Technical Field

The invention is in the field of compositions for topical application to keratin surfaces containing Indium Nitride coated particles. Background of the Invention

The undesirable effects of ultraviolet radiation on skin are well known. Ultraviolet light is electromagnetic radiation with wavelengths ranging from 100 to 400 nm. UV wavelengths are shorter than those of visible light (which ranges from 400 to 700 nm) but longer than the wavelengths found in X-rays. UV light can be further categorized into UVA, UVB, and UVC. UVA light has wavelengths ranging from 315 to 400 nm. UVB light has wavelengths ranging from 280 to 315 nm. UVC has wavelengths ranging from 100 to 280 nm. UV light can also be categorized by near UV ("NUV") which is 300 to 400 nm, middle UV ("MUV") which is 200 to 300, and far UV ("FUV") which is 122 to 200 nm. It has been shown that exposure to UV light can result in immediate skin tanning or burning and, over time and repeated exposure, increase skin photo aging, which manifests in conditions such as wrinkles, lines, skin laxity and uneven pigmentation.

However, less well documented are the effects of infrared ("IR") light on skin. IR light spans wavelengths ranging from 760 nm to 1 mm and is subdivided into three regions of increasing wavelength: IR-A from 760 nm to 1400nm, IR-B from 1400 to 3000 nm, and IR-C from 3000 nm to 1 mm. The solar energy that reaches the earth's surface spans the UV, visible, and IR wavelength ranges. Nearly one half of that solar energy is in the IR range and transmitted in the form of heat. It is known that chronic heat exposure can cause certain skin conditions similar to what is seen in photo-aged skin. For example, a condition known as erythema ab igne results in symptoms such as hyperpigmentation, reticulated erythema, scaling, and telangiectasis in skin surfaces that are exposed to IR radiation over longer periods of time. People who spend a lot of time in heat conditions, such as bakers or jewelers, often exhibit this condition, which may also be referred to as "baker' s arms", "hot water bottle rash" or "toasted skin syndrome". Cho, et al., Effects of Infrared Radiation and Heat on Human Skin Aging in vivo, The Society for Investigative Dermatology, Vol. 14, pages 15-19, 2009, reports that IR-A can penetrate epidermal and dermal layers and reach subcutaneous tissues without noticeably increasing skin temperature. IR-B and IR-C are absorbed mostly in epidermal layers and cause increased skin temperature. Cho further states that repeated exposure to near IR has been shown to cause decreased type I procollagen expression and decreased expression of TGF-βΙ, β2 and β3 in human skin in vivo. Cho also reports that exposure to IR radiation can impact expression of MMP-1, cause degradation of extracellular proteins such as collagen and elastin fibers, decreased fibrillin production, elastosis, angiogenesis, and so on.

For at least these reasons it is desirable to create topical products that protect keratin surfaces such as skin or hair from IR radiation either alone or in conjunction with UV radiation protective effects.

Indium Nitride ("InN") is sometimes referred to as a ternary Group Ill/Group V semiconductor which is said to have applications in high speed electronics or solar cells. It has a molecular weight of 128.82 daltons and a CAS No. 25617-98-5. InN is not known for use in consumer products, and particularly not in topical consumer products for protecting skin against IR radiation, or in compositions that are designed to protect skin from both UV and IR radiation.

It is an object of the invention to provide particles coated with InN that have IR radiation protective effects when formulated into products for topical application to keratin surfaces. In one embodiment of the invention the particles coated with InN are chemical or physical sunscreens in particulate form. In this case the particles exhibit both UV and IR protective effects. The InN coated particles protect keratin surfaces from the adverse effects of IR radiation from all sources, but particularly solar IR radiation.

It is a further object of the invention to provide a topical composition for protecting keratin surfaces from the adverse effects of IR radiation containing InN coated particles in an amount sufficient to protect against IR radiation.

It is a further object of the invention to provide a topical composition for protecting keratin surfaces from the adverse effects of UV and IR radiation containing chemical or physical sunscreen particles coated with InN.

It is a further object of the invention to provide a method for protecting keratin surfaces from the adverse effects of IR radiation exposure by topically applying a composition containing InN coated particles.

It is a further object of the invention to provide a method for protecting keratin surfaces from the adverse effects of UV and IR radiation by topically applying a composition containing InN coated chemical or physical sunscreen particles.

Background of the Invention

The invention is directed to a solid or hollow particle ranging from 0.001 to 200 microns in diameter coated with Indium Nitride ("InN"). The particle may be a pigment or powder. In one embodiment the particle may be a sunscreen such as zinc or titanium dioxide.

The invention is also directed to a topical composition containing a solid or hollow particle coated with InN. The topical composition preferably blocks IR radiation, and in one preferred embodiment the particle coated with InN is sunscreen particle and blocks both UV radiation due to the sunscreen particle with the InN film coating blocking the IR radiation. The invention is also directed to a topical UV protective composition containing a particle coated with InN.

The invention is also directed to a method for protecting skin against solar IR radiation by topically applying a composition comprising at least one InN coated particle.

The invention is also directed to a method for protecting skin from solar UV and IR radiation by topically applying a composition comprising at least one chemical or physical sunscreen in particulate form which is coated with InN.

Detailed Description

Definitions

All documents referred to herein are incorporated by reference in their entirety unless otherwise stated.

All percentages referred to herein are percentages by weight unless otherwise indicated.

The term "block" means, with respect to IR or UV radiation, that the radiation is blocked either in whole or in part from causing undesirable effects in the keratin surface either by physically blocking the radiation from reaching the surface, absorbing the radiation when it reaches the surface, or reflecting the radiation when it reaches the keratin surface.

