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    • 专利摘要:
    PRODUCT FOR ORAL HYGIENE AND TOOTH WHITENING WITH SILICA PARTICLES IN CORE COATING. The present invention provides an oral hygiene and tooth whitening composition comprising: (i) a dye that has a blue to blue-violet color with an angle of shade in the CIELAB system ranging from 200 to 320 degrees; (ii) core-coated silica particles, wherein each core-coated silica particle comprises a silica core and a surface of the silica core is etched with metal silicate; (iii) an orally acceptable carrier vehicle comprising a non-aqueous solvent; and wherein the composition comprises water in an amount of 3 wt% to 30 wt%.
    公开号:BR112016013522B1
    申请号:R112016013522-9
    申请日:2014-12-19
    公开日:2020-11-10
    发明作者:Venda Maloney；Suman Chopra；Hallena Strotman；Guisheng Pan
    申请人:Colgate-Palmolive Company；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED PATENT APPLICATIONS
    [0001] This application claims priority to US Provisional Patent Application Serial Number 61 / 918,938, filed on December 20, 2013; Provisional US Patent Application Serial Number 61 / 918,925, filed on December 20, 2013; International Application PCT number US2014 / 071298, filed on December 18, 2014; International Application PCT number US2014 / 071304, filed on December 18, 2014; and International Application number PCT / US2014 / 071337, filed on December 1, 2014, all of which are incorporated into this document as a reference. BACKGROUND
    [0002] Many individuals are dissatisfied with their current tooth color. Thus, there is a desire for whiter teeth, which can be obtained through the use of tooth whitening products. The whitening effect can be effected by chemical alteration or removal of the stain and / or alteration of the visual perception of the color of the teeth, it being known in the literature that the visual perception of a white substance can be altered through the deposition of an optical brightener, pigment blue or blue dye, especially one where the tint angle (on the CIELAB scale) of the reflected or emitted light is between 200 to 320 degrees. This effect is commonly used in laundry detergent products, which makes white clothes look "whiter" to the human eye. The same concept has been applied to tooth whitening. The whitish natural or yellowish color of the teeth can be almost white or the natural yellow of the teeth can appear whiter through the deposition of a blue substance on the teeth. The use of pigments with a deposition aid, such as Gantrez® (maleic anhydride copolymers with methyl vinyl ether) in the toothpaste to make teeth whiter is disclosed in EP1935395B1.
    [0003] It was demonstrated in EP1935395 that the deposition of the blue substance from aqueous solutions on the teeth is optimal, if the blue substance has limited solubility in saliva, as is the case with a blue pigment. In addition, deposition has been shown to be optimal if a high molecular weight polymer (MW> 200,000 Da) such as polymers of the Gantrez type, PEG, and cellulose ethers is present in the formulation to help the pigment adhere to the tooth . It is also known that other polymers, specifically low molecular weight hydroxypropylmethylcellulose polymers, can increase the deposition of blue pigment on teeth especially when the blue pigment is encapsulated within the matrix of a polymer strip.
    [0004] Dyes have significantly different properties compared to pigments, in particular, dyes are much more soluble in water than pigments. This solubility of the dyes makes them much more difficult to be deposited and retained on the teeth. US patent 6,030,222 discloses dyes that deposit on teeth when mixed with specific vehicles. US Patent Application Publication 2012/0093905 discloses dyes coupled to certain polymers.
    [0005] Blue dye, such as FD&C Blue # 1 or FD&C Blue # 5, has a different chemical structure from the blue pigment 15, so it has a different solubility in water. In fact, the solubility of FD&C Blue # 1 dye is> 20 g / 100 mL in water, compared to <0.1 g / 100 mL for blue pigment 15. The higher solubility of blue dye in water, compared to the blue pigment will logically make it more difficult to deposit and retain the blue dye on the teeth in the hydrated environment of the oral cavity. To increase the deposition of blue dye, Unilever filed a patent application in which the blue dye is covalently attached to the polymeric structure (US2012 / 0093905 Al). Luster White Now markets a toothpaste that claims instant teeth whitening in which a PVM / MA Copolymer is included in the formulation to presumably increase the retention of FD&C Blue # 1 in the teeth. Another patent granted (US6030222) claims to increase teeth whitening by absorbing the blue dye inside the pores of the teeth, preferably from a hydrophilic vehicle that helps the absorption of complementary dyes in the aqueous environment surrounding the teeth.
    [0006] It would be desirable for oral hygiene products that whiten teeth containing dyes that could produce effects of superior temporary tooth whitening when incorporated into oral hygiene products. BRIEF SUMMARY
    [0007] In one aspect, the present invention provides an oral hygiene and tooth whitening composition comprising: (i) a dye that has a blue to blue-violet color with an angle of shade in the CIELAB system ranging from 200 to 320 degrees ; (ii) core-coated silica particles, wherein each core-coated silica particle comprises a silica core and a surface of the silica core is etched with metal silicate; (iii) an orally acceptable carrier vehicle comprising a non-aqueous solvent; and wherein the composition comprises water in an amount of 3 wt% to 30 wt%.
    [0008] In another aspect, the present invention provides a process for the preparation of a composition as defined in any of the preceding claims, the process comprising: i) mixing an amount of silica particles in water with an amount of a base, the base comprising a metal ion, for producing the core-coated silica particles wherein each coated-silica particle comprises a silica core and a surface of the silica core is etched with metal silicate; ii) mixing the core-coated silica particles formed in step i) with an orally acceptable carrier vehicle comprising a non-aqueous solvent, a dye that has a blue to blue-violet color with a tint angle in the CIELAB system that it ranges from 200 to 320 degrees, and an amount of water to produce a composition comprising from 3% by weight to 30% by weight of water.
    [0009] In another aspect, the present invention provides a method for teeth whitening which comprises administering a composition according to the present invention to the oral cavity of a patient in need.
    [0010] Other areas of application of the present invention will be evident from the detailed description provided hereinafter. It should be understood that the detailed description and the specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. DETAILED DESCRIPTION
    [0011] The following description of the preferred embodiments is of an exemplary nature only and in no way intends to limit the invention, its application or uses.
    [0012] The present invention provides a dental whitening oral hygiene composition comprising; (i) a dye showing a blue to blue violet color with an angle of shade in the CIELAB system ranging from 200 to 320 degrees; (ii) core-coated silica particles, wherein each core-coated silica particle comprises a silica core and a surface of the silica core is etched with the metal silicate; (iii) an orally acceptable carrier vehicle comprising a non-aqueous solvent; and wherein the composition comprises water in an amount ranging from 3% by weight to 30% by weight.
