | Nov 2009 | B2 |
7628998 | Shah | Dec 2009 | B2 |
7682604 | Ogawa | Mar 2010 | B2 |
7691196 | Pfaff | Apr 2010 | B2 |
7708823 | Kniess | May 2010 | B2 |
7745003 | Hennemann | Jun 2010 | B2 |
7767214 | Simon | Aug 2010 | B2 |
7772214 | Vatter | Aug 2010 | B2 |
7780955 | Cassin | Aug 2010 | B2 |
7794740 | Cohen | Sep 2010 | B2 |
7799746 | Patel | Sep 2010 | B2 |
7820150 | Kohlhase | Oct 2010 | B2 |
7828890 | Henglein | Nov 2010 | B2 |
7850775 | Hollman | Dec 2010 | B2 |
7875112 | Huber | Jan 2011 | B2 |
7959727 | Bujard | Jun 2011 | B2 |
7993443 | Fuller | Aug 2011 | B2 |
7993444 | Fuller | Aug 2011 | B2 |
7998266 | Morimitsu | Aug 2011 | B2 |
8007583 | Fuller | Aug 2011 | B2 |
8016934 | Misaki | Sep 2011 | B2 |
8067090 | Domnick | Nov 2011 | B2 |
8083846 | Zimmermann | Dec 2011 | B2 |
8088212 | Bagala, Sr. | Jan 2012 | B2 |
8088214 | Fuller | Jan 2012 | B2 |
8114211 | Handrosch | Feb 2012 | B2 |
8114388 | Simon | Feb 2012 | B2 |
8129021 | Kaupp | Mar 2012 | B2 |
8147853 | Taylor | Apr 2012 | B2 |
8158566 | Wei | Apr 2012 | B2 |
20010001174 | Andes | May 2001 | A1 |
20020018790 | Vatter | Feb 2002 | A1 |
20020018791 | Vatter | Feb 2002 | A1 |
20020033117 | Inoue | Mar 2002 | A1 |
20020064509 | Grimm | May 2002 | A1 |
20020134282 | Ostertag | Sep 2002 | A1 |
20020169244 | Ostertag | Nov 2002 | A1 |
20030017124 | Agostini | Jan 2003 | A1 |
20030017280 | Poetsch | Jan 2003 | A1 |
20030064039 | Kolodziej | Apr 2003 | A1 |
20030075079 | Sommer | Apr 2003 | A1 |
20030091813 | Fuller | May 2003 | A1 |
20030118622 | Ramin | Jun 2003 | A1 |
20030157041 | Dreher | Aug 2003 | A1 |
20030157042 | Collin | Aug 2003 | A1 |
20030209169 | Andes | Nov 2003 | A1 |
20030211058 | Matts | Nov 2003 | A1 |
20040052743 | Schmidt | Mar 2004 | A1 |
20040057915 | Gers Barlag | Mar 2004 | A1 |
20040076650 | Blin | Apr 2004 | A1 |
20040105827 | Grimm | Jun 2004 | A1 |
20040177788 | Rick | Sep 2004 | A1 |
20040191198 | Hochstein | Sep 2004 | A1 |
20040194663 | Li | Oct 2004 | A1 |
20040219116 | Reynders | Nov 2004 | A1 |
20040223991 | Wei | Nov 2004 | A1 |
20040223993 | Clapp | Nov 2004 | A1 |
20040234564 | Blin | Nov 2004 | A1 |
20040234565 | Stella | Nov 2004 | A1 |
20040241118 | Simon | Dec 2004 | A1 |
20040258640 | Simon | Dec 2004 | A1 |
20050001203 | Bertaux | Jan 2005 | A1 |
20050008595 | Duffournier | Jan 2005 | A1 |
20050061205 | Kobayashi | Mar 2005 | A1 |
20050112072 | Wang | May 2005 | A1 |
20050142084 | Ganguly | Jun 2005 | A1 |
20050143269 | Wei | Jun 2005 | A1 |
20050164896 | Dabkowski | Jul 2005 | A1 |
20050175562 | Hadasch | Aug 2005 | A1 |
20050176850 | Schmidt | Aug 2005 | A1 |
20050204958 | Kuebelbeck | Sep 2005 | A1 |
20050220735 | Tsaur | Oct 2005 | A1 |
20050220736 | Polonka | Oct 2005 | A1 |
20050252410 | Bujard | Nov 2005 | A1 |
20050268405 | Brun | Dec 2005 | A1 |
20050273947 | Brun | Dec 2005 | A1 |
20050276768 | Wei | Dec 2005 | A1 |
