Coated powder with high light stability
阅读说明：本技术 具有高光稳定性的经涂覆的粉末 (Coated powder with high light stability ) 是由 H.W.萨卡斯 A.R.霍伯 N.H.霍夫曼 于 2018-04-10 设计创作，主要内容包括：经涂覆的粉末包括：(a)颗粒,和(b)在颗粒的表面上的涂层,其包括(1)二氧化硅部分、(2)选自单有机氧基硅烷部分、双有机氧基硅烷部分和三有机氧基硅烷部分的有机氧基硅烷部分以及(3)聚(二烷基)硅氧烷部分。有机氧基硅烷部分和二氧化硅部分的以SiO<Sub>2</Sub>当量计的重量量为总的经涂覆的粉末的重量的至少0.0625％,基于每m<Sup>2</Sup>/g的待涂覆的颗粒的比表面积。(The coated powder comprises: (a) a particle, and (b) a coating on a surface of the particle comprising (1) a silica moiety, (2) an organoxysilane moiety selected from a monoorganoxysilane moiety, a diorganoxysilane moiety, and a triorganoxysilane moiety, and (3) a poly (dialkyl) siloxane moiety. Of organooxysilane moieties and silica moieties with SiO 2 The equivalent amount by weight is at least 0.0625% of the total coated powder weight, based on the weight per m 2 Per g of the specific surface area of the particles to be coated.)
1. A coated powder comprising:
(a) granules, and
(b) a coating on the surface of the particle comprising
(1) A portion of the silicon dioxide is present,
(2) an organooxysilane moiety selected from the group consisting of a mono-organooxysilane moiety, a bis-organooxysilane moiety, and a tri-organooxysilane moiety, and
(3) a poly (dialkyl) siloxane moiety,
wherein the organooxysilane moiety and the silica moiety are in SiO2The equivalent amount by weight is at least 0.0625% of the total coated powder weight, based on the weight per m2Per g of the specific surface area of the particles to be coated.
2. A method of making a coated powder comprising coating particles with a polymer by polymerizing a composition comprising:
(i) the particles are selected from the group consisting of,
(ii) a first alkoxysilane selected from the group consisting of tetraalkoxysilanes, poly (tetraalkoxysilanes) and mixtures thereof,
(iii) an organoalkoxysilane selected from the group consisting of mono-, di-, tri-organoalkoxysilanes and mixtures thereof, and
(iv) a second alkoxysilane selected from the group consisting of poly (dialkyl) siloxanes and mixtures thereof,
wherein the organooxysilane moiety and the silica moiety are in SiO2The equivalent amount by weight is at least 0.0625% of the total coated powder weight, based on the weight per m2Per g of the specific surface area of the particles to be coated.
3. A coated powder comprising:
(a) granules, and
(b) a coating on the surface of the particle comprising
(1) A portion of the silicon dioxide is present,
(2) an organooxysilane moiety selected from the group consisting of a mono-organooxysilane moiety, a bis-organooxysilane moiety, and a tri-organooxysilane moiety, and
(3) a poly (dialkyl) siloxane moiety,
wherein the coated powder is ultra-photostable.
4. The coated powder or process of any of the preceding claims, wherein the particles comprise at least one selected from ZnO, TiO2And oxides of mixtures thereof.
5. The coated powder or process of any of the preceding claims, wherein the particles have an average particle size of 10-500 nm.
6. The coated powder or process of any of the preceding claims, wherein the particles have an average particle size of 15-150 nm.
7. The coated powder or method of any of the preceding claims, wherein the organooxysilane moieties are each of the formula R1 nSiO4-nWherein n is 1, 2 or 3, and each R1The groups are independently selected from alkyl, alkenyl, alkynyl, aryl and heterocyclyl, and/or each R1The radicals having from 1 to 18 carbon atoms and being independently selected from alkyl, alkenyl and aryl radicals, and/or each R1The groups are independently selected from alkyl, aryl, vinyl, glycidoxyalkyl, methacryloxyalkyl, aminoalkyl and mercaptoalkyl.
8. The coated powder or method of any of the preceding claims, wherein the poly (dialkyl) siloxane moieties are each of the formula O (SiR)2 2)(R2 2SiO)n(SiR2 2) O or O (SiR)2 2)(R2 2SiO)n(SiR2 2)ORcWherein n is an integer of 2 to 14, each R2The radical is alkyl, and RcSelected from the group consisting of H, methyl, ethyl and propyl, and/or organooxysilanes contain propyl silane moieties and the poly (dialkyl) siloxanes include polydimethylsiloxanes.
9. The coated powder or process of any of the preceding claims, wherein the poly (dialkyl) siliconThe alkylene oxide has the formula RcO(SiR2 2)(R2 2SiO)n(SiR2 2)ORcWherein m is an integer of 2 to 14, each R2The radical is alkyl, and each RcThe group is alkyl or H, and/or the poly (dialkyl) siloxane is polydimethylsiloxane or polydiethylsiloxane, and/or the poly (dialkyl) siloxane is linear.
10. The method of any of the preceding claims, wherein polymerizing comprises heating the composition in a sealed evacuated container.
11. The method of any of the preceding claims, wherein polymerizing further comprises:
maintaining the composition at a temperature sufficient to evaporate a portion of the composition;
filling the vessel with a stream of inert gas; and
the vessel is cooled.
12. A dispersion comprising:
(1) the coated powder of any of the preceding claims,
(2) a fluid, and
(3) optionally an antioxidant.
13. A water-in-oil or oil-in-water emulsion comprising the coated powder of any of the preceding claims and a liquid carrier.
14. A cosmetic/dermatological composition comprising the coated powder of any of the preceding claims.
15. A composition comprising the coated powder of any of the preceding claims and an antioxidant.
16. The dispersion or emulsion of any of the preceding claims comprising an antioxidant.
17. A dispersion, emulsion or composition according to any of the preceding claims, further comprising an additional antioxidant.
18. A dispersion, emulsion or composition according to any of the preceding claims wherein the antioxidant is selected from the group consisting of vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytonutrients and antioxidant hormones.
19. A dispersion, emulsion or composition according to any of the preceding claims wherein the antioxidant is selected from ascorbic acid, tocopherol, green tea extract, hydroxytyrosol, retinol, retinal, retinoic acid (retinoic acid) and quercetin dehydrate.
20. A method of protecting skin from light comprising coating the skin with a composition comprising the coated powder, dispersion, emulsion, or composition of any of the preceding claims.
21. A method of protecting a keratin material comprising coating the keratin material with a composition comprising the coated powder, dispersion, emulsion or composition of any preceding claim.
22. A method of protecting human skin comprising coating the skin with a composition comprising the coated powder, dispersion, emulsion or composition of any of the preceding claims.
23. A method of inhibiting lipid peroxidation comprising applying to skin a composition comprising the coated powder, dispersion, emulsion or composition of any of the preceding claims.
24. A method of preventing or reducing wrinkles and folds on skin comprising applying to the skin a composition comprising the coated powder, dispersion, emulsion or composition of any of the preceding claims.
25. A method of preventing loss of skin elasticity comprising applying to the skin a composition comprising the coated powder, dispersion, emulsion or composition of any of the preceding claims.
26. A method of preventing thinning of skin comprising applying to the skin a composition comprising the coated powder, dispersion, emulsion or composition of any of the foregoing claims.
27. A method of protecting an antioxidant comprising mixing the antioxidant with the coated powder, dispersion, emulsion or composition of any of the preceding claims.
28. A dispersion, emulsion or composition according to any preceding claim, wherein the liquid carrier is cosmetically acceptable and/or the liquid carrier comprises a material selected from alkyl benzoates, fatty acid esters, natural product oils, silicone oils and mixtures thereof and/or the liquid carrier comprises a material selected from ethyl benzoates, linear alkyl benzoates, capric/caprylic triglycerides and mixtures thereof.