The term "keratin surfaces" means skin, hair, or nails.

The term "topical" when used to refer to the composition means any composition that is applied to a keratin surface such as skin, hair, or nails.

Indium Nitride The InN used in the invention may be in the form of a powder, and in one form a black crystalline solid powder. The melting point is about 1100° C. InN particles may be found in the nano range (7 to 75 nm) or standard fine grain powder particle sizes ranging from 0.1 to 15 microns, or agglomerated particles usually having a particle size greater than 30 microns, for example from 15 to 50 microns. The particles may be in the form of dispersions in water or organic solvents including mono- or dihydric alcohols such as ethanol, isopropanol, butylene glycol, propylene glycol, and the like. Other suitable forms include particles of various sizes such as nanoparticles (around 18 nm, or sizes less than 50 nm in diameter), particles of about 40-50 microns or more particularly having 43 microns, also referred to as -325 mesh. Indium nitride may be purchased from a variety of commercial sources including Sigma Aldrich.

Particles

In the preferred embodiment of the invention the InN is coated onto particles used in cosmetics. Such particles may be pigments, powders, or combinations thereof. These particles may range from 0.001 to 200 microns in diameter. All, or a portion of the particles may be coated with InN. The particles coated with InN may include those set forth below:

A. Powders

The particles may be colored or non-colored (for example white) non-pigmented powders. Suitable non-pigmented powders include zinc oxide or titanium dioxide (which may be micronized, e.g. having a particle size of from about 0.01 to 1 micron and are generally known for having SPF properties, particularly UVA), bismuth oxychloride, titanated mica, fumed silica, spherical silica, polymethylmethacrylate, micronized teflon, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium aluminum silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate, calcium silicate, dextran, kaolin, nylon, silica silylate, silk powder, sericite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder, or mixtures thereof. The above mentioned powders may be also be surface treated with lecithin, amino acids, mineral oil, silicone, or various other agents either alone or in combination, which coat the powder surface and render the particles more lipophilic in nature.

B. Pigments

The particles may comprise various organic and/or inorganic pigments. The organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthroquinone, and xanthine dyes which are designated as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc. Organic pigments generally consist of insoluble metallic salts of certified color additives, referred to as the Lakes. Inorganic pigments include iron oxides, ultramarines, chromium, chromium hydroxide colors, and mixtures thereof. Iron oxides of red, blue, yellow, brown, black, and mixtures thereof are suitable.

Composite particles may be suitable as well. Examples include spherical particles having a gaseous center sold under the trade name Expancel® 551, 820, 920, and DE having INCI names acrylonitrile/vinyl chloride/isobutene copolymer, acrylonitrile/vinylidene chloride/isobutene copolymer, acrylic acid/acrylonitrogens copolymer, isobutene/copolymer of acrylonitrile/methacrylate/acrylate copolymer, isobutene/copolymer of

acrylonitrile/methacrylate/acrylate/water, and so on. If desired, these particles may be impregnated with other particles such as chemical or physical sunscreens according to the method set forth in Sojka, et al, U.S. Patent Application No. US2007/0071978. Also suitable are particles referred to as Sunspheres® which are polymeric particles from styrene/acrylates copolymer sold by Dow Chemical Corporation. The styrene/acrylates copolymer particles have a particle size ranging from about 300 to 500 nanometers, more particularly about 400 nanometers. They may be coated with ingredients such as nonionic surfactants or glycols.

The Coating Method

The InN may be coated on the particles in a variety of ways. It is preferred that the coating process be one that is operable at temperatures typically used in the preparation of cosmetic ingredients and formulations, which preferably range from room temperature to 350° C. In particular, in one embodiment the temperature at which the InN coating is applied most desirably does not exceed 300° C.

One process for coating InN onto the particles involves simply mixing IN power with the particles to form mixtures of InN and particles. This may be accomplished by physically combining the particles desired for treatment with the InN. Ratios include from 5 to 80 parts particles to 80 to 5 parts InN.

Another process for coating InN onto the particles may accomplished by a process referred to as physical vapor deposition ("PVD") or sputter deposition which is a form of PVD. PVD uses physical forces to apply layers or coatings to the particulates. In PVD the desired particles may be prepared by drying them in an oven at sufficient temperature to remove any residual water. The drying may take place at temperatures ranging from 70 to 300° C, or at about 125° C. for a period of time to evaporate moisture. Depending on how much moisture is in the particles, this time can range from 1 to 24 hours. The dry particles are then put into a vacuum chamber and air is removed. A background pressure ranging from 10 ^"6 to 10 ^"4 torr may be used. A sputtering gas is then introduced. One example of a suitable gas may halogens such as argon or carbon tetrafluoride, and the like. The sputtering gas is added in an amount sufficient to obtain the desired background pressure in the system, which may range from 1 to 20 millitorr. The InN is then introduced into the chamber. In one

embodiment the vacuum sputtering system may be operated in DC magnetron mode. The particles are tumbled slowly in the sputtering target with time and power chosen to produce coatings that are thick enough to provide particles that have the desired particle size.

Sputtering times can range widely, from 2 to 25 hours with power levels also varying from 1 to 10 kilowatts. When the target is InN it preferably takes place in an oxygen free

environment. After sputtering is concluded, if desired, the particles can be heated in air to dry. PVD is an effective and efficient coating process and provides a continuous, uniform, and strongly adherent coating of the InN on the treated particles. PVD systems suitable for sputter coatings may be purchased from PVD Products, Wilmington, MA. Examples of such systems include Magnetron Sputter Deposition Systems that may be in rectangular or cylindrical configurations and options for sputtering up or sputtering down. The chambers may be vacuum or cryogenic.