20050276779 | Blin | Dec 2005 | A1 |
20060005742 | Moeschl | Jan 2006 | A1 |
20060013838 | Peng | Jan 2006 | A1 |
20060027140 | Kniess | Feb 2006 | A1 |
20060032404 | Kniess | Feb 2006 | A1 |
20060034787 | Bujard | Feb 2006 | A1 |
20060047018 | Li | Mar 2006 | A1 |
20060051204 | Lyons | Mar 2006 | A1 |
20060051304 | Peng | Mar 2006 | A1 |
20060088483 | Thevenet | Apr 2006 | A1 |
20060144294 | Misaki | Jul 2006 | A1 |
20060147390 | Schreiber | Jul 2006 | A1 |
20060156949 | Pfaff | Jul 2006 | A1 |
20060159920 | Reynders | Jul 2006 | A1 |
20060225609 | Rueger | Oct 2006 | A1 |
20060241211 | Coughlin | Oct 2006 | A1 |
20060280705 | Bruechert | Dec 2006 | A1 |
20060280706 | Sebillotte Arnaud | Dec 2006 | A1 |
20070028799 | Kniess | Feb 2007 | A1 |
20070048237 | Song | Mar 2007 | A1 |
20070065381 | Elsbrock | Mar 2007 | A1 |
20070077218 | Weinling | Apr 2007 | A1 |
20070134174 | Irwin | Jun 2007 | A1 |
20070134177 | Zimmermann | Jun 2007 | A1 |
20070141001 | Clapp | Jun 2007 | A1 |
20070141002 | Montezinos | Jun 2007 | A1 |
20070166534 | Entenmann | Jul 2007 | A1 |
20070225424 | Schulz | Sep 2007 | A1 |
20070248560 | Livoreil | Oct 2007 | A1 |
20070274938 | Alfano | Nov 2007 | A1 |
20070297996 | Tanner | Dec 2007 | A1 |
20080019933 | Thevenet | Jan 2008 | A1 |
20080038360 | Zukowski | Feb 2008 | A1 |
20080044366 | Dumousseaux | Feb 2008 | A1 |
20080081057 | Chevalier | Apr 2008 | A1 |
20080102269 | Herzing | May 2008 | A1 |
20080105272 | Thevenet | May 2008 | A1 |
20080127429 | Brun | Jun 2008 | A1 |
20080168924 | Melson | Jul 2008 | A1 |
20080181921 | DeLuca | Jul 2008 | A1 |
20080200560 | Kniess | Aug 2008 | A1 |
20080207772 | Kniess | Aug 2008 | A1 |
20080210133 | Roesler | Sep 2008 | A1 |
20080213322 | Birman | Sep 2008 | A1 |
20080226574 | Thevenet | Sep 2008 | A1 |
20080247977 | Le Gendre | Oct 2008 | A1 |
20080249209 | Trummer | Oct 2008 | A1 |
20080279796 | Handrosch | Nov 2008 | A1 |
20080279899 | Geffroy | Nov 2008 | A1 |
20080292567 | Schuster | Nov 2008 | A1 |
20080295737 | Henglein | Dec 2008 | A1 |
20080314284 | Li | Dec 2008 | A1 |
20080319089 | Muller | Dec 2008 | A1 |
20090011035 | Zukowski | Jan 2009 | A1 |
20090013906 | Fischer | Jan 2009 | A1 |
20090028808 | Cetti | Jan 2009 | A1 |
20090028809 | Cetti | Jan 2009 | A1 |
20090030113 | Glockner | Jan 2009 | A1 |
20090035241 | Cassin | Feb 2009 | A1 |
20090041695 | Dumousseaux | Feb 2009 | A1 |
20090053164 | Opper-Linnert | Feb 2009 | A1 |
20090056591 | Schmidt | Mar 2009 | A1 |
20090123403 | Barba | May 2009 | A1 |
20090185992 | Conan | Jul 2009 | A1 |
20090196841 | Song | Aug 2009 | A1 |
20090208436 | Hollman | Aug 2009 | A1 |
20090220557 | Pfaff | Sep 2009 | A1 |
20090246294 | Hochstein | Oct 2009 | A1 |
20090249979 | Kaupp | Oct 2009 | A1 |
20090252695 | Peng | Oct 2009 | A1 |
20090252772 | Henglein | Oct 2009 | A1 |
20090311209 | Bujard | Dec 2009 | A1 |
20100011992 | Bujard | Jan 2010 | A1 |