29. The dispersion of any of the preceding claims, wherein the dispersion when measured at 25 ℃ is 0.1sec-1To 100sec-1Has a viscosity of at most 50,000cP, and/or at 0.1sec when measured at 25 ℃-1To 100sec-1Has a viscosity of at most 10,000cP measured at a shear rate, and/or which further comprises a dispersing aid, and/or which is selected from stearic acid, stearate esters, palmitic acid, palmitate esters, oleic acid, oleate esters, polyhydroxy stearic acid, phosphate esters, linear alkyl substituted amines, triglycerides, polyvinyl glycerides, and mixtures thereof.
30. The coated powder, dispersion, emulsion, or composition of any of the foregoing claims, further comprising a resin.
31. The coated powder, dispersion, emulsion, composition or method of any preceding claim, wherein the particles comprise effect pigments, and/or the effect pigments comprise mica and titanium dioxide.
32. A dispersion, emulsion or composition according to any of the preceding claims, wherein the composition is a paint, stain, coating or ink.
33. The dispersion, emulsion or composition of any of the preceding claims, comprising at least one extract selected from the group consisting of a plant extract, a plant biological extract and a protist extract, and/or the at least one extract is an algae extract.
34. A dispersion, emulsion or composition according to any of the preceding claims, wherein the composition is an anhydrous formulation, and/or the composition is an aerosol foam cream, lotion, paste or gel, and/or the composition is a spray, and/or the composition is a stick or powder.
Background
Particles are added to enhance and modify the properties of many different types of compositions and products. Examples include ultraviolet light (UV) absorbing particles, pigments, colorants, fillers, matting agents, optical diffusing particles, abrasion resistant particles, viscosity modifiers, magnetic particles, and reflective particles.
Oxide-containing particles are particularly suitable as additives, in particular particles containing zinc oxide, titanium oxide, silicon oxide, aluminum oxide, iron oxide and/or rare earth metal oxides. These oxides are thermodynamically stable, generally do not react with oxygen that is prevalent in the environment, and are less reactive with water than many other oxide and non-oxide materials. These oxide materials have been used as pigments and abrasives for hundreds of years.
Particles composed of certain metal oxides (most notably titanium oxide) are of particular interest because they are generally colorless and transparent to visible light and provide protection against exposure to UV light; however, these oxides tend to have poor photostability due to their photocatalytic behavior. Metal oxides exposed to UV radiation produce an increase in free radicals. These free radicals can cause instability of the formulation itself. In addition, free radicals can lead to the formation of hydroperoxides and other peroxide radicals that are known to cause contact dermatitis and severe allergic reactions. These radicals can also trigger chain reactions, generating Reactive Oxygen Species (ROS). These highly reactive derivatives react with cellular components including lipid membranes and are thought to be the source of photoaging and skin cancer that may appear later in life. ROS deplete and destroy the non-enzymatic and enzymatic antioxidant defense systems and cause permanent gene damage. Other components in the cosmetic composition may also have low photostability, thereby generating additional free radicals on the skin surface.
It has been found that coating the particles improves the photostability of the particles. The coated (coated) powder is used for the preparation of cosmetic compositions for application to the skin, for example compositions for protecting the skin from UV radiation (e.g. sunscreens).
The particles can be coated to produce a coated powder with chemical stability, photostability, and the ability to form high weight loaded dispersions with low viscosity. For example, it was found that the coating (cladding) resulted in chemical stability, light stability, and that such coated particles could be used to form high weight loaded dispersions with low viscosity. The coating comprises (1) a silica moiety, (2) an organoxysilane moiety selected from the group consisting of a monoorganoxysilane moiety, a diorganooxysilane moiety, and a triorganoxysilane moiety, and (3) a poly (dialkyl) siloxane moiety. See, for example, U.S. patent No.9,139,737.
Antioxidants commonly used in cosmetic skin care products undergo an oxidation process under UV radiation, thereby losing their effectiveness. The addition of a coated powder that blocks and absorbs UV radiation can reduce oxidation of the antioxidant by UV radiation. However, many UV blocking particles exhibit photocatalytic activity, such as zinc oxide and titanium oxide, and can cause the generation of peroxide radicals inside the cosmetic composition. This may compromise the stability and efficacy of the antioxidant due to the rapid reaction between the antioxidant and the free radicals or products produced from the free radicals.
Disclosure of Invention
In a first aspect, the present invention is a coated powder comprising: (a) a particle, and (b) a coating on a surface of the particle comprising (1) a silica moiety, (2) an organoxysilane moiety selected from a monoorganoxysilane moiety, a diorganoxysilane moiety, and a triorganoxysilane moiety, and (3) a poly (dialkyl) siloxane moiety. Of organooxysilane moieties and silica moieties in SiO2The equivalent amount by weight is at least 0.0625% of the total coated powder weight, based on the weight per m2Per g of the specific surface area of the particles to be coated.
In a second aspect, the invention is a dispersion comprising (1) a coated powder, (2) a fluid, and (3) an antioxidant.
In a third aspect, the present invention is a method of making a coated powder comprising coating particles with a polymer by polymerizing a composition comprising: (i) particles, (ii) a first alkoxysilane selected from the group consisting of tetraalkoxysilanes, poly (tetraalkoxysilanes), and mixtures thereof, (iii) an organoalkoxysilane selected from the group consisting of mono-, di-, tri-organoalkoxysilanes, and mixtures thereof, and (iv) a second alkoxysilane selected from the group consisting of poly (dialkyl) siloxanes, and mixtures thereof. Of organooxysilane moieties and silica moieties in SiO2The equivalent amount by weight is at least 0.0625% of the total coated powder weight, based on the weight per m2Per g of the specific surface area of the particles to be coated.
In a fourth aspect, the present invention is a super light stable coated powder.
In a fifth aspect, the invention is a method of protecting skin from light comprising coating the skin with a composition comprising the coated powder.
In a sixth aspect, the present invention is a method of protecting a keratin material comprising coating the keratin material with a composition comprising the coated powder.
In a seventh aspect, the invention is a method of protecting skin from light comprising coating the skin with the dispersion.
In an eighth aspect, the present invention is a method of inhibiting lipid peroxidation comprising applying to the skin a composition comprising the coated powder.
In a ninth aspect, the invention is a method of preventing or reducing wrinkles and folds on skin comprising applying to the skin a composition comprising the coated powder.
In a tenth aspect, the invention is a method of preventing loss of skin elasticity comprising applying to the skin a composition comprising the coated powder.
In an eleventh aspect, the present invention is a method of preventing skin thinning comprising applying to the skin a composition comprising the coated powder.
Definition of
The term "nanoparticle" means a particle having a particle size of at most 999 nm. Preferably, the nanoparticles have a particle size of 10nm to 500 nm.
The term "microparticles" means particles having a particle size of 1 μm to 100 μm.
Unless otherwise indicated, the term "particle size" means the average diameter of an image of a particle as viewed by an electron microscope. The term "average particle size" means the average of the particle sizes of a collection of particles.
By "high solids content" or "high weight loading" is meant that the composition concerned has at least 50% by weight of solid particles.
"alkyl" (or alkyl- (alk-) or alk-) refers to a substituted or unsubstituted straight, branched or cyclic hydrocarbon chain, preferably containing from 1 to 22 carbon atoms. More preferred alkyl groups are lower alkyl groups, e.g., alkyl groups containing 1 to 10 carbon atoms. Preferred cycloalkyl groups have 3 to 10, preferably 3 to 6 carbon atoms in their ring structure. Suitable examples of unsubstituted alkyl groups include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tert-butyl, sec-butyl, cyclobutyl, pentyl, cyclopentyl, hexyl and cyclohexyl.