    [0013] We found, surprisingly, that when the silica surface chemistry is modified with a strong base, the resulting particle can increase the blue dye retention on the surface, providing a new bleaching agent. This new material consisting of silica-etched silica core is referred to as core-coated silica (CSS). It is understood that in some embodiments the blue dye forms a non-covalent complex with the CSS particles, particularly when the dye comprises a metal ion. Dye
    [0014] The dye must have an angle of hue, h, in the C1ELAB system from 200 to 320 degrees, more specifically between 250 and 290 degrees. The dye can be a blue dye, such as FD&C Blue # 1, FD&C Blue # 2, FD&C Blue # 4, Food Blue Cl 5, Acid Blue 1, or mixtures thereof. The dye may comprise a mixture of one or more blue dyes and one or more red dyes,
    [0015] A detailed description of the tint angle can be found on page 57 of Color Chemistry (Synthesis, Properties and Applications of Organic Dyes and Pigments), 3rd edition by H. Zollinger published by Wiley-VCH (2001). Although the preferred individual dyes are blue or violet, the same effect can be achieved by mixing dyes outside this range h; for example, such a shade angle can also be obtained by mixing a red and blue dye to produce a blue or blue-violet shade. Typically, the dye is able to reflect enough light, so that the treated tooth is noticeably whiter than its initial color. Preferably, the dye is colored in such a way that its natural color is within the violet-red to green-blue color, typically violet to blue.
    [0016] The preferred dyes are water-soluble dyes. The term "water soluble" in this particular context, in general, means that the dye has an aqueous solubility of at least 10 g / L at 25 ° C, more preferably at least 100 g / L at 25 ° C (where solubility is determined in tin-buffered distilled water). Triarylmethane dyes are examples of water soluble dyes useful in the present invention. In some embodiments, dyes useful in the present invention are anionic triphenylmethane dyes, and especially diaminotiphenylmethane dyes containing from two to four sulfonate groups, such as those corresponding to the general formula (I):
    where Ri, R2, R3 and R4 are monovalent radicals that are independently selected from the hydrogen (- H), hydroxyl (-0H), halo (eg -Cl) and sulfonate (- S03 ") groups, with the proviso that that at least two of Ri to Ri are sulfonate groups.
    [0017] An example of a dye useful in this document is FD&C Blue # 1, also known as FCF Bright Blue (Blue 1) as well as other trade names that correspond to the general formula (I), where R2 is -H and Ri , R3 and R4 are sulfonate groups. FD&C Blue # 1 (CAS Number [3844-45-9]) is a food coloring and other substances to induce a color change. It is indicated by the number E133 and has a color index of 42090 (Cl 42090). It has the appearance of a reddish blue powder. It is soluble in water and the solution has a maximum absorption of about 628 nanometers. The same is a synthetic dye produced using petroleum aromatic hydrocarbons. The same is usually a disodium salt. Diamonium salt (D&C Blue # 4) has CAS number [2650-18-2]. Calcium and potassium salts are also known. Other dyes useful in this document are FD&C Blue # 2 (indigo Carmine, Cl 73015, CAS number [860-22-0]), CI Blue 5 food (42051 Cl also known as Blue acid 3, CAS number, [3536- 49 -0]), Blue acid 1 (Cl 42045, CAS number [129-17-9]) and the like. In some embodiments, the dye is FD&C Blue # 1, FD&C Blue # 2, D&C Blue # 4, CI Blue 5 food, Blue acid 1 or their mixtures.
    [0018] Dye mixes can also be used, even if an individual dye has a shade angle outside the desired range, as long as the dye mix is within the range. For example, red dyes, for example, FD&C Red # 3, FD&C Red # 40 and the like can be employed. In an FD&C Blue # 1 mode it is used in combination with FD&C Red # 40.
    [0019] Delta b * is a magnitude of color change along a yellow-blue axis, delta b * negative corresponds to reduced yellowing.
    [0020] The amount of dye in the oral hygiene composition can be 0.001-2% by weight, 0.002-1.5% by weight, 0.003-1.25% by weight, 0.004-1% by weight, 0.005-0 , 5% by weight, 0.0075-0.25% by weight, from 0.01 to 0.1% by weight, from 0.02 to 0.07% by weight, or 0.03-0.05% in weight. In some embodiments, the amount of dye in the oral hygiene composition is about 0.03% by weight. In some embodiments, the amount of dye in the oral hygiene composition is about 0.05% by weight. The dye can be spread evenly throughout the composition, or it can be dispersed in a second phase, such as a strip or other coextruded second phase. Such "double-phase" compositions have the advantage that the phases can be of different colors, presenting a product that is visually more attractive to the consumer.
    [0021] In some embodiments a blue pigment can be used instead of a dye.
    [0022] In some embodiments, the composition is free of peroxide-based bleaching agents. By "free from peroxide-based bleaching agents", it is meant that the composition contains less than 0.1% by weight, less than 0.05% by weight, or less than 0.01% by weight of agents peroxide-based bleaching; or substantially no peroxide-based bleaching agent; or that the composition does not contain peroxide-based bleaching agents. The teeth whitening effect of the oral hygiene compositions of the invention is provided by the presence of the dye, rather than by the presence of any peroxide-based whitening agents. DESCRIPTION OF SILICA PARTICLES IN CORE COATING
    [0023] The silica particles in the core coating are prepared by etching the silica (SiO2) with a base to form the structured colloidal core (Silica) - coating (metal silicate). For example, using NaOH as a base, structured colloids from the core (SiO2) - coating (Na2SiO3) are formed. The reaction is as follows:

    [0024] Na2SiO3 molecules contribute 2 negative charges with 2 Na + contractions on the surface of the silica particle in colloidal core coating
    [0025] A surface of the silica core is etched with metal silicate. The term "etched" means that a surface of the silica core is dissolved, and metal silicate is formed on top of the silica core. The process for making the core-coated silica particles comprises etching the original silica to form the metal silicate, such as Na2SiO3. The reaction of the silica particle with base causes a reduction in the diameter of the silica particle to form a silica core and the metal silicate is formed on top of the silica core. The Na2SiO3 layers are not additional layers coated on top of the original silica surface.