20100047291 | Hochstein | Feb 2010 | A1 |
20100047300 | Kaupp | Feb 2010 | A1 |
20100089291 | Kang | Apr 2010 | A1 |
20100095868 | Kaupp | Apr 2010 | A1 |
20100104610 | Dueva-Koganov | Apr 2010 | A1 |
20100116169 | Kaupp | May 2010 | A1 |
20100129412 | Kitamura | May 2010 | A1 |
20100136068 | Perier | Jun 2010 | A1 |
20100158830 | Wei | Jun 2010 | A1 |
20100178308 | Iwasa | Jul 2010 | A1 |
20100183535 | Goetz | Jul 2010 | A1 |
20100192802 | Bujard | Aug 2010 | A1 |
20100196296 | Geissler | Aug 2010 | A1 |
20100197805 | Cassin | Aug 2010 | A1 |
20100203093 | Bujard | Aug 2010 | A1 |
20100209464 | Maderazzo | Aug 2010 | A1 |
20100218703 | Bujard | Sep 2010 | A1 |
20100221205 | Blin | Sep 2010 | A1 |
20100297045 | Kaupp | Nov 2010 | A1 |
20100322883 | Gohier | Dec 2010 | A1 |
20100322981 | Bujard | Dec 2010 | A1 |
20110033400 | Ehlis | Feb 2011 | A1 |
20110064779 | Gruener | Mar 2011 | A1 |
20110070273 | Zheng | Mar 2011 | A1 |
20110112234 | Hall-Goulle | May 2011 | A1 |
20110113984 | Fuller, Jr. | May 2011 | A1 |
20110118384 | Bugnon | May 2011 | A1 |
20110212042 | Maitra | Sep 2011 | A1 |
20110223218 | Jones | Sep 2011 | A1 |
20110226161 | Schumacher | Sep 2011 | A1 |
20110236332 | Dop | Sep 2011 | A1 |
20110237683 | Schmid | Sep 2011 | A1 |
20110251293 | Trummer | Oct 2011 | A1 |
20110269845 | Bujard | Nov 2011 | A1 |
20110298207 | Despland | Dec 2011 | A1 |
20110306678 | Liu | Dec 2011 | A1 |
20120027862 | Schmidt | Feb 2012 | A1 |
20120039833 | Brennan | Feb 2012 | A1 |
20120091702 | Shimizu | Apr 2012 | A1 |
Number | Date | Country |
---|---|---|
959109 | Feb 1977 | EP |
95889 | Sep 1984 | EP |
246523 | Jan 1991 | EP |
307747 | May 1992 | EP |
381047 | Aug 1994 | EP |
555325 | Nov 1994 | EP |
562329 | Jul 1995 | EP |
580022 | Jan 1996 | EP |
632110 | Sep 1996 | EP |
655486 | Aug 1997 | EP |
686674 | Jan 1998 | EP |
686675 | Feb 1998 | EP |
736073 | Mar 1998 | EP |
690105 | Sep 1998 | EP |
804512 | Jan 1999 | EP |
616626 | Nov 1999 | EP |
741170 | Dec 1999 | EP |
579091 | Jan 2000 | EP |
768343 | Feb 2001 | EP |
763573 | Jul 2001 | EP |
848044 | May 2002 | EP |
1063959 | Nov 2002 | EP |
1017755 | Jan 2003 | EP |
940451 | Feb 2003 | EP |
1038941 | May 2003 | EP |
948571 | Jun 2003 | EP |
1165698 | Jul 2003 | EP |
1230309 | Sep 2003 | EP |
1078975 | Oct 2003 | EP |
1009776 | Dec 2003 | EP |
1078974 | Mar 2004 | EP |
919599 | Sep 2004 | EP |
1479730 | Nov 2004 | EP |
1479731 | Nov 2004 | EP |
1155097 | Jan 2005 | EP |
1235882 | Jan 2005 | EP |
1299079 | Jun 2005 | EP |
1040821 | Oct 2005 | EP |
1216277 | Nov 2005 | EP |
1595921 | Nov 2005 | EP |
753545 | May 2006 | EP |
1333790 | Aug 2006 | EP |
1110535 | Feb 2007 | EP |
1097699 | May 2007 | EP |
1727864 | Jul 2007 | EP |
1682622 | Aug 2007 | EP |
1457192 | Feb 2008 | EP |
1633443 | Mar 2008 | EP |
1430906 | Jun 2008 | EP |
1459112 | Oct 2009 | EP |
1339375 | Nov 2009 | EP |
2266527 | Dec 2010 | EP |