"alkenyl" means a substituted or unsubstituted, straight, branched, or cyclic unsaturated hydrocarbon chain containing at least one double bond, and preferably having 2 to 22, more preferably 2 to 6 carbon atoms. Exemplary unsubstituted alkenyl groups include vinyl (or vinyl) (-CH ═ CH)2) 1-propenyl, 2-propenyl (or allyl) (-CH)2-CH＝CH2)1, 3-butadienyl (-CH ═ CHCH ═ CH)2) 1-butenyl (-CH ═ CHCH)2CH3) Hexenyl, pentenyl and 1,3, 5-hexanetrienyl. Preferred cycloalkenyl groups contain 5 to 8 carbon atoms and at least one double bond. Examples of cycloalkenyl groups include cyclohexadienyl, cyclohexenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclohexadienyl, cycloheptadienyl, and cyclooctatrienyl.
"alkynyl" refers to a substituted or unsubstituted, straight, branched, or cyclic unsaturated hydrocarbon chain containing at least one triple bond, and preferably having from 2 to 22, more preferably from 2 to 6 carbon atoms.
"aryl" means any aromatic carbocyclic or heteroaromatic group, preferably having 3 to 10 carbon atoms. The aryl group can be cyclic (e.g., phenyl (or Ph)) or polycyclic (e.g., naphthyl), and can be unsubstituted or substituted. Preferred aryl groups include phenyl, naphthyl, furyl, thienyl, pyridyl, indolyl, quinolinyl, or isoquinolinyl.
"heterocyclic group" means a stable, saturated, partially unsaturated or aromatic ring, preferably containing 5 to 10, more preferably 5 or 6 atoms. The ring may be substituted 1 or more times (preferably 1, 2, 3,4 or 5 times) with a substituent. The rings may be monocyclic, bicyclic or polycyclic. The heterocyclic group consists of carbon atoms and 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur. The heteroatom may be protected or unprotected. Examples of useful heterocyclic groups include substituted or unsubstituted acridine, benzothiazoline, benzimidazole, benzofuran, benzothiophene, benzothiazole, benzothiophenyl, carbazole, cinnoline, furan, imidazole, 1H-indazole, indole, isoindole, isoquinoline, isothiazole, morpholine, oxazole, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, pteridine, purine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, quinazoline, quinoline, quinoxaline, thiazole, 1,3, 4-thiadiazole, thiophene, 1,3, 5-triazine and triazole
By "substituted" is meant that the moiety contains at least one, preferably 1-3 substituents. Suitable substituents include hydrogen (H) and hydroxy (-OH), amino (-NH), and like2) Oxy (-O-), carbonyl (-CO-), mercapto (-SH), alkyl, alkenyl, alkynyl, alkoxy (-OR), halogen, nitrile, nitro, aryl and heterocyclic groups.
Titanium dioxide (TiO)2) The light stability of (c) was measured using the following test. This test is called "TiO2Photostability test ". First, a stock solution of 25% resorcinol in ethanol was prepared. 8.9g (+ -0.01 g) of Finsolv TN and 0.1g (+ -0.005 g) of Hostaphat KW340D were added to a glass scintillation vial. The capped vial was then placed in an oven at 50 ℃ until the Hostaphat KW340D dissolved and the solution was homogeneous (approximately 15 minutes). After the bottle is removed from the oven, the bottle is removed1.0g (+ -0.01 g) of the coated titanium dioxide powder was added to the solution. The solution was placed in an ultrasonic bath and sonicated for 15 minutes. 1.0g (+ -0.01 g) of 25% resorcinol in ethanol from the first step was added to the scintillation vial and mixed well by hand until homogeneous. The quartz cuvette was filled with the mixture and covered with a Teflon lid. The mixture is then tested using a MiltonRoy Color Mate Color Colorimeter or a suitable equivalent Colorimeter. The colorimeter was calibrated using white tile calibration standards prior to testing the mixtures. After recording the results of the "pre-irradiation sample", the cuvette containing the sample was placed in a QUV weathering tester. The UVB bulb was then used at 1.23Wm in a Q-Labs QUV aging tester-2s-1The mixture was exposed to UV light precisely for 15 minutes at a constant temperature of 50 ℃. The test mixture was then removed to allow immediate color measurement in a colorimeter. Photostability can be expressed as the total color change (Δ E in la b color space) relative to the standard for a specified UV exposure time. Δ E is calculated from the following expression, defined according to CIE 76:
wherein
To test for TiO removal2The photostability of most compositions (components) other than those described, such as zinc oxide (ZnO), can be tested using the following test. This test is called the "DPPH photostability test". First, 0.025g ± 0.001g of coated ZnO powder was added to four 50mL disposable plastic beakers. 0.0125% DPPH (bis (phenyl) - (2,4,6-trinitrophenyl) imido ammonium (azonium) (di (phenyl) - (2,4,6-trinitrophenyl) also known as diphenylpicrylhydrazino; CAS number 1898-66-4) was prepared in BCS (ethylene glycol butyl ether) solution. 19.975 g. + -. 0.001 of 0.0125% DPPH in BCS solution was added to each beaker containing the coated powder. It was mixed well with a glass stir bar and each beaker was sonicated for 20 seconds to ensure good dispersion of the powder throughout the solution. After sonication, the samples were transferred to a labeled scintillation vial. The pre-irradiated samples were measured on a calibrated Milton ray Color Mate Colorimeter or a suitable equivalent Colorimeter. After the measurement is performed, the sample is irradiated. The UVA or UVB bulbs were then used at 0.35Wm in a Q-Labs QUV aging tester-2s-1The test mixture was accurately exposed to UV light for 10 minutes at a constant temperature of 50 ℃. UVA bulbs were used to test particles that filter UVA radiation, while UVB bulbs were used to test particles that filter UVB radiation. Finally, the irradiated sample was measured on a colorimeter. In this case, the photostability after UV exposure is indicated by the persistence of violet color due to the absorption band of the dye at 520 nm. Photostability can be expressed as the total color change (Δ E in la b color space) relative to the standard for a specified UV exposure time. Δ E is calculated from the following expression, defined according to CIE 76:
wherein
A modified version of the foregoing test was used to measure the light stability of the coated effect pigments. This test is referred to as the "effect pigment light stability test". This modification is necessary to eliminate the noise in the colorimetric measurement caused by the reflectance of the interference pigments themselves in the sample. The test is described below. 0.0125% DPPH (bis (phenyl) - (2,4,6-trinitrophenyl) imido ammonium (azonium), also known as diphenylpicrylhydrazino; CAS number 1898-66-4) was prepared in BCS (ethylene glycol butyl ether) solution. An aliquot of 20ml DPPH solution was transferred to a labeled scintillation vial. The samples were measured on a calibrated Milton ray Color MateCoolor or suitable equivalent colorimeter. Next, 0.025g ± 0.001g of the coated effect pigment powder was added to four 50mL disposable plastic beakers. 19.975 g. + -. 0.001 of 0.0125% DPPH in BCS solution was added to each beaker containing the coated powder. It was mixed well with a glass stir bar and each beaker was sonicated for 20 seconds to ensure good dispersion of the powder throughout the solution. After sonication, each sample was transferred to a labeled scintillation vial. The UVB bulb was then used at 0.35Wm in a Q-Labs QUV aging tester-2s-1The test mixture was accurately exposed to UV light for 10 minutes at a constant temperature of 50 ℃. The irradiated sample is then filtered through a suitable 1 μm filter to remove effect pigments, which can interfere with color measurements. Finally, the filtered irradiated sample was measured on a colorimeter. As previously described, photostability after UV exposure is indicated by the persistence of violet color due to the absorption band of the dye at 520 nm. Light stabilityCan be expressed as the total color change (Δ E in la b color space) relative to the standard for a specified UV exposure time. Δ E is calculated from the following expression, defined according to CIE 76:
wherein
Chemical reactivity was measured using the following chemical reactivity test. A20 g glass vial was filled with 4.5g of a stock solution of 5% n-propyl gallate (3,4, 5-trihydroxybenzoic acid propyl ester, Aldrich) in isopropanol. One gram of half of the powder to be evaluated was added to the glass bottle. The vial is then agitated, for example by placing it in a bath sonicator for 30 seconds. The mixture was allowed to stand for 30 minutes. The sample was then gently mixed using a pipette and transferred to a cuvette (polycarbonate, polystyrene or glass) with an optical path length of 1 cm. Total Color change (. DELTA.E) was then measured against the factory white standard using a Data Color-International Spectraflash SF3000 Colorimeter. Chemical reactivity is expressed as the total color change (Δ Ε). A powder is considered to be chemically reactive in an application if the chemical reactivity test results in the appearance of a brownish yellow color with a delta E value of greater than 20.