    [0026] Typically, metal silicate is: i. a metal silicate of a monovalent metal ion; or ii. a metal silicate; a monovalent metal ion and one or more than one divalent metal ion, a trivalent metal ion and a tetravalent metal ion.
    [0027] The metal silicate optionally comprises the formula M12SiO3.xH2O, where M is a Group 1 metal, ex is 0 to 10. The metal silicate can be anhydrous, that is, x = 0, or can be hydrated. Preferably, M is Na or K.
    [0028] The surface of the silica core can be the outer surface of the silica core (see Figure I).
    [0029] Alternatively, or in addition, the surface of the silica core can be an internal surface of the silica core (see Figure 2).
    [0030] In one embodiment, the external depth of 10 nm of each particle comprises 0.1 to 10, optionally 0.1 to 2% by weight of M12SiO3.x H20.
    [0031] In one embodiment, the external depth of 10 nm of each particle presents the general formula: (Sio2) p [oo * N 1, ir „oiri | .qii: o where 0 * is oxygen in the form of silicate ; M is a Group I metal ion; p, o, n, h, jeq are the atomic percentages of each component (p is the atomic percentage of SiO2, 0 is the atomic percentage of oxygen in the form of silicate, m is the atomic percentage of the metal in group 1, h is the atomic percentage of H +, j is the atomic percentage of OH 'and q is the atomic percentage of H20); and the total charge for each silica particle in the core coating is zero.
    [0032] Normally the atomic percentage for each component, except H + is determined by electron spectroscopy for chemical analysis (ESCA).
    [0033] Optionally, the external depth of 10 nm of each particle has one of the following compositions; (SiO2) 30.3oNao, 4i. 8.7 0H2O (SiO2) 30, svNao, 3 6 • 7.63H2O (Sio2) 23.25 [O * 11/73 .H1O / 26N13z2o]. 5.33H2O
    [0034] In one embodiment, metal silicate is a silicate of a monovalent metal ion and one or more of a divalent metal ion, a trivalent metal ion, and a tetravalent metal ion. These types of CSS particles are typically formed when monovalent ions are displaced by divalent and / or trivalent ions and / or tetravalent ions.
    [0035] Typically, metal silicate comprises a Group 2 metal ion silicate, a transition metal ion, a Group 13 metal ion, a Group 14 metal ion or mixtures thereof. Optionally, the metal silicate comprises a silicate of Ca, Mg, Zn, Sn, Sr, Al3 +, Zr4 +, Ti4 +, Fe3 +, Fe2 +, Mo2 +, Co2 +, Ni2 +, Mn2 +, Cu2 +, Pd2 +, Mo, Ru or mixtures thereof.
    [0036] Optionally, the metal silicate comprises the formula M2SiO3.xH2O where M2 is a divalent metal ion and x is 0 to 10. M2 can be selected from the group consisting of Zn, Ca, Mg, Sn and Sr, optionally where M2 is Zn.
    [0037] In another embodiment, each core of the core coated silica particle comprises a core of silica and a surface of the silica core etched with metal silicate, the core coated silica particles prepared by: i) the mixture of an amount of silica particles in water with an amount of a base, the base comprising a monovalent metal ion, to produce silica coated particles, each silica coated particle containing a silica core and a surface of the silica core etched with a monovalent metal ion silicate; and ii) the reaction of the core-coated silica particles formed in step i) with a metal salt comprising a second metal ion, to form core-coated silica particles comprising silicate of the second metal ion on the surface of the silica core.
    [0038] It will be understood that the second metal ion typically displaces the monovalent metal ion, from the metal silicate on the surface of the silica core. There can be 5-95% by weight of the monovalent metal ion displaced by the second metal ion, optionally, 25 to 65% by weight. The amount of monovalent metal ion displaced by the second metal ion can be 1, 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, or 80% by weight.
    [0039] In a preferred embodiment, the monovalent metal ion is a Group I metal ion. Particularly preferred as the monovalent metal ion is a potassium ion or sodium ion.
    [0040] The base is not particularly limited, since it comprises the monovalent metal ion. The foundation is typically a strong foundation. The base can be selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, disodium phosphate, potassium phosphate, dipotassium phosphate, tetrasodium pyrophosphate, pyrophosphate and tetrapotassium pyrophosphate. Sodium or potassium hydroxide are preferred bases. The base can have a pKb value in the range of 0.1 to 3. For example, sodium hydroxide has a pKb of 0.2, and potassium hydroxide has a pKb of 0.5.
    [0041] The second metal ion is not particularly limited as long as it can displace the monovalent metal ion from the monovalent metal ion silicate. The second metal ion can be a divalent metal ion, a trivalent metal ion, a tetravalent metal ion or mixtures thereof. Most preferably, the second metal ion is a divalent metal ion. The second metal ion can be a Group 2 metal ion, a transition metal ion, a Group 13 metal ion, a Group 14 metal ion or mixtures thereof. Preferably, the second metal ion is Ca2 +, Mg2 +, Zn2 +, Sn2 +, Sr2 +, Al3 +, Zr4 +, Ti4 +, Fe3 +, Fe2 +, Mo2 +, Co2 +, Ni2 +, Mn2 +, Cu2 +, Pd2 +, MO2 +, RU2 + or mixtures thereof. In a specifically preferred embodiment, the following metal ion is Zn2 +.
    [0042] When changing the first and second metal ions, silica particles in core coating with different uses can be supplied. For example, Zn-CSS are useful as antibacterial agents and anti-odor agents, with a flavor profile that is better than the flavor profile of zinc salts, such as ZnCl2. The CSS particles retain their anti-odor properties and / or properties when in the dye composition. For example, blue toothpaste was prepared using Blue # 1 dye and it reduced bad odor / or exterminated bacteria in saliva with the same effectiveness as Total toothpaste.
    [0043] Silicates can be hydrated or anhydrous
    [0044] It will be understood that the ability of metal silicate ions on an internal or external surface of the CSS particles to be displaced is also behind the utility of the CSS particles as anti-tartar agents. Free calcium ions in saliva displaced monovalent metal ions and / or the second metal ions from the CSS particles, leading to a reduction in the concentration of calcium ions in the saliva. This leads to a reduction in the formation of Ca3 (PO4) 2, the main constituent of tartar. CSS particles with a higher percentage by weight of metal silicate are better tartar control agents because they contain more sites available for chelating calcium ions.