Also suitable as a coating method are chemical vapor deposition ("CVD") which is formation of a thin film on a substrate by chemical reaction of vapor phase precursors. The reaction occurs in the gas phase and on the substrate. CVD deposition of InN films onto particles may be achieved by the process set forth in Wang and Lin, ChemPhysChem Vol. 5, pp 1615-1618, 2004. More specifically InN is deposited using trimethyl indium ("TMIn") and HN ₃ by low pressure organometallic CVD.

It is also possible to coat particles using thermal methods, although in this case the particle to be coated must not be degraded upon exposure to the high temperatures required to deposit the coating. These temperatures may range from 300 to 1,000° C. In this application the InN is heated with the particle in a high temperature furnace which causes the InN to deposit on the surface of the particle. The temperature typically ranges from 1000 to 1200° C.

Pulsed laser deposition in high vacuum chamber which may be accompanied by reactive and ion-assisted sputtering is also a suitable deposition method.

Another suitable process is electrospinning sol-gel prepared InN coatings on substrates followed by thermal processing as set forth in Zhang, et al., Optical Materials 26 (2004) pages 47-55. In this process sol-gel InN is prepared and spin coating is used to apply the coating to the particles followed by heat treatment at temperatures ranging from 175 to 600° C.

The InN may be coated onto the particles with a suitable process that does not degrade the particles and is otherwise compatible with the InN, the particle and the other ingredients used in the process. The coating may range in thickness from 0.1 to 1000 nanometers, or from 0.5 to 25% of the total particle by weight.

The Compositions

The InN coated particles may be incorporated into a variety of compositions that may be in the anhydrous, emulsion, gel, or solution form. The InN particles may range from 0.1 to 60%, preferably from about 0.5 to 50%, more preferably from about 1 to 40% by weight of the total composition.

The topical composition may contain other ingredients including but not limited to those set forth below:

A. Oils

In the event the compositions of the invention are in anhydrous or emulsion form, the composition will comprise an oil phase. Oily ingredients are desirable for the skin moisturizing and protective properties and may be present in amounts ranging from 0.1 to 80%. Suitable oils include silicones, esters, vegetable oils, synthetic oils, including but not limited to those set forth herein. The oils may be volatile or nonvolatile, and are preferably in the form of a pourable liquid at room temperature. The term "volatile" means that the oil has a measurable vapor pressure, or a vapor pressure of at least about 2 mm. of mercury at 20° C. The term "nonvolatile" means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20° C.

Suitable volatile oils generally have a viscosity ranging from about 0.5 to 5 centistokes 25° C. and include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof. Examples include linear, cyclic, or branched volatile silicones available from commercial sources such as Dow Corning Corporation and General Electric. The Dow Corning linear volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids include hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviated est)), octamethyltrisiloxane (1.0 est), decamethyltetrasiloxane (1.5 est), dodecamethylpentasiloxane (2 est) and mixtures thereof, with all viscosity measurements being at 25° C. Branched volatile silicones include methyl trimethicone which may be purchased from Shin-Etsu Silicones under the tradename TMF-1.5, having a viscosity of 1.5 centistokes at 25° C.

Also suitable are volatile straight or branched chain paraffinic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and Cs-2o isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference. A variety of nonvolatile oils are also suitable and may have a viscosity of greater than about 5 to 10 centistokes at 25° C, and may range in viscosity up to about 1,000,000 centipoise at 25° C. Examples of nonvolatile oils include, but are not limited to esters, in the mono-, di-, or triester form including hexyl laurate, butyl isostearate, hexadecyl isostearate, cetyl palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl isononanoate, steary lactate, stearyl octanoate, stearyl stearate, isononyl isononanoate, diisotearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, dioctyl malate, arachidonic, citric, or behenic acids, such as triarachidin, tributyl citrate, triisostearyl citrate, tri C12-13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.

Esters suitable for use in the composition are further described in the C.T.F.A.

Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition, 2006, under the

classification of "Esters".

Hydrocarbons are also suitable and include paraffinic hydrocarbons and olefins, preferably those having greater than about 20 carbon atoms. Examples of such hydrocarbon oils include C24-28 olefins, C30-45 olefins, C20-40 isoparaffins, hydrogenated polyisobutene, polyisobutene, polydecene, hydrogenated polydecene, mineral oil, pentahydrosqualene, squalene, squalane, and mixtures thereof. In one preferred embodiment such hydrocarbons have a molecular weight ranging from about 300 to 1000 Daltons.

Synthetic or naturally occurring glyceryl esters of fatty acids, or triglycerides, are also suitable for use in the compositions. Both vegetable and animal sources may be used.

Examples of such oils include castor oil, lanolin oil, C10-18 triglycerides, caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil, sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil, walnut oil, and the like. Also suitable are synthetic or semi- synthetic glyceryl esters, such as fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, mono-, di- or triesters of polyols such as glycerin. In an example, a fatty (Ci _2-22 ) carboxylic acid is reacted with one or more repeating glyceryl groups, glyceryl stearate, diglyceryl diiosostearate, polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryl tetraisostearate, glyceryl trioctanoate, diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on.