Hydrophobicity was measured using the following hydrophobicity test (this test is a visible water floating test commonly used in the cosmetic industry and is described in U.S. patent No.4,454,288). About 30mL of deionized water was placed in a glass jar. About 3.0g ± 0.30g of the powder to be tested was added to the glass jar. The glass jar was tightly sealed and the sample was rotated about 4 to 5 times and shaken vigorously 4 to 5 times to achieve intimate contact between the water and the powder. A powder is considered to be hydrophobic if it is buoyant (floats on the surface of the water) and after 15 minutes the water is clear. The sample is slightly hydrophobic if the powder is not buoyant but the water is clear after 15 minutes, or if the powder is buoyant but the water is not clear after 15 minutes.
The flowability of the dispersion of the powder was measured using the following run-off distance test. In ethylhexyl benzoate (
The viscosity of the dispersion of the powder was measured using the following viscosity test. In capric/caprylic triglycerides (C), (D), (E), (
The specific surface area of the particles is expressed in m2The/g is measured and determined using the Brunauer-Emmett-Teller (BET) method.
SiO2Equivalent means that all silicon in the coating is converted to SiO2SiO present later2The weight of (c). For example, partially "in SiO2Equivalent weight amounts "means that all silicon forming the coating is converted to SiO2And measured to determine the percentage of each portion in the coated powder.
Antioxidant capacity (AP) was measured using the AP method developed by Gematria laboratories (Berlin, DE). The method provides for determining the overall antioxidant capacity of active ingredients (i.e., plant extracts, vitamins, etc.) by monitoring the reducing activity of DPPH, a stable test radical, with Electron Spin Resonance (ESR) spectroscopy. The AP method utilizes the well-known DPPH method, the main difference being that both antioxidant capacity and antioxidant activity are used to characterize the antioxidants tested. For this purpose, the active ingredients at different concentrations were analyzed in real time by ESR spectroscopy, and the reduction in the spin of the test radicals was tracked accordingly for each group. With this innovative technique, important kinetic information is additionally obtained, which is completely ignored by most other test systems. Thus, both the reaction time and the reduction potential of the antioxidant contribute to the calculation of AP.
AP ═ (RA × N spin)/(w)c×tr)
AP can be represented by the above equation, where RA is a constant reduction amplitude (1/e)2) N spin is from DPAmount of reduced free radical, w, characterized by free electrons (spins) of PHcIs the characteristic weight of the antioxidant product and trIs the reduction time (Jung et al, 2006). The resulting AP is expressed in Antioxidant Units (AU), where 1AU corresponds to the activity of a solution of 1ppm pure vitamin C (ascorbic acid) as a reference. This method allows the use of a rapid and universally applicable technique for measuring AP for a series of very different classes of substances.
Drawings
FIG. 1 is a graph of the relative percentage of free radicals as a function of UV radiation time.
Fig. 2 is a graph of the relative AP values of various antioxidants after UV irradiation when combined with ZnO with an octyltriethoxysilane coating or ZnO with a multifunctional coating.
Detailed Description
TiO2And other selected metal oxides would be desirable for use in UV protective topical skin compositions and other UV protective coatings. However, to be commercially desirable, such coated powders need to be (a) light stable so that they do not significantly change color during exposure to UV light; (b) is chemically non-reactive such that it does not react with or discolor the composition during storage; (c) high weight loading dispersions can be formed that allow high SPF values with minimal introduction of carrier fluid, and cost effective transportation and storage, but which are sufficiently low in viscosity to be easily handled and mixed when preparing consumer compositions.
Although the multifunctional coated powders and high dispersion solids described in US patent No 9,139,737 are a significant improvement over other existing coated powders, they can be further improved by increasing the light stability of the coated powder. Furthermore, the addition of an antioxidant to the UV protecting composition will reduce the amount of induced free radicals caused by UV radiation exposure.
In addition to being chemically stable and having the ability to form high weight loaded dispersions, the present application utilizes coated powders that have excellent photostability. The coated powder is ultra-light stable. The coated powder can be used to form a composition containing an antioxidant and which reduces antioxidant loss when exposed to light.
The coated powder is polymer-coated particles prepared by polymerizing a composition containing particles and at least three components: (A) a first alkoxysilane selected from the group consisting of tetraalkoxysilanes, poly (tetraalkoxysilanes), and mixtures thereof, (B) an organoalkoxysilane selected from the group consisting of mono-organoalkoxysilanes, bis-organoalkoxysilanes, tri-organoalkoxysilanes, and mixtures thereof, and (C) a second alkoxysilane selected from the group consisting of poly (dialkyl) siloxanes, and mixtures thereof.
The coating formed contained portions corresponding to each of the three components: (A) a silica moiety, (B) an organoxysilane moiety selected from the group consisting of a monoorganoxysilane moiety, a diorganooxysilane moiety, and a triorganoxysilane moiety, and (C) a poly (dialkyl) siloxane moiety. The coated powder can be used to form a dispersion in a cosmetically acceptable fluid that has high solids (high solids) and low viscosity.
When at least a specific amount of Si (in SiO) is present from all silanes2Weight equivalent) was found to have excellent photostability when present in the coating. The composition range of each component is based on SiO2And (3) equivalent weight. SiO derived from all silane moieties (i.e., silica moieties and organooxysilane moieties)2Must be greater than or equal to at least 0.0625% by weight of the total coated powder, per m2Per g of the specific surface area of the particles to be coated. The silane moieties may be mono-, di-, tri-, and tetra-functional.
The coated powder can be used to form a dispersion in a fluid having a high solids and a low viscosity. The dispersions are useful for preparing cosmetic compositions for application to the skin, for example compositions for protecting the skin from UV radiation (e.g. sunscreens). Materials considered to be cosmetically acceptable are those listed as INCI (International Nomenclature of Cosmetic Ingredients). Examples of cosmetically acceptable fluids are Ethylhexyl Benzoate (EB), Linear Alkyl Benzoates (LAB), caprylic/capric triglyceride (CCT), squalane, natural product oils and various silicone fluids. Natural product oils are oils derived from seeds, legumes, fruits, flowers, bark, leaves, and the like, including derivatives thereof. Examples of natural product oils are olive oil and soybean oil.
The coated powders and dispersions of the coated powders can be used in a variety of products. It can be added to dermatological compositions to provide UV protection to the skin, especially in the presence of TiO2And ZnO; the coated powder may also be added to compositions such as inorganic pigments. The coated powder can also be added to shampoos, lotions, gels, hair sprays, aerosol foam creams or lotions for washing, dyeing and styling the hair, while also providing UV protection to the hair. It can be added to paints, sealants and other coatings for wood, plastics and other building materials; also in the presence of TiO2And ZnO, UV protection is provided. It can also be added to resins, filled polymers and plastics, and inks. When the metal oxide is magnetic, a magnetic fluid may be prepared, for example in the case of certain iron oxides and rare earth oxides.