    [0045] In one embodiment, the monovalent metal ion silicate formed in step i) comprises the formula M12SiO3.xH2O where M1 is a monovalent metal ion, optionally a metal ion of group 1 and x is 0 to 10. M1 is preferably Na + or K +.
    [0046] The silicate of the second metal ion formed in step ii) typically comprises the formula M2SiO3.x H20 where M is a divalent metal ion, eg 0 to 10. M is preferably selected from the group consisting of Zn2 +, Ca2 +, Mg2 +, Sn2 + and Sr2 +.
    [0047] The metal salt can be selected from the group consisting of a metal acetate, metal borate, metal butyrate, metal carbonate, metal halide, metal citrate, metal format, metal gluconate, metal glycerate, metal glycolate, metal lactate, metal oxide, metal phosphate, metal picolinate, metal propionate, metal salicylate, metal silicate, metal stearate, metal tartrate, metal undecylenate and mixtures thereof . In a preferred embodiment, the metal salt is a metal halide. Most preferably, the metal halide is a metal chloride. Examples are ZnCl2, SnCl2, SrCl2, A1C13, FeCl3, TiCl4 and ZrCl4. In a particularly preferred embodiment, the metal salt is a zinc salt. The metal salt can be a zinc salt selected from the group consisting of zinc acetate, zinc borate, zinc butyrate, zinc carbonate, zinc chloride, zinc citrate, zinc formate, zinc gluconate, zinc glycerate , zinc glycolate, zinc lactate, zinc oxide, zinc phosphate, zinc pieolinate, zinc propionate, zinc salicylate, zinc silicate, zinc stearate, zinc tartrate, zinc undecylenate and mixtures thereof. The most preferred zinc salt is zinc chloride.
    [0048] In a preferred embodiment, the silicate of the second metal ion comprises ZnSiO3.xH2O, where x is 0 to 10.
    [0049] In one embodiment the surface of the silica core is the outer surface of the silica core. In addition or as an alternative, the surface of the silica core may be an internal surface of the silica core.
    [0050] The silicate of the second metal ion may comprise at least 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight , or 95% by weight of total metal silicate of the CSS particles.
    [0051] The external depth of 10 nm of each particle can comprise from 0.1 to 10% by weight of metal silicate. In one embodiment, the external 10 nm depth of each particle has the general formula:
    where 0 * is oxygen in the form of silicate; N is a monovalent metal ion; M is a divalent metal ion; U is a trivalent metal ion; V is a tetravalent metal ion; p, o, n, m, u, v, h, jeq are the atomic percentages of each component; and the total charge for each silica particle in the core coating is zero.
    [0052] The atomic percentage for each component except H + is typically determined by electron spectroscopy for chemical analysis (ESCA). In one example, using ESCA data, the following elements were detected: O58.815126 / 520 * 7.3sNa3z igZn4; 6 5011.49
    [0053] When setting the total electrical charge to zero by adding H + and water, we conclude that in one modality, the external depth of 10 nm of each particle can have the following composition: (SÍO2) 26/52 [0 * 7 , 3δNa3, iβZUi, 65CI1,49H3,73] 3.7 7H2O
    [0054] In one embodiment, the silica particles in the core coating comprise up to 20% by weight of total metal.
    [0055] In one embodiment, the value of d (0.5) of the particles is from 5 nm to 50 pm.
    [0056] The d (0.5) value of the particles can be from 26 pm to 40 pm. Particles having a value of d (0.5) within this range are generally translucent. Translucent particles are those that allow light to pass through, although it is not possible to see the image through the particles. This differs from transparent compositions that allow light to pass through and an image can be seen through the composition. Methods for determining particle size are well known in the art. For example, particle size can be determined using light scattering methodologies, such as using Mastersizer 2000, Hydro 2000S, Malvern Instruments Limited.
    [0057] The d (0.5) value of the particles can be from 18 pm to 25 pm. The d (0.5) value of the particles can be from 10 pm to 15 pm. The d (0.5) value of the particles can be from 5 nm to 0.12 nm.
    [0058] The d (0.5) or d50 of the particles is the diameter (typically in microns) that divides the distribution with half the population above and below half this diameter. It should be noted that this parameter is a value for a population of particles, and that the diameter of an individual particle can be greater or less than the d (0.5) values described here. The DV50 (or Dv0.5) is the average for a volume distribution. DN50 is used for numerical distributions, and Ds50 is used for surface distributions. In the present context, d (0.5) will be used to refer to the average particle size for a volume distribution.
    [0059] The value of d (0, l) of the particles is the diameter that divides the distribution with 10% of the population below and 90% above this diameter.
    [0060] The value of d (0.9) of the particles is the diameter that divides the distribution with 90% of the population below and 10% above this diameter.
    [0061] A value used to describe the distribution width of the particle size distribution is the extension: Extension = (d (0.9) -d (0.1)) / d (0.5).
    [0062] The length of the core-coated silica particles according to the present invention is typically 1.5 to 3.
    [0063] In a preferred embodiment, CSS has a d (0.1) between 10 and 13 pm, a d (0.5) from 30 to 33 pm, and a d (0.9) from 61 to 64 pm.
    [0064] In another preferred embodiment, CSS has a d (0.1) from 6 to 9 pm, a d (0.5) from 18 to 21 pm, eumd (0.9) from 41 to 45 pm.
    [0065] In another preferred embodiment, CSS has a d (0.1) from 3 to 5 pm, a d (0.5) from 11 to 14 pm, and a d (0.9) from 33 to 3 pm .
    [0066] In the preferred embodiments, the d (0.5) value of the CSS particles is less than the average diameter of a human dentin tubule. This allows the CSS particles to enter the dentinal tubules, which may be exposed, damaging the protective enamel layer. In human teeth, the dentinal tubules taper from the inside to the outermost surface, and have an average diameter of 2.5 pm near the pulp, 1.2 pm in the middle of the dentin, and 0.9 pm at the dentin junction - nail polish (see http://www.slideshare.net/DrAbusallamah/history-ofo- dentin). Thus, the d (0.5) value of the CSS particles is preferably less than 0.9 pm. In a particularly preferred embodiment, the d (0.5) value of the CSS particles is less than the average diameter of a human enamel tubule. Enamel tubules typically have an average diameter of 50 to 100 nm. Thus, the d (0.5) value of the CSS particles is preferably 5 to 20 nm, optionally 5 to 12 nm. Preferably, when the CSS particles are intended to enter the enamel tubules, these particles are prepared from fumed silica. The fumed silica is composed of panicles having a d (0.5) in the range of 5 to 20 nm, which agglomerate into larger particles having a d (0.5) in the micrometer range.