Nonvolatile silicone oils, both water soluble and water insoluble, are also suitable for use in the composition. Such silicones preferably have a viscosity ranging from about greater than 5 to 800,000 est, preferably 20 to 200,000 est at 25° C. Examples include dimethicone, phenyl dimethicone, diphenyl dimethicone, phenyl trimethicone, or trimethylsiloxyphenyl dimethicone. Other examples include alkyl dimethicones such as cetyl dimethicone, and the like wherein at Phenyl trimethicone can be purchased from Dow Corning Corporation under the tradename 556 Fluid. Trimethylsiloxyphenyl dimethicone can be purchased from Wacker- Chemie under the tradename PDM-1000. Cetyl dimethicone, also referred to as a liquid silicone wax, may be purchased from Dow Corning as Fluid 2502, or from DeGussa Care & Surface Specialties under the trade names Abil Wax 9801, or 9814. In the case where the compositions are in the form of aqueous solutions, dispersions or emulsions, in addition to water the aqueous phase may contain one or more aqueous phase structuring agents, that is, an agent that increases the viscosity or thickens, the aqueous phase of the composition. Suitable ranges of aqueous phase structuring agent, if present, are from about 0.01 to 30%, preferably from about 0.1 to 20%, more preferably from about 0.5 to 15% by weight of the total composition. Examples of such agents include various acrylate based thickening agents, natural or synthetic gums, polysaccharides such as agar, agarose, alicaligenes polysaccharides, algin, alginic acid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum, pectin, trehelose, gelatin, and so on.

One type of suitable acrylate based polymeric thickener is sold by Clariant under the Aristoflex trademark such as Aristoflex AVC, which is ammonium

acryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the same polymer has found in AVC dispersed in mixture containing caprylic/capric triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; or Aristoflex HMB which is ammonium

acryloyldimethyltaurate/beheneth-25 methacrylate crosspolymer, and the like.

Also suitable as the aqueous phase thickening agents are various polyethylene glycols (PEG) derivatives where the degree of polymerization ranges from 1,000 to 200,000. Such ingredients are indicated by the designation "PEG" followed by the degree of polymerization in thousands, such as PEG-45M, which means PEG having 45,000 repeating ethylene oxide units. Examples of suitable PEG derivatives include PEG 2M, 5M, 7M, 9M, 14M, 20M, 23M, 25M, 45M, 65M, 90M, 115M, 160M, 180M, and the like. In the case where the composition is anhydrous or in the form of an emulsion, it may be desirable to include oil phase structuring agents. The term "oil phase structuring agent" means an ingredient or combination of ingredients, soluble or dispersible in the oil phase, which will increase the viscosity, or structure, the oil phase. The structuring agent itself may be present in the liquid, semi-solid, or solid form. Suggested ranges of structuring agent are from about 0.01 to 20%, preferably from about 0.05 to 15%, more preferably from about 0.1- 10% by weight of the total composition. Suitable oil phase structuring agents include those that are silicone based or organic based.

Silicone based structuring agents include silicone elastomers, silicone gums, silicone waxes, linear silicones having a degree of polymerization that provides the silicone with a degree of viscosity such that when incorporated into the cosmetic composition it is capable of increasing the viscosity of the oil phase.

Silicone elastomers include vinyl dimethicone/methicone silesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105, hybrid silicone powders that contain a fluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro- silicone elastomer, and hybrid silicone powders that contain a phenyl group such as Shin-Etsu's KSP- 300, which is a phenyl substituted silicone elastomer; and Dow Coming's DC 9506.

Examples of silicone elastomer powders dispersed in a silicone compatible vehicle include dimethicone/vinyl dimethicone crosspolymers supplied by a variety of suppliers including Dow Corning Corporation under the tradenames 9040 or 9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Silicones under the tradenames KSG-15, 16, 18. KSG-15 has the CTFA name cyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG- 18 has the INCI name phenyl trimethicone/dimethicone/phenyl vinyl dimethicone crossoplymer. Silicone elastomers may also be purchased from Grant Industries under the Gransil trademark. Also suitable are silicone elastomers having long chain alkyl substitutions such as lauryl dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu under the tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44. Cross-linked organopolysiloxane elastomers useful in the present invention and processes for making them are further described in U.S. Pat. No. 4,970,252 to Sakuta et al., issued Nov. 13, 1990; U.S. Pat. No. 5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No. 5,654,362 to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese Patent Application JP 61-18708, assigned to Pola Kasei Kogyo KK, each of which are herein incorporated by reference in its entirety.

Also suitable are silicone gums. The term "gum" means a silicone polymer having a degree of polymerization sufficient to provide a silicone having a gum- like texture. In certain cases the silicone polymer forming the gum may be crosslinked. The silicone gum typically has a viscosity ranging from about 500,000 to 100 million est at 25° C, preferably from about 600,000 to 20 million, more preferably from about 600,000 to 12 million est. All ranges mentioned herein include all subranges, e.g. 550,000; 925,000; 3.5 million. Such silicone gums may be purchased in pure form from a variety of silicone manufacturers including Wacker-Chemie or Dow Corning, and the like. Such silicone gums include those sold by Wacker-Belsil under the trade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096. A silicone gum where X is OH, also referred to as dimethiconol, is available from Dow Corning Corporation under the trade name 1401. The silicone gum may also be purchased in the form of a solution or dispersion in a silicone compatible vehicle such as volatile or nonvolatile silicone. An example of such a mixture may be purchased from Barnet Silicones under the HL-88 tradename, having the INCI name dimethicone.