The particles preferably comprise metal oxides such as zinc oxide, titanium oxide, silicon oxide, aluminum oxide, iron oxide, bismuth oxide, cerium oxide, rare earth oxides, binary and ternary mixed metal oxides that absorb infrared light, and mixtures thereof. Examples include ZnO, TiO2，SiO2，Al2O3，Fe2O3，CeO2，SnO2Zirconium-cerium oxide, mixed zirconium-rare earth oxides containing cerium, aluminosilicates (including amorphous aluminosilicates, crystalline aluminosilicates and pumice) and other silicates, aluminum oxides including alumina, aluminosilicates, magnesium aluminum oxides (e.g., spinel), zinc oxide doped with trivalent metal cations (including aluminum doped ZnO), Antimony Tin Oxide (ATO), Indium Tin Oxide (ITO), fluorine doped tin oxide and doped tungsten oxide. Oxide minerals such as mica and natural mineral oxides may also be used. It is also possible to use a metal,other ceramic compositions, including carbides and nitrides and mixtures thereof, and mixtures with oxides.
The particles may be effect pigments. The effect pigments are typically plate or platelet-shaped pigment particles coated with a thin layer of a second material having a higher refractive index. The composition of the bottom sheet is typically mica, synthetic mica, silica or alumina. The coating is typically titanium dioxide (typically in the anatase form), iron oxide or bismuth oxychloride. The color of the pigment is controlled by the thickness of the coating. The size of the effect pigments is generally from 1 to 100. mu.m. The pigments are also known as pearlescent pigments and interference pigments. These Materials are commercially available (from EMD Performance Materials)
Preferably the particles have a particle size of up to 999nm, including particle sizes of up to 100, 200 and 500nm, more preferably a particle size of 10nm to 500nm, most preferably a particle size of 15nm to 250nm, for example 20, 30, 40, 50, 60, 70, 80, 90 and 100 nm. Preferably, the particles have an average particle size of at most 999nm, including average particle sizes of at most 100, 200 and 500nm, more preferably an average particle size of from 10nm to 500nm, most preferably an average particle size of from 15nm to 250nm, for example 20, 30, 40, 50, 60, 70, 80, 90 and 100 nm. Alternatively, the particle size of the particles may be 1 μm to 100 μm. Preferably, the average size of the particles is from 1 to 10 μm.
The particles may be coated by polymerizing the composition, preferably in the absence of a solvent and with at least some of the composition in the gas phase. The composition includes (a) a first alkoxysilane selected from the group consisting of tetraalkoxysilanes, poly (tetraalkoxysilanes), and mixtures thereof, (B) an organoalkoxysilane selected from the group consisting of mono-, di-, tri-organoalkoxysilanes, and mixtures thereof, and (C) a second alkoxysilane selected from the group consisting of poly (dialkyl) siloxanes, and mixtures thereof.
Preferably, the first alkoxysilane is present in an amount of 0.1 to 8% by weight of the coated powder, more preferably 0.5 to 7% by weight of the coated powder, and most preferably 1.0 to 5% by weight of the coated powder, including 1.5, 2, 2.5, 3, 3.5, 4 and 4.5%. Preferably, the organoalkoxysilane is present in an amount of 0.01 to 5% by weight of the coated particle, more preferably 0.05 to 3% by weight of the coated powder, and most preferably 0.1 to 1% by weight of the coated powder, including 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9%. Preferably, the second alkoxysilane is present in an amount of 0.1 to 10 wt% of the coated powder, more preferably 0.5 to 5 wt% of the coated powder, and most preferably 0.75 to 2.5 wt% of the coated powder, including 1.0, 1.25, 1.5, 1.75, 2.0 and 2.25%.
The first alkoxysilane may be a tetraalkoxysilane, a poly (tetraalkoxysilane), or a mixture thereof. The tetraalkoxysilane is of the formula (R)aO)4A compound of Si, wherein each RaAre organic radicals which may be identical or different and each R isaPreferred are alkyl groups having from 1 to 22 carbon atoms, more preferably from 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms, including methyl, ethyl and propyl. One example is Tetraethoxysilane (TEOS). Poly (tetraalkoxysilane) is an oligomer of one or more tetraalkoxysilanes formed by partial hydrolysis. Preferably, the poly (tetraalkoxysilane) contains from 2 to 14 monomer units, more preferably from 4 to 10 monomer units, including 5, 6, 7, 8 and 9.
The first alkoxysilane may contain a silica moiety. The silica moiety being Si (O) bonded to 4 atoms4Radicals and may also be present in clusters (cluster), for exampleSuch as [ OSi (O)2)]nO, wherein n is 2 to 14, more preferably 4 to 10, including 5, 6, 7, 8 and 9.
The organoalkoxysilane is selected from the group consisting of a mono-organoalkoxysilane, a bis-organoalkoxysilane, a tri-organoalkoxysilane, and mixtures thereof. The organoalkoxysilane is of the formula R1 nSi(ORb)4-nWherein n is 1, 2 or 3. R1Are organic groups such as alkyl (e.g., straight chain alkyl, branched chain alkyl, cyclic alkyl, glycidoxyalkyl, methacryloxyalkyl, and aminoalkyl), aryl, vinyl, and heteroaryl. R1Examples of (b) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Preferably, R1Containing from 1 to 22 carbon atoms, more preferably from 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms. Each RbAre organic radicals which may be identical or different and each R isbPreferred are alkyl groups having from 1 to 22 carbon atoms, more preferably from 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms, including methyl, ethyl and propyl. An example of an organoalkoxysilane is triethoxyoctylsilane.
The organoalkoxysilane may contain an organooxysilane moiety. The organooxysilane moiety is R bonded to "4-n" other atoms1 nSi(O)4-nWherein n is an integer of 1, 2 or 3. R1Are organic groups such as alkyl (e.g., straight chain alkyl, branched chain alkyl, cyclic alkyl, glycidoxyalkyl, methacryloxyalkyl, and aminoalkyl), aryl, vinyl, and heteroaryl. R1Examples of (b) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Preferably, R1 contains 1 to 22 carbon atoms, more preferably 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms. Organooxysilane moietiesAn example of (b) is octyl silane.
The second alkoxysilane is selected from the group consisting of poly (dialkyl) siloxanes and mixtures thereof. The poly (dialkyl) siloxane is preferably of formula RcO(SiR2 2)(R2 2SiO)n(SiR2 2)ORcWherein n is an integer from 2 to 14, preferably from 4 to 10, including 5, 6, 7, 8 and 9. Each R2Is an organic radical, e.g. methyl, ethyl or phenyl, and each RcIs an end capping group, such as alkyl, including methyl, ethyl, and propyl to form alkoxy, or H to form hydroxyl; both hydroxyl and alkoxy groups are reactive groups. Also possible are 1 to 3R2The radicals are hydroxyl and/or alkoxy. R2And RcEach independently preferably contains from 1 to 22 carbon atoms, more preferably from 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms. Preferably, the poly (dialkyl) siloxane is polydimethylsiloxane or polydiethylsiloxane. Preferably, the poly (dialkyl) siloxane has a weight average molecular weight of 200 to 10,000, more preferably 500 to 5,000.
The second alkoxysilane may contain a poly (dialkyl) siloxane moiety. The poly (dialkyl) siloxane moiety being O (SiR) bonded to other atoms2 2)(R2 2SiO)n(SiR2 2) O or O (SiR)2 2)(R2 2SiO)n(SiR2 2)ORcGroups wherein n is an integer from 2 to 14, preferably from 4 to 10, including 5, 6, 7, 8 and 9. Each R2Independently an organic group, such as methyl, ethyl or phenyl, and each RcIs an end capping group, such as alkyl, including methyl, ethyl, and propyl to form alkoxy, or H to form hydroxyl; both hydroxyl and alkoxy groups are reactive groups. Also possible are 1 to 3R2The radicals are hydroxyl and/or alkoxy. R2And RcEach independently preferably contains from 1 to 22 carbon atoms, more preferably from 1 to 10 carbon atoms, including 2, 3,4,5, 6, 7, 8 and 9 carbon atoms. Preferably, the poly (dialkyl) siloxane moiety is a polydimethylsiloxane moiety or a polydiethylsiliconAn alkylene oxide moiety.