    [0067] The CSS particles can be spherical or substantially spherical, however, it will be understood that the particles can have other shapes, for example, rod, needle, or ellipsoidal shapes. The particles can be irregularly shaped. The particles can also form aggregates of a larger size.
    [0068] The metal silicate may comprise a plurality of M2SiO3 .xH20 monolayers. The number of single layers can be 2 to 100, 2 to 40, 2 to 12 or 12 to 40 monolayers.
    [0069] The particle may comprise 2, 4, 16, 32 or 36 surface metal silicate monolayers.
    [0070] The silica is preferably selected from the group consisting of a precipitated silica, a fumed silica and a fused silica.
    [0071] Silica particles in core coating preferably have a high surface charge density and ion exchange capacity. Optionally, the silica particles in the core coating have a total cation exchange capacity of 0.5 to 5.0 meq / g. Core-coated silica particles with a high cation exchange capacity are particularly preferred, as this allows CSS to exchange metal ions, such as Na + on their surface for calcium ions in saliva, inhibiting the formation of Tartarus.
    [0072] In one embodiment, the silica particles in the core coating have a turbidity of 0.0 to 0.2 from a wavelength of 300 to 800 nm, using a 0.20 mm UV optical quartz cell . These particles can be described as translucent or transparent.
    [0073] In another embodiment, the silica particles in the core coating have a turbidity of 0.8 to 1.6, at a wavelength of 300 to 800 nm, using a 0.20 mm UV optical quartz cell. These particles can be described as semi-opaque. In another embodiment, the silica particles in the core coating have a turbidity of 1.8 to 2.4 at a wavelength of 300 to 800 nm, using a 0.20 mm UV optical quartz cell. These particles can be described as opaque.
    [0074] In preferred embodiments, the amount of silica particles in the core coating is 0.001 to 10% by weight, or 0.01 to 5% by weight, or 0.05 to 5% by weight, or 0.1 to 5% by weight, or from 0.5 to 5% by weight, or 0.5 to 3% by weight, or 1 to 2% by weight, or about 1% by weight of the composition. Orally Acceptable Carrier Vehicle
    [0075] The oral hygiene compositions of the invention include a carrier or base in which the dye particles and silica particles in the core coating are incorporated. The carrier vehicle can be present in an amount of 40-99% by weight or 55-85% by weight, based on the total weight of the composition. It has surprisingly been found that when the dye is incorporated into a non-aqueous carrier, containing little or substantially no water, the whitening effect of the tooth is enhanced. In some embodiments, orally acceptable carrier vehicles comprise alcohols, polyhydric alcohols, such as glycerol, sorbitol, xylitol, propylene glycol, polyols, ketones, aldehydes, carboxylic acids or salts thereof, amines or mixtures thereof. In one embodiment, the carrier comprises glycerol. Such materials normally also function as humectants.
    [0076] In some aspects of the present invention, small amounts of water are present, for example, from 3% by weight to 30% by weight, 5 to 17% by weight, 10 to 17% by weight, 5 to 15% by weight. weight, 5% by weight to less than 10% by weight, 5 to 7% by weight, or about 7% by weight, about 0.10% by weight, or about 15% by weight.
    [0077] It is surprising that the low water content of the compositions of the invention allows improved release of the dye to the teeth, since the dyes are soluble in water. It is not intended to be linked to any particular theory or mechanism, but it is believed that the use of the compositions of the invention, with little or no water, boosts the dye in the aqueous spaces of the tooth enamel.
    [0078] The orally acceptable carrier vehicle may optionally include several other ingredients that are generally incorporated in toothpastes. Examples of such other ingredients include carrier polymers, humectants, abrasives, thickening silicas or any combination of two or more of these. The term "orally acceptable" refers to a material or ingredient that can be applied to the oral cavity in a safe manner during normal use. Vehicle Polymers
    [0079] Carrier polymers may comprise one or more anionic or nonionic polymers, and may also include additional polymers to adjust the viscosity of the formulation or to increase the solubility of other ingredients.
    Suitable carrier polymers include polyethylene glycols, polysaccharides (eg cellulose derivatives, eg carboxymethyl cellulose or polysaccharide gums, eg xanthan gum or carrageen gum). Acid polymers, for example, polyacrylate gels, can be provided in the form of their free acids or completely neutralized water-soluble alkali metal (eg, potassium and sodium) or ammonium salts. Anionic polymers can be present in an amount of from about 0.001 to about 5%, more particularly about 0.01 to 5%, more particularly about 0.05 to 4%, more particularly about 0.05 to 3% of the composition. Examples of such agents are disclosed in US Patent numbers 5,188,821 and 5,192,531; and include synthetic anionic polymeric polycarboxylates, such as 1: 4 to 4: 1 copolymers of maleic anhydride or acid with another ethylenically unsaturated, polymerizable monomer, preferably methyl vinyl ether / maleic anhydride having a molecular weight (MW) of about 30,000 to about 1,000,000, more preferably about 300,000 to about 800,000. These copolymers are available, for example, as Gantrez (R), for example, AN 139 (MW 500,000), AN 119 (MW 250,000) and preferably S-97 Pharmaceutical Grade (MW 700,000) available from ISP Technologies, Inc., Bound Brook, NJ 08805. Other operating polymers include those, such as 1: 1 maleic anhydride copolymers with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone, or ethylene, the latter being available, for example , such as Monsanto EMA number 1103, MW 10,000 and EMA Grade 61, and 1: 1 acrylic acid copolymers with methyl or hydroxyethyl methacrylate, methyl or ethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone. Generally suitable are olefinically polymerized or ethylenically unsaturated carboxylic acids containing an olefinic carbon-carbon double bond and at least one carboxyl group, that is, an acid containing an olefinic double bond that readily works in polymerization due to its presence in the monomer molecule, either in the alpha-beta position relative to a carboxyl group or as part of a terminal methylene group. Illustrative of such acids are acrylic, methacrylic, ethacrylic, alpha-chloroacrylic, crotonic, beta-acryloxy-propionic, sorbic, alpha-chlororsorbic, cinnamic, beta-styrylacrylic, muconic, itaconic, citraconic, mesaconic, glutaconic, aconitic, alpha -phenylacrylic, 2-benzyl acrylic, 2-cyclohexylacrylic, angelic, umbelic, fumaric, maleic and anhydrides. Other different olefinic monomers copolymerizable with these carboxylic monomers include vinyl acetate, vinyl chloride, dimethyl maleate and the like. Copolymers contain sufficient carboxylic salt groups for water solubility. Another class of polymeric agents includes a composition that contains the acrylamide homopolymers and / or unsaturated sulfonic acid homopolymers and substituted salts thereof, in particular, where the polymers are based on the unsaturated sulfonic acids selected from acrylamido sulfonic acids, such such as, 2-acrylamide-2-methylpropane acid having a molecular weight of about 1,000 to about 2,000,000, described in US Patent No. 4,842,847, June 27, 1989 to Zahid, incorporated herein by reference. Another useful class of polymeric agents includes polyamino acids containing proportions of anionic surface-active amino acids, such as aspartic acid, glutamic acid and phosphoserine, (in addition to the basic amino acid polymers), for example, as disclosed in US Patent No. 4,866,161 to Sikes and others incorporated into this document as a reference.