Silicone waxes are also suitable and include alkyl silicone waxes which are semi-solids or solids at room temperature. The term "alkyl silicone wax" means a polydimethylsiloxane having a substituted long chain alkyl (such as C16 to 30) that confers a semi-solid or solid property to the siloxane. Examples of such silicone waxes include stearyl dimethicone, which may be purchased from DeGussa Care & Surface Specialties under the tradename Abil Wax 9800 or from Dow Corning under the tradename 2503. Another example is bis-stearyl dimethicone, which may be purchased from Gransil Industries under the tradename Gransil A- 18, or behenyl dimethicone, behenoxy dimethicone.

Natural or synthetic waxes such as animal, vegetable, or mineral waxes may be used. Preferably such waxes will have a higher melting point such as from about 35 to 150° C, more preferably from about 65 to 100° C. Examples of such waxes include waxes made by Fischer- Tropsch synthesis, such as polyethylene or synthetic wax; or various vegetable waxes such as bayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnauba wax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, grape wax, and polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or PEG- 12 carnauba wax; or fatty acids or fatty alcohols, including esters thereof, such as hydroxystearic acids (for example 12-hydroxy stearic acid), tristearin, tribehenin, and so on.

Synthetic montmorillonite minerals such as hectorite, bentonite, and quaternized derivatives thereof, which are obtained by reacting the minerals with a quaternary ammonium compound, such as stearalkonium bentonite, hectorites, quaternized hectorites such as

Quaternium-18 hectorite, attapulgite, carbonates such as propylene carbonate, bentones, and the like are suitable as well as silicas, silicates, silica silylate, and alkali metal or alkaline earth metal derivatives thereof. These silicas and silicates are generally found in the particulate form and include silica, silica silylate, magnesium aluminum silicate, and the like. The composition may contain one or more organic surfactants, especially if in the emulsion form. However, such surfactants may be used if the compositions are anhydrous also, and will assist in dispersing ingredients that have polarity, for example pigments. Such surfactants may be silicone or organic based. The surfactants will aid in the formation of stable emulsions of either the water-in-oil or oil-in- water form. If present, the surfactant may range from about 0.001 to 30%, preferably from about 0.005 to 25%, more preferably from about 0.1 to 20% by weight of the total composition.

The composition may comprise one or more nonionic organic surfactants. Suitable nonionic surfactants include alkoxylated alcohols, or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide. Preferably the alcohol is either a fatty alcohol having 6 to 30 carbon atoms. Examples of such ingredients include Steareth 2-100, which is formed by the reaction of stearyl alcohol and ethylene oxide and the number of ethylene oxide units ranges from 2 to 100; Beheneth 5-30 which is formed by the reaction of behenyl alcohol and ethylene oxide where the number of repeating ethylene oxide units is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, and so on.

Other alkoxylated alcohols are formed by the reaction of fatty acids and mono-, di- or polyhydric alcohols with an alkylene oxide. For example, the reaction products of C ₆ -3o fatty carboxylic acids and polyhydric alcohols which are monosaccharides such as glucose, galactose, methyl glucose, and the like, with an alkoxylated alcohol. Examples include polymeric alkylene glycols reacted with glyceryl fatty acid esters such as PEG glyceryl oleates, PEG glyceryl stearate; or PEG polyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein the number of repeating ethylene glycol units ranges from 3 to 1000.

Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular ethoxylation of sorbitan provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates. For example, the polyalkyoxylated sorbitan can be esterified with C6-30, preferably C12-22 fatty acids. Examples of such ingredients include Polysorbates 20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and so on.

It may also be desirable to include one or more humectants in the composition. If present, such humectants may range from about 0.001 to 25%, preferably from about 0.005 to 20%, more preferably from about 0.1 to 15% by weight of the total composition. Examples of suitable humectants include glycols, sugars, and the like. Suitable glycols are in monomeric or polymeric form and include polyethylene and polypropylene glycols such as PEG 4-200, which are polyethylene glycols having from 4 to 200 repeating ethylene oxide units; as well as Ci-6 alkylene glycols such as propylene glycol, butylene glycol, pentylene glycol, and the like. Suitable sugars, some of which are also polyhydric alcohols, are also suitable humectants. Examples of such sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Also suitable is urea. Preferably, the humectants used in the composition of the invention are Ci_ ₆ , preferably C2-4 alkylene glycols, most particularly butylene glycol.

It may be desirable to include one or more botanical extracts in the compositions. If so, suggested ranges are from about 0.0001 to 10%, preferably about 0.0005 to 8%, more preferably about 0.001 to 5% by weight of the total composition. Suitable botanical extracts include extracts from plants (herbs, roots, flowers, fruits, seeds) such as flowers, fruits, vegetables, and so on, including yeast ferment extract, Padina Pavonica extract, thermus thermophilis ferment extract, Camelina sativa seed oil, Boswellia serrata extract, olive extract, Aribodopsis Thaliana extract, Acacia Dealbata extract, Acer Saccharinum (sugar maple), acidopholus, acorus, aesculus, Alicaligenes polysaccharides, agaricus, agave, agrimonia, algae, aloe, citrus, brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear, lemon, lime, pea, seaweed, caffeine, green tea, chamomile, willowbark, mulberry, poppy, and those set forth on pages 1646 through 1660 of the CTFA Cosmetic Ingredient Handbook, Eighth Edition, Volume 2. Further specific examples include, but are not limited to, Glycyrrhiza glabra, Salix nigra, Macrocycstis pyrifera, Pyrus mains, Saxifraga sarmentosa, Vitis vinifera, Morus nigra, Scutellaria baicalensis, Anthemis nobilis, Salvia sclarea, Rosmarinus officianalis, Citrus medica limonum, Panax ginseng, Siegesbeckia orientalis, Fructus mume, Ascophyllum nodosum, Bifida ferment lysate, Glycine soja extract, Beta vulgaris, Haberlea rhodopensis, Polygonum cuspidatum, Citrus aurantium dulcis, Selaginella tamariscina, Humulus lupulus, Citrus reticulata peel, Punica granatum, Asparagopsis, Curcuma longa, Menyanthes trifoliata, Helianthus annuus, Hordeum vulgare, Cucumis sativus, Evernia prunastri, Evernia furfuracea, and mixtures thereof.