Typically, the particles and the three components of the composition are thoroughly mixed together and then placed in a sealed container. The vessel is then evacuated and heated to a temperature at which at least two components form a vapor. The temperature is maintained for a sufficient time to allow polymerization and formation of a coating on the particles, preferably with continuous mixing during the polymerization process. Conducting the polymerization reaction for a longer duration allows for more complete coverage of the particle surface. The vessel is then filled with a stream of inert gas which allows volatile byproducts, such as alcohol, to be removed and subsequently allowed to cool to room temperature. The resulting polymer coating contains portions of each of three silanes: (1) a silica moiety, (2) an organoxysilane moiety selected from the group consisting of a monoorganoxysilane moiety, a diorganooxysilane moiety, and a triorganoxysilane moiety, and (3) a poly (dialkyl) siloxane moiety.
Preferably, the temperature of polymerization is from 80 ℃ to 120 ℃, more preferably from 90 ℃ to 110 ℃, including 92, 94, 96, 98, 100, 102, 104, 106 and 108 ℃. The time of polymerization is preferably 0.5 to 10 hours, more preferably 1 to 6 hours, including 2, 3,4 and 5 hours.
After the polymerization process, the coated powder was heated to 120 ℃ to evaporate any volatile compounds. This drying reduces the weight by a very small amount. For determining the SiO of the silicon in the coating2Equivalent amount, heating the coated powder to a temperature of 600 ℃ to 800 ℃. The process may be carried out in a hot gravimetric plant or other plant. Combustion in air to 600 ℃ or 800 ℃ will convert all silicon containing moieties in the coated powder to SiO2. The composition of the ignited powder can be confirmed by various analytical methods.
A variety of techniques can be used to analyze the coated powders of the present invention. The inorganic oxide particles can be dissolved with various acids, the relative amounts of polymer and inorganic oxide determined, and the remaining polymer coating can then be examined using FTIR (Fourier transform Infrared Spectroscopy) to determine the presence of different fractions and the relative amount of each fraction. Other techniques, such as mass spectrometry, TGA (thermogravimetric analysis) or ICP (inductively coupled plasma spectrometry) can also be used to establish the ratio relative to the monomer units. The baseline can be established by using standards of known composition.
The coated powder can also be analyzed by solid state NMR and examined13C and29si NMR signals to determine the presence of different moieties and the relative amounts of each moiety. Further, the inorganic oxide particles may be dissolved with various acids, and the remaining polymer coating may be analyzed by NMR to check13C and29si NMR signals to determine the presence of different moieties and the relative amounts of each moiety. The baseline can be established by using standards of known composition.
The properties of the coated powder can be checked using a photostability test, a chemical reactivity test, and a hydrophobicity test. If the light stability of the coated powder is Δ E ≦ 15, preferably Δ E ═ 1 to 14, including Δ E ═ 2, 3,4,5, 6, 7, 8, 9, 10, 11, 12, and 13, then the coating is applied to TiO2The coated powder was ultra-photostable under the photostability test. The coated powder is ultra-light stable under the DPPH light stability test if the light stability of the coated powder is Δ E ≦ 4.5, preferably Δ E ≦ 1 to 4, including Δ E ≦ 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, and 1.0. The coated powder is ultra-light stable under the effect pigment light stability test if the light stability of the coated powder is Δ E ≦ 1.15, preferably Δ E ≦ 0.5 to 1.0, including 1.05, 0.95, 0.85, 0.75, 0.65, and 0.55. Preferably, the chemical reactivity of the coated powder is Δ E ═ 0 to 20, more preferably Δ E ═ 0 to 17, most preferably Δ E ═ 0, 1, 2, 3,4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. The coated powder is preferably hydrophobic or slightly hydrophobic, most preferably hydrophobic.
The coated powder can be used to form a dispersion with a non-polar liquid, preferably a cosmetic oil, such as capric/caprylic triglyceride, linear alkyl benzoate, ethylhexyl benzoate, natural product oils and silicone oils. Preferably, the dispersion contains at least 40 wt% of the coated powder (solids), more preferably at least 50 wt% of the coated powder (solids), including at least 55 wt% of the coated powder (solids), at least 60 wt% of the coated powder (solids), and at least 65 wt% of the coated powder (solids), such as 50-65 wt% of the coated powder (solids) and 55-60 wt% of the coated powder (solids). Such dispersions can be prepared by a variety of conventional mixing methods, including mixing with a rotor-stator machine, planetary mixing, high pressure homogenizer, ultrasonic mixing, and media milling. A co-emulsifier or dispersant may be included in the dispersion. Examples include tricereareth-4phosphate (Hostaphat KW 340D; Clariant) at solids of 5-15 wt.%.
Surprisingly, the high solids dispersion of the coated powder has a relatively low viscosity. Preferably, the viscosity is at most 60,000cP, more preferably at most 30,000cP, most preferably at most 6,000 cP. Examples include viscosities of 1,000 to 50,000cP and 5,000 to 30,000 cP.
A preferred aspect of the invention comprises adding an antioxidant to the dispersion containing the coated powder. When exposed to UV radiation, antioxidants are oxidized, resulting in a decrease in antioxidant capacity. In addition, zinc oxide and other metal oxides are photoreactive and generate free radicals upon exposure to UV radiation. The metal oxide, in combination with the antioxidant, has a greater loss of AP than the antioxidant alone. However, by combining the coated powder with an antioxidant, the relative AP value of the dispersion remains higher than the relative AP value of the antioxidant alone. Because the coated powder is ultra-light stable, the combination of coated powder and antioxidant together exhibit a synergistic effect. Antioxidants can be effective because UV radiation is blocked or absorbed by the particles, thereby maintaining the AP value.
The dispersion may contain one or more antioxidants. Antioxidants can include vitamins, antioxidant minerals, antioxidant proteins, antioxidant enzymes and coenzymes, phytonutrients, antioxidant hormones, mycosporine-like amino acids (MAA), seaweed-derived antioxidants, and other types of antioxidants. Antioxidants can be water soluble, fat soluble or both lipid and water soluble. Suitable vitamins include vitamin a (including retinoic acid and carotenoids), vitamin C (ascorbic acid), vitamin E (tocopherol), and vitamin K. Suitable retinoids include retinol, retinoic acid (tretinoin), retinal, and retinyl palmitate. Suitable minerals include copper, manganese, iodide, and zinc. Suitable enzymes and coenzymes include melatonin, superoxide dismutase, catalase, and glutathione peroxidase. Suitable phytonutrients include carotenoids, flavonoids, phenolic acids, and non-flavonoid phenols. Suitable carotenoids include alpha-carotene, retinol, astaxanthin, beta-carotene, canthaxanthin, lutein, lycopene and zeaxanthin. Suitable flavonoids include hindered phenols, apigenin, luteolin, tangeretin, isorhamnetin, kaempferol, myricetin, proanthocyanidins, quercetin, eriodictyol, hesperetin, naringenin, catechin, gallocatechin, epicatechin, epigallocatechin, thearubigin, daidzein, genistein, glycitein, resveratrol, pterostilbene, anthocyanidins, delphinidins, malvidins, pelargonidin and petunias. Suitable phenolic acids include phenols, polyphenols, alkylated phenols and hindered phenols. Suitable phenols include butylated hydroxyanisole, butylated hydroxytoluene, cannabinoids, capsaicin, carvacrol, cresol, estradiol, eugenol, gallic acid, guaiacol, thymol, tyrosine and sesamol. Gallic acid includes salts and esters of gallic acid, also known as gallic acid esters (salts). Suitable non-flavonoid phenols include curcumin, flavonoid lignans, xanthone and eugenol. Suitable mycosporine-like amino acids (MAAs) include mono-substituted MAAs, such as mycosporine-glycine and mycosporine-taurine, di-substituted MAAs, such as palythinic acid and shinorine, and derivatized MAAs, such as palythine-threonine sulfate and palythine-threonine glycoside. Examples of suitable MAAs can be found in Wada et al (2015). Antioxidants derived from seaweed include ascorbate, glutathione, brown algae polyphenols, goosefoot phenol (eckol), eckstolonol, prenyltoluquinone, tetraprenyltoluquinone, sarginnobrol a, fucodiphlethol, terpenes, phycocyanin, phycobilin, fucoxanthin, brown algae polyphenols (phthalonins), and lutein. Other potential organic antioxidants include bilirubin, citric acid, oxalic acid, phytic acid, n-acetylcysteine, uric acid, green tea, hydroxy-tyrosol, dihydro-quercetin, ubiquinone, glutathione, alpha-lipoic acid, folic acid, ellagic acid, caffeic acid, and phytoestrogens. The above antioxidants also include any salt, ester or acid form of the antioxidant.