    [0084] In preparing oral hygiene compositions, it is sometimes necessary to add some thickening material to provide a desired consistency or to stabilize or increase the performance of the formulation. In certain embodiments, the thickeners are polymers carboxyvinyl, carrageenan, hydroxyethylcellulose and water-soluble salts of cellulose ethers, such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Natural gums, such as Karaya gum, gum arabic and tragacanth gum can also be incorporated. Colloidal magnesium aluminum silicate or finely divided silica can be used as a component of the thickening composition to further improve the texture of the composition. In certain embodiments, thickening agents are used in an amount of about 0.5% to about 5.0% by weight, of the total composition. Orally acceptable carrier polymers suitable for use in the present invention will generally dissolve or disperse in water at a temperature of 25 ° C.
    [0085] The amount of orally acceptable carrier polymer in the compositions of the present invention, whether enhancers, deposition aids, thickeners or the like, or a combination thereof, suitably ranges from about 0.001 to 10% by weight, more particularly about from 0.005 to 5% by weight, more particularly about 1 to 5% by weight, and more particularly about 1 to 3% by weight.
    [0086] The composition may further comprise an additional agent selected from fluorine, arginine in the form of a free or orally acceptable salt, an antibacterial agent, an anti-inflammatory agent, and a combination of two or more of these.
    [0087] The composition can be in the form of a toothpaste.
    [0088] In one embodiment the composition is a toothpaste comprising one or more of abrasive, surfactant, foaming agent, vitamin, polymer, enzyme, humectant, thickener, antimicrobial agent, preservative, flavoring, and / or a combination of two or more of these.
    [0089] The composition may be free of peroxide-based bleaching agents. Humectants
    [0090] Within certain modalities of oral compositions, it is also desirable to incorporate a humectant to prevent the composition from becoming stiff upon exposure to air. Certain humectants can also impart sweetness or desirable flavor to toothpaste compositions. The humectant, in a pure humectant base, generally includes about 15% to about 70% in one embodiment or about 30% to about 65% by weight, in another embodiment, of the toothpaste composition. Suitable humectants include edible polyhydric alcohols, such as glycerin, sorbitol, xylitol, propylene glycol, as well as other polyols and mixtures of these humectants. Mixtures of glycerin and sorbitol can be used, in certain embodiments, as the wetting component of the toothpaste compositions described herein. Abrasives
    [0091] The compositions of the invention may comprise a calcium phosphate abrasive, for example, tricalcium phosphate (Ca3 (PO4) 2), hydroxyapatite (Caio (P04) 6 (OH) 2), or dicalcium phosphate dihydrate (CaHPO4.2H2O , also sometimes referred to in this document as DiCal) or calcium pyrophosphate. The compositions can include one or more additional abrasives, for example, silica abrasives, such as, precipitated silicas having an average particle size of up to about 20 microns, such as Zeodent 115®, marketed by I.M. Huber. Other useful abrasives include sodium metaphosphate, potassium metaphosphate, aluminum silicate, calcined alumina, bentonite or other silicon materials or combinations thereof. The silica abrasive polishing materials useful in this document, as well as other abrasives, generally have an average particle size ranging from about 0.1 to about 30 microns, about 5 to about 15 microns. Silica abrasives can be precipitated silica or silica gels, such as the silica xerogels described in US Patent No. 3,538,230, by Pader et al. And US Patent No. 3,862,307 to Digiulio, both of which are incorporated herein by reference. Private silica Xerogels are marketed under the trade name Syloid® by W.R. Grace & Co., Davison Chemical Division. Precipitated silica materials include those marketed by IM Huber Corp under the trade name Zeodent®, including silica under the designation Zeodent 115 and 119. These silica abrasives are described in US Patent No. 4,340,583, granted to Wason, incorporated into the this document as a reference. In certain embodiments, abrasive materials useful for practicing oral hygiene compositions according to the invention include precipitated silica and amorphous silica gels having an oil absorption value of less than about 100 cm3 / 100 g of silica and in the range of about 45 cm3 / 100 g to about 70 cm3 / 100 g of silica. Oil absorption values are measured using the ASTA Rub-Ou D281 method. In certain embodiments, silicas are colloidal particles with an average particle size (d (0.5)) of about 3 microns and about 12 microns and about 5 to about 10 microns. Low oil absorption silica abrasives particularly useful in the practice of the invention are marketed under the trade name Sylodent XWA® by Davison Chemical Division of W.R. Grace & Co., Baltimore, Md. 21203. Sylodent 650 XWA®, a silica hydrogel, composed of colloidal silica particles having a water content of 29% by weight, on average about 7 to about 10 microns. diameter, and an oil absorption of less than about 70 cm 3/100 g of silica is an example of a low oil absorption silica abrasive useful in the practice of the present invention. The abrasive is present in the oral hygiene composition of the present invention at a concentration of about 10 to about 60% by weight, in another embodiment from about 20 to about 45% by weight, and in another embodiment of about from 30 to about 50% by weight. Product Shape
    [0092] Examples of product forms suitable for compositions of the invention include toothpastes. The term "dentifrice" generally indicates formulations that are used to clean the surfaces of the oral cavity. The dentifrice is an oral composition that is not intentionally swollen for purposes of systemic administration of therapeutic agents, but is applied to the oral cavity, used to treat the oral cavity and then expectorated. Typically, toothpaste is used in conjunction with a cleaning implement, such as a toothbrush, generally applying the same to the brush bristles and then brushing the accessible surfaces of the oral cavity. Preferably, the toothpaste is in the form of a paste or gel (or a combination thereof). Active Agents
    [0093] The effective concentration of the active ingredients used in this document will depend on the specific agent and the delivery system employed. Furthermore, it is understood that toothpaste, for example, will typically be diluted with water when used, while mouthwash or topical pharmaceutical preparation will typically not be. Thus, an effective concentration of active in a toothpaste, for example, will usually be 5-15 times greater than that required for a mouthwash. The concentration will also depend on the exact salt or polymer selected. For example, when the active agent is provided in the form of salt, the counterion will affect the weight of the salt, so that the counterion is heavier, more salt by weight will be needed to provide the same concentration of active ion in the final product. Active agents can include one or more of a fluoride ion source, an anti-calculating agent, an amino acid, an antibacterial agent and the like.