2217665 | Jun 2011 | EP |
1189586 | Oct 2011 | EP |
1268177 | Jul 1978 | GB |
1430701 | Sep 1978 | GB |
1464060 | Nov 1978 | GB |
1517230 | Mar 1981 | GB |
1533430 | Jan 1998 | GB |
2055879 | May 1998 | GB |
1525793 | Jul 2005 | GB |
10194912 | Mar 1972 | JP |
10259116 | Apr 1976 | JP |
11116438 | Feb 1977 | JP |
0543417 | Feb 1993 | JP |
7309715 | Nov 1995 | JP |
8217638 | Aug 1996 | JP |
8269357 | Oct 1996 | JP |
9012430 | Jan 1997 | JP |
9194754 | Jul 1997 | JP |
9309819 | Dec 1997 | JP |
2005187417 | Jul 1998 | JP |
10017438 | Sep 1998 | JP |
10114867 | Apr 1999 | JP |
11116441 | Apr 1999 | JP |
11124314 | May 1999 | JP |
11222414 | Aug 1999 | JP |
2000034203 | Feb 2000 | JP |
2001039847 | Feb 2001 | JP |
2001288039 | Oct 2001 | JP |
2002003357 | Jan 2002 | JP |
2002087935 | Mar 2002 | JP |
2002241228 | Aug 2002 | JP |
2003003089 | Jan 2003 | JP |
2003026537 | Jan 2003 | JP |
2003171232 | Jun 2003 | JP |
2003171575 | Jun 2003 | JP |
2003212723 | Jul 2003 | JP |
2003213156 | Jul 2003 | JP |
2003261423 | Sep 2003 | JP |
2004010541 | Jan 2004 | JP |
2004123682 | Apr 2004 | JP |
2004238337 | Aug 2004 | JP |
2004339185 | Dec 2004 | JP |
2005126328 | May 2005 | JP |
2005255633 | Sep 2005 | JP |
2005314390 | Nov 2005 | JP |
2005314391 | Nov 2005 | JP |
2005314392 | Nov 2005 | JP |
2005314394 | Nov 2005 | JP |
2005314396 | Nov 2005 | JP |
2005350407 | Dec 2005 | JP |
2006045562 | Feb 2006 | JP |
2006328070 | Dec 2006 | JP |
2007126482 | May 2007 | JP |
2007291066 | Nov 2007 | JP |
2008230997 | Oct 2008 | JP |
2008255012 | Oct 2008 | JP |
2009173606 | Aug 2009 | JP |
2009185029 | Aug 2009 | JP |
2009280507 | Dec 2009 | JP |
2009280542 | Dec 2009 | JP |
2010083792 | Apr 2010 | JP |
2010105936 | May 2010 | JP |
2010126445 | Jun 2010 | JP |
2010235489 | Oct 2010 | JP |
2010235530 | Oct 2010 | JP |
2010280607 | Dec 2010 | JP |
WO 9603962 | Feb 1996 | WO |
WO 9634917 | Nov 1996 | WO |
WO 9739066 | Oct 1997 | WO |
WO 9850471 | Nov 1998 | WO |
WO 0051551 | Sep 2000 | WO |
WO 0075240 | Dec 2000 | WO |
WO 0216505 | Feb 2002 | WO |
WO 2004007624 | Jan 2004 | WO |
WO 2004100922 | Nov 2004 | WO |
WO 2006097352 | Sep 2006 | WO |
WO 2007031970 | Mar 2007 | WO |
WO 2007055529 | May 2007 | WO |
WO 2007093334 | Aug 2007 | WO |
WO 2007118570 | Oct 2007 | WO |
WO 2007140897 | Dec 2007 | WO |
WO 2008007334 | Apr 2008 | WO |
WO 2008074654 | Jun 2008 | WO |
WO 2008092529 | Aug 2008 | WO |
WO 2008132042 | Nov 2008 | WO |
WO 2008135383 | Nov 2008 | WO |
WO 2009071529 | Jun 2009 | WO |
WO 2009135784 | Nov 2009 | WO |
WO 2009152907 | Dec 2009 | WO |
WO 2010050194 | May 2010 | WO |
WO 2010057968 | May 2010 | WO |
WO 2010063430 | Jun 2010 | WO |
WO 2010146570 | Dec 2010 | WO |
WO 2011079160 | Jun 2011 | WO |
WO 2011085780 | Jul 2011 | WO |
WO 2011095326 | Aug 2011 | WO |
WO 2012046798 | Apr 2012 | WO |
Number | Date | Country | |
---|---|---|---|
20140271739 A1 | Sep 2014 | US |