The dispersion may contain one or more plant extracts. "plant extract" is a substance obtained from a plant. Preferably, the plant extract imparts color. The plant extract must be compatible with the non-aqueous composition; is stable in the air; the skin is not polluted; the use amount is non-irritant to the skin; and the using amount is nontoxic. The purity level of the plant extract is at least 95%. Examples of suitable plant extracts include curcumin, lycopene, beta-carotene, lutein, zeaxanthin, mesozeaxanthin and anthocyanins. Sources of curcumin include turmeric. Sources of lycopene include beet, cherry, wolfberry, pink grapefruit, pomegranate, raspberry, red cabbage, red onion, strawberry, tomato, and watermelon. Sources of beta-carotene include apricot, cantaloupe, carrot, orange, papaya, peach, persimmon, pumpkin, sweet potato, squash, and yam. Sources of lutein, zeaxanthin and mesozeaxanthin include avocado, broccoli, brussels sprouts, kale, green beans, green leafy vegetables, orange peppers, peas, spinach, yellow corn and zucchini. Sources of anthocyanins include beet, blackcurrant, blueberry, cherry, eggplant, fig, grape, plum, prune, red cabbage, and red currant. The plant extract can be chemically modified by hydrolysis, hydrogenation, esterification or saponification. If the plant extract that normally imparts color has been chemically modified, it may no longer impart color. For example, curcumin imparts a yellow color, but tetrahydrocurcumin, which has been hydrogenated, is colorless.
The dispersion may contain one or more plant biological extracts. "plant biological extract" is a natural extract of a plant that provides flavor and may also provide color. The plant biological extract must be compatible with the non-aqueous composition; is stable in the air; the skin is not polluted; the use amount is non-irritant to the skin; and the using amount is nontoxic. The synthetic form of the plant biological extract is not within the scope of the term "plant biological extract". Examples of suitable plant biological extracts include Arnica montana extract (Arnica montana), basil extract (Ocimum basilicum), Boswellia extract (Boswellia sacra), marigold extract (Calendula officinalis), chamomile extract (Anthemis nobilis), cinnamon oil (cinmamium verum), clove oil (Syzygium aromaticum), Coptis chinensis extract (Coptisapplenii), Echinacea purpurea extract (Echinacea purpurea), eucalyptus oil (Eucalyptus globulus), ginger root extract (Zingiber officinale), grape seed extract (Vitis vinifera), green tea extract (Camilia sinensis), archaea resin extract (Commiphora wilii), horse chestnut seed extract (Aesculus hicula), Japanese Polygonum cuspidatum extract (Polygonum cuspidatum), Glycyrrhiza extract (Acacia oleracea), olive leaf extract (Acacia oleracea), and olive leaf extract (Acacia oleracea), olive leaf extract (Acacia mangium leaf), and olive leaf extract (Acacia oleracea) of fruits, and olive leaf extract (Acacia mangium leaf extract (Acacia) of the plant biological extract (A. officinalis), and the extract of the plant biological extracts of the plant, the plant biological extracts of the plant, such as the plant biological extracts of the plant of the, Pomegranate extract (Punica grantum L.), rosemary extract (Rosmarinus officinalis), sage extract (Salvia officinalis), sandalwood extract (Santalum album), turmeric extract (Curcuma longa) and witch hazel extract (Hamamelis japonica). All of the above examples may include different species of the same genus of plants. For example, Hamamelis virginiana extract may be obtained from Hamamelis japonicus (Hamamelis japonica), Hamamelis elliptica (Hamamelis ovalis), Hamamelis mollis, or Hamamelis virginiana (Hamamelis virginiana).
The composition optionally includes a plant extract. The plant extract may be selected to provide color. Non-color imparting plant extracts may also be included in the composition. The plant extract must be compatible with the non-aqueous composition; is stable in the air; the skin is not polluted; the use amount is non-irritant to the skin; and the using amount is nontoxic. The purity level of the plant extract is at least 95%. Examples of suitable plant extracts include curcumin, lycopene, beta-carotene, lutein, zeaxanthin, mesozeaxanthin and anthocyanins. Sources of curcumin include turmeric. Sources of lycopene include beet, cherry, wolfberry, pink grapefruit, pomegranate, raspberry, red cabbage, red onion, strawberry, tomato, and watermelon. Sources of beta-carotene include apricot, cantaloupe, carrot, orange, papaya, peach, persimmon, pumpkin, sweet potato, squash, and yam. Sources of lutein, zeaxanthin and mesozeaxanthin include avocado, broccoli, brussels sprouts, kale, green beans, green leafy vegetables, orange peppers, peas, spinach, yellow corn and zucchini. Sources of anthocyanins include beet, blackcurrant, blueberry, cherry, eggplant, fig, grape, plum, prune, red cabbage, and red currant. The plant extract can be chemically modified by hydrolysis, hydrogenation, esterification or saponification. If the plant extract that normally imparts color (e.g., curcumin) has been chemically modified, it may no longer impart color, e.g., tetrahydrocurcumin is colorless. The composition may contain 0.01% to 5.0% of the plant extract, preferably 0.01% to 1.0% of the plant extract, including 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% and 0.20% of the plant extract.
The composition optionally includes a plant biological extract. The plant biological extract provides fragrance and may also provide color. The plant biological extract must be compatible with non-aqueous compositions (e.g. lipophilic or hydrophobic); is stable in the air; the skin is not polluted; the use amount is non-irritant to the skin; and the using amount is nontoxic. Examples of suitable plant biological extracts include Arnica montana extract (Arnica montana), basil extract (Ocimum basilicum), boswellia extract (boswellia sacra), Calendula officinalis extract (Calendula officinalis), chamomile extract (Anthemis nobilis), cinnamon oil (cinmamium verum), clove oil (Syzygium aromaticum), coptis chinensis extract (coptisaprifolia), Echinacea extract (Echinacea purpurea), eucalyptus oil (Eucalyptus globulus), ginger root extract (Zingiber officinale), grape seed extract (Vitis vinifera), green tea extract (Camilia), archaea resin extract (Commiphora wilii), horse chestnut seed extract (Aesculus hicula), Japanese knotweed extract (Polygonum cuspidatum), Glycyrrhiza extract (Carica), olive leaf extract (Acacia oleracea), and olive leaf extract (Acacia oleracea), olive leaf extract (Acacia oleracea) and olive leaf extract (Acacia oleracea) of fruits, Pomegranate extract (Punica grantum L.), rosemary extract (Rosmarinus officinalis), sage extract (Salvia officinalis), sandalwood extract (Santalum album), turmeric extract (Curcuma longa) and witch hazel extract (Hamamelis japonica). The dispersion may optionally include an extract from an algal species. These species include Hijikia fusiformis, Spirulina platensis (Spirolinia), Aphanizomenon (Aphanizomnon), Spirulina maxima (Spirolinia maxima), Sargashimurium Brewamani, S.siliquastrum, Sargassu (Rhodomela convectorides), Sargassu (Symphyta latiuscula), Kappaphycus alvarezzi (Kappaphycus alvarezzi), Boyococcus braunii (Boyococcus braunii), Dunaliella salina (Dunaliella salina), Cystoseira crinite, Blackia nigra (Ecklonia stolonifera), Sargassum thunbergii (Sargassum thunbergii), S.thunngiii and fucoside (Ecklonia cava). The composition may contain from 0.10% to 10.0% of a plant biological extract, preferably from 2.0% to 6.0% of a plant biological extract, including 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9% and 4.0% of a plant biological extract.