    [0094] Arginine, when present, can be present at levels of, for example, about 1 to about 10% by weight for a consumer toothpaste or about 7% to about 20% by weight for a product for prescription or professional treatment.
    [0095] Fluorine when present can be present in levels of, for example, about 25 to about 25,000 ppm of fluorine ions. For consumer toothpaste, the fluoride level can be between about 500 to about 1,600 ppm or between about 500 to about 1,000 ppm or between about 1,000 ppm to about 1,500 ppm, for example, about 1,100 ppm or 1,450 ppm. The appropriate level of fluoride will depend on the specific application. A toothpaste or coating for professional application would have as much as 5,000 or even about 25,000 fluoride, for example, a range of about 3,000 ppm to about 8,000 ppm of fluoride.
    [0096] Antibacterial agents can be included in the oral composition of the present invention and specifically non-cationic halogenated diphenyl ester agents that are desirable for effectiveness and safety considerations, such as 2 ', 4,4' trichloro-2-hydroxy-diphenyl ether (Triclosan) and 2,2'-dihydroxy-5,5 'dibromophenyl ether. Other antibacterial agents, for example, zinc salts, can be included in the compositions of the present invention. The antibacterial agent, when present in the oral composition, is present in concentrations of about 0.05 to about 2% by weight and preferably 0.1 to about 1% by weight. For example, a triclosan toothpaste can contain about 0.3% by weight of triclosan.
    [0097] The agents used to decrease the sensitivity of teeth, such as potassium chloride, potassium nitrate, potassium citrate, dipotassium oxalate or zinc phosphate can also be included in the oral compositions of the present invention in concentrations of about 0.1 to about 10% by weight. Fluoride ion source:
    [0098] Compositions for oral hygiene may further include one or more sources of fluoride ions, for example, soluble fluoride salts. A wide variety of materials that yield fluoride ions can be used as a source of soluble fluoride in the present compositions. Examples of suitable materials that yield fluoride ions are found in US Patent No. 3,535,421 to Briner and others; 4,885,155 to Parran, Jr. et al. And US Patent No. 3,678,154 to Widder and others incorporated herein by reference. Representative sources of fluoride ions include, but are not limited to stannous fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate, amine fluoride, ammonium fluoride and combinations thereof. In certain embodiments, the fluoride ion source includes stannous fluoride, sodium fluoride, sodium monofluorophosphate, as well as mixtures thereof. In certain embodiments, the oral care composition of the invention may also contain a source of fluoride ions or fluoride-providing ingredient in amounts sufficient to provide about 25 ppm to about 25,000 ppm fluoride ions, generally at least about 500 ppm, for example, about 500 to about 2,000 ppm, for example, about 1,000 to about 1,600 ppm, for example, about 1,450 ppm. The appropriate level of fluorine will depend on the particular application. The toothpaste for general use in general is usually about 1,000 to about 1,500 ppm, with the pediatric toothpaste showing slightly less. A toothpaste or coating for professional application could have as much as about 5,000 or even about 25,000 ppm of fluoride.
    [0099] Fluoride ion sources can be added to the compositions of the invention at a level of about 0.01% by weight to about 10% by weight. In one embodiment, about 0.03% by weight to about 5% by weight and in another embodiment about 0.1% by weight to about 1% by weight of the composition, in another embodiment. The weights of the fluoride salts to provide the appropriate level of fluoride ion will, of course, vary according to the weight of the salt counterion. Foaming Agents
    [00100] The oral hygiene compositions of this invention may also include an agent for increasing the amount of foam that is produced when the oral cavity is brushed. Illustrative examples of agents that increase the amount of foam include, but are not limited to, polyoxyethylene and certain polymers including, but not limited to, alginate polymers. The polyoxyethylene can increase the amount of foam and the thickness of the foam generated by the oral hygiene carrier component of the present invention. Polyoxyethylene is also known as polyethylene glycol ("PEG"), or polyethylene oxide. The polyoxyethylenes suitable for this invention will have a molecular weight of about 200,000 to about 7,000,000. In one embodiment, the molecular weight will be about 600,000 to about 2,000,000 and in another mode about 800,000 to about 1,000,000. Polyox® is the trade name for high molecular weight polyoxyethylene produced by Union Carbide. The polyoxyethylene can be present in an amount of about 1% to about 90%, in an embodiment of about 5% to about 50% and in another embodiment of about 10% to about 20% by weight, of the carrier component of the oral hygiene compositions of the present invention. The dosage of the foaming agent in the oral care composition (i.e., a single dose) is about 0.01 to about 0.9%, by weight, about 0.05 to about 0.5 % by weight, and in another embodiment from about 0.1 to about 0.2% by weight. Anti-calculation agents
    [00101] The oral composition may include at least one anticalculation composition, such as one or more of the anticalculation compositions cited in US Patent No. 5,292,526 entitled "Antibacterial Anti-plaque Anticalculus Oral Composition" which is incorporated herein by reference . In various embodiments, the anti-calculation composition includes one or more polyphosphates. The anti-calculation composition can include at least a partially or fully neutralized alkali metal or ammonium tripolyphosphate or hexametaphosphate salt present in the oral composition in an effective anti-calculation amount. The anti-calculation composition can also include at least one water-soluble, linear, molecularly dehydrated polyphosphate salt effective in an anti-calculation amount. The anti-calculation composition may also include a mixture of potassium and sodium salts, at least one of which is present in an effective anti-calculation amount and as a polyphosphate anti-calculation agent. The anticalculation composition can also contain an effective amount of molecularly dehydrated, molecularly dehydrated polyphosphate salt present in a mixture of sodium and potassium salts. Other useful anti-calculating agents include polycarboxylate polymers and polyvinyl methyl ether / maleic anhydride (PVME / MA) copolymers, such as GANTREZ (R). Surfactants
    [00102] Compositions useful in the present invention may contain anionic and / or non-ionic surfactants, for example: i. water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of coconut oil fatty acid monoglyceride, such as sodium N-methyl-N-cocoyl-taurate, sodium cocomonoglyceride sulfate, ii . upper alkyl sulfates, such as sodium lauryl sulfate, iii. higher alkyl ether sulphates, for example, of the formula CH3 (CH2) mCH2 (OCH2CH2) nOSO3X, where m is 6-16, for example, 10, n is 1-6, for example, 2, 3 or 4, and X is Na or K, for example, sodium laureth-2 sulfate (CH3 (CH2) 1OCH2 (OCH2CH2) 2OSO3Na), iv. higher alkylarylsulfonates, such as sodium dodecyl benzene sulfonate (sodium lauryl benzene sulfonate). v. higher alkyl sulfoacetates, such as sodium lauryl sulfoacetate (sodium dodecyl sulfoacetate), 1,2-dihydroxypropane sulfonate higher fatty acid esters, sulfocolaurate (N-2-ethyl sulfoacetamide potassium laurate) and sodium lauryl sarcocinate.