It may also be desirable to include one or more sunscreens in the compositions of the invention. Such sunscreens include chemical UVA or UVB sunscreens or physical sunscreens in the particulate form.

The term "UVA sunscreen" means a chemical compound that blocks UV radiation in the wavelength range of about 320 to 400 nm. Preferred UVA sunscreens are

dibenzoylmethane compounds including 4-methyldibenzoylmethane, 2- methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4- dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 4,4'-diisopropylbenzoylmethane, 2-methyl-5- isopropyl-4'-methoxydibenzoymethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, and so on. Particularly preferred is 4-tert-butyl-4'-methoxydibenzoylmethane, also referred to as Avobenzone. Avobenzone is commercial available from Givaudan-Roure under the trademark Parsol 1789, and Merck & Co. under the tradename Eusolex 9020.

Other types of UVA sunscreens include dicamphor sulfonic acid derivatives, such as ecamsule, a sunscreen sold under the trade name Mexoryl™, which is terephthalylidene dicamphor sulfonic acid.

The composition may contain from about 0.001-20%, preferably 0.005-5%, more preferably about 0.005-3% by weight of the composition of UVA sunscreen. In the preferred embodiment of the invention the UVA sunscreen is Avobenzone, and it is present at not greater than about 3% by weight of the total composition.

The term "UVB sunscreen" means a compound that blocks UV radiation in the wavelength range of from about 290 to 320 nm. A variety of UVB chemical sunscreens exist including alpha-cyano-beta,beta-diphenyl acrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which is hereby incorporated by reference in its entirety. One particular example of an alpha-cyano-beta,beta-diphenyl acrylic acid ester is Octocrylene, which is 2-ethylhexyl 2- cyano-3,3-diphenylacrylate. In certain cases the composition may contain no more than about 10% by weight of the total composition of octocrylene. Suitable amounts range from about 0.001-10% by weight. Octocrylene may be purchased from BASF under the tradename Uvinul N-539. Other suitable sunscreens include benzylidene camphor derivatives as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety. Such benzylidene camphor derivatives have the general formula:

wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred is 4-methylbenzylidene camphor, which is a lipid soluble UVB sunscreen compound sold under the tradename Eusolex 6300 by Merck.

Also suitable are cinnamate derivatives having the general formula:

CH=CH-C-R _!

0 wherein R and Ri are each independently a Ci _-20 straight or branched chain alkyl. Preferred is where R is methyl and Ri is a branched chain Ci_io, preferably Cs alkyl. The preferred compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate or octyl methoxycinnamate. The compound may be purchased from Givaudan Corporation under the tradename Parsol MCX, or BASF under the tradename Uvinul MC 80. Also suitable are mono-, di-, and triethanolamine derivatives of such methoxy cinnamates including diethanolamine methoxycinnamate. Cinoxate, the aromatic ether derivative of the above compound is also acceptable. If present, the Cinoxate should be found at no more than about 3% by weight of the total composition.

Also suitable as UVB screening agents are various benzophenone derivatives having the general formula:

wherein R through R ₉ are each independently H, OH, Na0 ₃ S, S0 ₃ H, S0 ₃ Na, CI, R", OR" where R" is Ci _-20 straight or branched chain alkyl Examples of such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Particularly preferred is where the benzophenone derivative is Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (also referred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium), and the like. Most preferred is Benzophenone 3.

Also suitable are certain menthyl salicylate derivatives having the general formula:

wherein Ri, R2, R ₃ , and R ₄ are each independently H, OH, Ν¾, or Ci-2 ₀ straight or branched chain alkyl. Particularly preferred is where Ri, R2, and R ₃ are methyl and R ₄ is hydroxyl or NH ₂ , the compound having the name homomenthyl salicylate (also known as Homosalate) or menthyl anthranilate. Homosalate is available commercially from Merck under the tradename Eusolex HMS and menthyl anthranilate is commercially available from Haarmann & Reimer under the tradename Heliopan. If present, the Homosalate should be found at no more than about 15% by weight of the total composition.

Various amino benzoic acid derivatives are suitable UVB absorbers including those having the general formula:

N R ₂ R ₃ wherein Ri, R2, and R3 are each independently H, Ci _-20 straight or branched chain alkyl which may be substituted with one or more hydroxy groups. Particularly preferred is wherein Ri is H or Ci-8 straight or branched alkyl, and R2 and R3 are H, or Ci _-8 straight or branched chain alkyl. Particularly preferred are PABA, ethyl hexyl dimethyl PABA (Padimate O),

ethyldihydroxypropyl PABA, and the like. If present Padimate O should be found at no more than about 8% by weight of the total composition.

Salicylate derivatives are also acceptable UVB absorbers. Such compounds have the general formula: wherein R is a straight or branched chain alkyl, including derivatives of the above compound formed from mono-, di-, or triethanolamines. Particular preferred are octyl salicylate, TEA-salicylate, DEA-salicylate, and mixtures thereof. Generally, the amount of the UVB chemical sunscreen present may range from about 0.001- 45%, preferably 0.005-40%, more preferably about 0.01-35% by weight of the total composition.