The composition optionally includes an oil-soluble antioxidant. When present, antioxidants are different from plant extracts. Examples of suitable antioxidants include carotene, catechin, lycopene, resveratrol, vitamin E or vitamin a. "vitamin E" may refer to any tocopherol or tocotrienol compound comprising the vitamin E compound family, such as alpha-tocopherol and gamma-tocotrienol. The composition may contain from 0.01% to 5.0% of an antioxidant, preferably from 0.1% to 3.0% of an antioxidant, including 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and 2.0% of an antioxidant.
The dispersion may contain one or more protist extracts. "protist extract" is a substance obtained from a protist. Protists include eukaryotes that are not animals, plants, or fungi. Preferably, the protist extract is a substance with a high astaxanthin content. Examples of suitable protist extracts include plankton extracts and algae extracts, particularly red algae extracts.
The dispersion may optionally include a protist extract. Preferably, the protist extract is a substance with a high astaxanthin content. Examples of suitable protist extracts include plankton extracts and algae extracts, particularly red algae extracts. The dispersion may contain 0.01% to 5.0% of the protist extract, preferably 0.1% to 3.0% of the protist extract, including 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and 2.0% of the protist extract. Cosmetic and dermatological preparations may comprise cosmetic ingredients, adjuvants and/or additives, such as, for example, co-emulsifiers, fats and waxes, stabilizers, thickeners, bioactive ingredients, film formers, fragrances, dyes, pearlescers, preservatives, pigments, electrolytes and pH regulators. Suitable coemulsifiers are preferably the known W/O and O/W emulsifiers, for example polyglycerol esters, sorbitan esters or partially esterified glycerol esters. Typical examples of fats are glycerides; waxes, such as beeswax, paraffin wax or microcrystalline wax, optionally in combination with a hydrophilic wax. Stabilizers include metal salts of fatty acids, such as magnesium stearate, aluminum stearate, and/or zinc stearate. Examples of thickeners include crosslinked polyacrylic acids and derivatives thereof, polysaccharides, such as xanthan gum, guar gum, agar, alginates and invaders (tyloses), carboxymethyl cellulose and hydroxyethyl cellulose, as well as fatty alcohols, monoglycerides and fatty acids, polyacrylates, polyvinyl alcohols and polyvinyl pyrrolidones. The bioactive components include plant extract, protein hydrolysate and vitamin complex. Conventional film formers include, for example, hydrocolloids such as chitosan, microcrystalline chitosan or quaternary chitosan (quaternary ammonium chitosan salts), polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic series and quaternary cellulose (quaternary ammonium cellulose salt) derivatives. Examples of preservatives include parabens, diazolidinyl urea, iodopropynyl butylcarbamate, and sorbic acid. Examples of pearlescent agents include glycol distearate, such as ethylene glycol distearate, fatty acids and fatty acid monoglycol esters. Dyes that can be used are substances that are suitable and approved for cosmetic purposes. Antioxidants such as amino acids, retinol, flavonoids, polyphenols, vitamin C and tocopherols may also be included.
Cosmetic and dermatological preparations may be in the form of solutions, dispersions or emulsions; for example, sunscreen formulations may be in liquid, paste or solid form, for example as water-in-oil creams, oil-in-water creams and lotions, aerosol foam creams, gels, oils, markers, powders, sprays or alcohol-water lotions. The solvents for these compositions include: water; oils, such as triglycerides of capric or caprylic acid, and castor oil; fats, waxes and other natural and synthetic fatty substances, esters of fatty acids with lower carbon number alcohols, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with lower carbon number alkanoic acids or fatty acids; lower polyols, alcohols or glycols, and ethers thereof, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether. Other examples include isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, diisopropyl adipate, n-hexyl laurate, n-decyl oleate, glyceryl stearate, isooctyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate and erucyl erucate.
Cosmetic and dermatological preparations may be in the form of solid sticks and may include natural or synthetic waxes, fatty alcohols or fatty acid esters, liquid oils such as paraffin oil, castor oil, isopropyl myristate, semi-solid ingredients such as petrolatum, lanolin, solid ingredients such as beeswax, ceresin and microcrystalline waxes and ozokerite, and high melting waxes including carnauba wax and candelilla wax.
The cosmetic formulation may be in the form of a gel and preferably comprises water, an organic thickener such as acacia, xanthan gum, sodium alginate, a cellulose derivative such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and an inorganic thickener such as an aluminium silicate, for example bentonite, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate.
The coated powders and dispersions may also be included in paints, sealants and other coatings, which may also contain binders, such as polyacrylates, polyurethanes, alkyd acids, polyepoxides, polysiloxanes, polyacrylonitriles and/or polyesters. Organic solvents including ethanol, butyl acetate, ethyl acetate, acetone, butanol, alkanes, methanol, propanol, and pentanol may also be present; ethers/acetals such as tetrahydrofuran and 1, 4-dioxane; ketones such as diacetone alcohol and methyl ethyl ketone; and polyol derivatives such as ethylene glycol, propylene glycol and diethylene glycol or mixtures thereof. These compositions are useful for coating a variety of substrates including wood, PVC (polyvinyl chloride), plastic, steel, aluminum, zinc, copper, MDF (medium density fiberboard), glass, and concrete. Depending on the coated powder included, the composition provides a substrate with a coating that may be transparent, UV resistant and/or provide greater scratch resistance.
The coated powders and dispersions can be blended with a resin to provide an organic polymer composite. Examples of the resin include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, AS (acrylonitrile styrene) resin, ABS (acrylonitrile butadiene styrene) resin, AES (acrylonitrile styrene) resin, polyvinylidene chloride, methacrylic resin, polyvinyl chloride, polyamide, polycarbonate, polyallyl ester, polyimide, polyacetal, polyetherketone, polyether sulfone, polyphenylene ether and polyphenylene sulfide, and mixtures thereof. Colorants, fluorescent agents and additives may also be present in these compositions, such as antioxidants, anti-aging agents, UV absorbers, lubricants, antistatic agents, surfactants, fillers (coated powders and dispersions may also be used as fillers), plasticizers, stabilizers, blowing agents, expanding agents, conductive powders, conductive staple fibers, deodorants, softeners, thickeners, viscosity reducers, diluents, water repellents, oil repellents, crosslinking agents and curing agents. These organic polymer compositions can be formed by a variety of techniques including injection molding, blow molding, extrusion molding, calender molding, flow molding, compression molding, melt-blown molding and spun-bonding, whereby shaped products such as fibers, threads, films, sheets, tapes, and injection molded products as well as shaped bodies such as hollow threads, tubes and bottles can be produced. Alternatively, the composition may be subjected to a secondary molding method commonly applied to thermoplastic resins, such as vacuum forming, air pressure forming and laminate molding.
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