Also suitable are certain esters of 2-phenyl ethanol and benzoic acid. One example is phenyethyl benzoate, which is sold under the tradename X-Tend 226®, by International Specialty Products.

If desired, the compositions of the invention may be formulated to have a certain SPF (sun protective factor) values ranging from about 1-50, preferably about 2-45, most preferably about 5-30. Calculation of SPF values is well known in the art. The compositions of the invention may contain vitamins and/or coenzymes, as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, more preferably 0.05-5% by weight of the total composition is suggested. Suitable vitamins include ascorbic acid and derivatives thereof such as ascorbyl palmitate, tetrahexydecyl ascorbate, and so on; the B vitamins such as thiamine, riboflavin, pyridoxin, niacin, niacinamide, nicotinic acid, nicotinic acid dinucleotide, and so on, as well as coenzymes such as thiamine pyrophoshate, flavin adenine dinucleotide, folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and derivatives thereof are suitable. Examples are retinyl palmitate, retinol, retinoic acid, as well as Vitamin A in the form of beta carotene. Also suitable is Vitamin E and derivatives thereof such as Vitamin E acetate, nicotinate, or other esters thereof. In addition, Vitamins D and K are suitable.

It may be desirable to include one or more film forming ingredients in the cosmetic compositions of the invention. Suitable film formers are ingredients that contribute to formation of a film on the keratinous surface. If present, such film formers may range from about 0.01 to 50%, preferably from about 0.1 to 40%, more preferably from about 0.5 to 35% by weight of the total composition. Suitable silicone resins include trimethylsiloxysilicate, polymethylsilsesquioxane, dimethicone silylate, and mixtures thereof.

It may also be desirable to incorporate one or more DNA repair enzymes into the composition of the invention. Suggested ranges are from about 0.00001 to about 35%, preferably from about 0.00005 to about 30%, more preferably from about 0.0001 to about 25% of one or more DNA repair enzymes.

DNA repair enzymes as disclosed in U.S. Patent Nos. 5,077,211 ; 5,190,762;

5,272,079; and 5,296,231, all of which are hereby incorporated by reference in their entirety, are suitable for use in the compositions and method of the invention. One example of such a DNA repair enzyme may be purchased from AGI Dermatics under the trade name

Roxisomes®, and has the INCI name Arabidopsis Thaliana extract. It may be present alone or in admixture with lecithin and water. This DNA repair enzyme is known to be effective in repairing 8-oxo-diGuanine base mutation damage.

Another type of DNA repair enzyme that may be used is one that is known to be effective in repairing 06-methyl guanine base mutation damage. It is sold by AGI/Dermatics under the tradename Adasomes®, and has the INCI name Lactobacillus ferment, which may be added to the composition of the invention by itself or in admixture with lecithin and water.

Another type of DNA repair enzyme that may be used is one that is known to be effective in repairing T-T dimers. The enzymes are present in mixtures of biological or botanical materials. Examples of such ingredients are sold by AGI/Dermatics under the tradenames Ultrasomes® or Photosomes®. Ultrasomes® comprises a mixture of Micrococcus lysate (an end product of the controlled lysis of a species of micrococcus), lecithin, and water. Photosomes® comprises a mixture of plankton extract (which is the extract of a biomass which includes enzymes from one or more of the following organisms: thalassoplankton, green micro-algae, diatoms, greenish-blue and nitrogen-fixing seaweed), water, and lecithin.

Another type of DNA repair enzyme may be a component of various inactivated bacterial lysates such as Bifida lysate or Bifida ferment lysate, the latter a lysate from Bifido bacteria which contains the metabolic products and cytoplasmic fractions when Bifido bacteria are cultured, inactivated and then disintegrated. This material has the INCI name Bifida Ferment Lysate.

The DNA repair enzymes may be present as components of botanical extracts, bacterial lysates, biological materials, and the like. For example, botanical extracts may contain DNA repair enzymes.

The compositions of the invention may be found in a variety of forms, such as anhydrous compositions, aqueous based solutions, serums, gels, skin creams or lotions, or color cosmetic compositions such as foundation makeup, mascara, lip color, blush, eyeshadow, and the like. Emulsions comprise from about 0.1 to 95%, preferably from about 1 to 90%, more preferably from about 2 to 85% water; and from about 0.1 to 95%, preferably from about 1 to 90%, more preferably from about 2 to 85% of one or more oils.

Suitable serums or gels will generally comprise from about 1-99% water, and optionally from about 0.001-30% of an aqueous phase thickening agent. The other ingredients mentioned herein may be present in the percentage ranges set forth. In the case where the cynaodiphenylacrylate is lipophilic it will be dispersed in the aqueous phase.

Typical skin creams or lotions comprise from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants. Preferably the surfactants are nonionic and may be in the form of oxyalkylenated organosiloxanes or organic nonionic surfactants. Typical color cosmetic compositions such as foundations, blush, eyeshadow and the like will preferably contain from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants in addition to from about 0.1 to 65% of particulates that are pigments or a combination of pigments and powders. Shampoos and conditioners contain large amounts of water, ranging from 10-

95%, as well as surfactants from 0.01 to 20% and, if desired, oils or other conditioning ingredients.

EXAMPLE 1

Sunscreen grade T1O2 particles having a diameter ranging from 0.01 to 10 microns and ZnO particles of the same diameter may be coated with InN. HN ₃ may prepared by acidification of NaN ₃ with 50% H ₃ PO ₄ and purified with a series of cold traps maintained at dry ice and liquid nitrogen temperatures as described in Bu et al. Nature, Vol. 353, pp 737 (1991) and Nature Vol. 424, pg. 338 (2001). The purified HN ₃ may be stored at dry ice temperature as a clear liquid. The vapors of the reagents over the crystalline TMLn at room temperature and liquid HN ₃ at dry ice temperature are used as the effusive beam sources. The vapors may be introduced into the system through two separate 1/8 inch stainless steel tubes above the substrates with gas flow rate controlled by a combined need and shut-off valve and monitored by low pressure transducer. InN films are directly grown over Ti02 particles in an oil-free high-vacuum chamber with a base pressure of 1x10-8 Torr evacuated with a Leybold turbomolecular pump (TURBOVAC 360). The sample is resistively heated up to 900K.

Deposition time ranges from 1-8 hours. If desired the T1O2 samples may be treated with UV radiation to facilitate deposition and minimize carbon contamination using a continuous UV light source and a 1000 Watt high pressure mercury xenon lamp. The particles may be cleaned with DI water, followed by optional annealing in a vacuum chamber. EXAMPLE 2

Red iron oxide, particle size about 15-30 microns are coated with InN by treating 500 mg of red iron oxide with InN according to the process set forth in Example 1. The resulting particles are dried in an oven at 300° C. for 20 minutes. The particles prepared in Examples 1 and 2 may be tested for transmittance of IR radiation using a NIR spectrophotometer having a range of 190 to 2700 nm. Jasco, Inc., V- 670 model.

EXAMPLE 3

The particles of Example 1 are incorporated into a sunscreen composition as follows:

Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 2.00 2.00

Ethyl macadamiate 2.00 2.00

Cetyl PEG/PPG 10/1 dimethicone 1.00 1.00

Dimethicone/dimethicone PEG/PPG 15 crosspolymer 0.50 0.50

Isostearic acid 0.40 0.40

Trisiloxane 0.36

Trimethylsiloxysilicate 0.33 0.33

Acrylates copolymer 0.30

Polyhydroxystearic acid 0.25 0.25

Xanthan gum 0.25 0.25

Dimethicone silylate 0.24

Disteardimonium hectorite 0.24

Dimethicone/vinyl dimethicone crosspolymer 0.15 0.15

Lecithin 0.01 0.01

The compositions were prepared by combining the ingredients well and mixing to form an emulsion.

EXAMPLE 4

An anhydrous product with SPF is prepared as follows:

Bis-diglyeryl polyacyladipate-2 5.29

Homosalate 5.00

Mica/Aluminum Dimyristate/triethoxcaprylylsilane/disodium stearoyi 5.00 glutamate

InN coated mica/methylmethacrylate crosspolymer 5.00

Ethylhexyl salicylate 5.00

Microcrystalline wax 4.50

Simmondsia Chinensis (jojoba) seed oil 4.00

Butyloctyl salicylate 4.00

Glyceryl hydrogenated rosinate 4.00

Oleic/linoleic/linolenic polyglyceride 4.00

HDI/trimethylol hexyllactone crosspolymer/silica 3.50

Avobenzone 3.00

Polyglyceryl-2 triisostearate 2.81

Octocrylene 2.79

Synthetic wax/synthetic beeswax/stearic acid 2.40

Ethyl macadamiate 2.00

Butyrospermum parkii (Shea Butter) 2.00

Beeswax 1.80

Methyl glucose sesquistearate 1.50

Dipentaerythrityl hexahydroxystearate/hexastearate/hexa rosinate 1.49

Glyceryl dilaurate 1.00

VP/Eicosene 1.00

Isononyl isononanoate QS

EXAMPLE 5 Skin treatment oil-in-water (1), and oil-in-water-in-silicone oil (2), creams may be prepared as follows:

Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 1.00

Wheat bran extract/olive extract 0.20 0.20

Cholesterol 0.20

Linoleic acid 0.20

Cholesterol/potassium sulfate 0.20

Theobroma grandiflorum seed butter 1.40

Lauryl PCA 0.01 1.00

Dimethicone 1.50

Glycerin 2.00

Butylene glycol 1.00

Hexylene glycol 0.05

InN coated mica/titanium dioxide 1.00 0.75

InN coated mica/titanium dioxide/triethoxycaprylyl silane 0.50

Pearl powder 0.001

Silica 0.50

N-acetyl glucosamine 1.00 1.00

Water/purified Aribodopsis Thaliana extract/lecithin 0.50 1.00

Aqueous solution acetyl hexapeptide-8 1.00 1.00

Yeast ferment extract 1.00 1.00

Water/lecithin/micrococcus lysate 0.50 0.50

Butylene glycol 0.50

Boswellia Serrata extract 0.05

Calophyllum Inophyllum (tamanu) seed oil 0.05

Sodium acrylate/sodium acryloyldimethyl taurate 1.00 1.00 copolymer/hydrogenated polydecene/laureth-8 Ammonium acrylodimethyltaurate/VP copolymer 0.70

The composition is prepared by combining the water phase and oil phase ingredients separately, then emulsifying to form an emulsion.

EXAMPLE 6 Emulsion foundation makeup compositions are prepared as follows:

The water, oil and pigment phases are separately prepared by low shear mixing. The phases are combined with high shear blending to form a foundation makeup composition.

While the invention has been described in connection with the preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.