    [00103] The term "upper alkyl" means, for example, C6_30 alkyl. In specific embodiments, the anionic surfactant is selected from sodium lauryl sulfate and sodium lauryl sulfate ether. The anionic surfactant may be present in an amount that is effective, for example,> 0.01% by weight of the formulation, but not at a concentration that is irritating to oral tissue, for example, <10%, and concentrations Optimal depend on the specific formulation and the specific surfactant. For example, the concentrations used for a mouthwash are typically on the order of one tenth of those used for a toothpaste. In one embodiment, the anionic surfactant is present in the toothpaste from about 0.3% to about 4.5% by weight, for example, about 1.5%.
    [00104] Non-ionic surfactants include non-anionic polyoxyethylene surfactants, such as Poloxamer 407, Steareth 30, Polysorbate 20 and PEG-40 castor oil in addition to amphoteric surfactants, such as cocaminopropyl betaine (tegobain) and products of condensation of cocamidopropyl betaine lauryl ethylene oxide glycoside with various hydrogen-containing compounds that are reactive with them and have long hydrophobic chains (for example, aliphatic chains of about 12 to 20 carbon atoms), which are condensation products (" ethoxamers ") contain hydrophilic polyoxyethylene fractions, such as condensation products of poly (ethylene oxide) with fatty acids, fatty alcohols and other fatty fractions, and with propylene oxide and polypropylene oxides (for example, Pluronic materials (R )).
    [00105] The compositions of the invention may optionally contain mixtures of surfactants, for example, comprising anionic surfactants and other surfactants which can be anionic, cationic, zwitterionic or non-ionic. Generally, surfactants are those that are reasonably stable over a wide pH range. Surfactants are described more fully, for example, in US Patent No. 3,959,458 to Agrícola and others; US Patent No. 3,937,807 to Haefele; and US Patent No. 4,051,234 to Gieske et al., which are hereby incorporated by reference. In certain embodiments, the anionic surfactants useful for this invention include the water-soluble salts of alkyl sulfates having about 10 to about 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated fatty acid monoglycerides with about from 10 to about 18 carbon atoms. Sodium lauryl sulfate, sodium lauroyl sarcosinate and sodium coconut monoglyceride sulfonates are examples of anionic surfactants of this type. In a particular embodiment, the composition of the invention, for example, Composition 1 and sequences comprise sodium lauryl sulfate.
    [00106] The surfactant or mixtures of compatible surfactants can be present in the compositions of the present invention in about 0.1% to about 5.0%, in another embodiment, about 0.3% to about 3, 0% and in another embodiment from about 0.5% to about 2.0% by weight of the total composition. Flavoring Agents
    [00107] The oral hygiene compositions of this invention may also include a flavoring agent. Flavoring agents that are used in the practice of the present invention include, but are not limited to, essential oils, as well as various flavoring aldehydes, esters, alcohols and similar materials. Examples of essential oils include mint, peppermint, wintergreen, sassafras, cloves, sage, eucalyptus, marjoram, cinnamon, lemon, grapefruit and orange oils. Chemicals like menthol, carvone and anethole are also useful. Certain modalities use peppermint and peppermint oils. The flavoring agent can be incorporated into the oral composition at a concentration of about 0.1 to about 5% by weight and about 0.5 to about 1.5% by weight. The dosage of the flavoring agent in the individual dosage oral hygiene composition (i.e., a single dose) is from about 0.001 to 0.05% by weight, and in another embodiment from about 0.005 to about 0.015% by weight. Other Optional Ingredients
    [00108] In addition to the components described above, the embodiments of this invention may contain a variety of optional toothpaste ingredients, some of which are described below. Optional ingredients include, for example, but are not limited to adhesives, foaming agents, flavoring agents, sweetening agents, additional anti-plaque agents, abrasives and coloring agents. These and other optional components are further described in US Patent No. 5,004,597 to Majeti; US Patent 3,959,458 to Agrícola et al. And US Patent 3,937,807 to Haefele, all of which are incorporated herein by reference. Process for Preparation of the Composition
    [00109] In a further aspect, the present invention provides a process for the preparation of a composition as defined in any of the preceding claims, the process comprising: i) mixing an amount of silica particles in water with an amount of a base, the base comprising a metal ion, to produce the core coated silica particles, wherein each core coated silica particle comprises a silica core and a silica core surface is etched with the silicate metal; ii) mixing the core-coated silica particles formed in step i) with an orally acceptable carrier vehicle comprising a non-aqueous solvent, a dye that has a blue to blue-violet color with a tint angle in the CIELAB system that it ranges from 200 to 320 degrees, and an amount of water to produce a composition comprising from 3% by weight to 30% by weight of water.
    [00110] Step i) of the invention may comprise mixing an amount of SiO2 particles in water with an amount of NaOH in solid or aqueous form, with or without a wetting agent, to produce the silica particle in the core coating . Sodium hydroxide reacts with the SiO2 particle surface to engrave a coating of Na2SiO3 layer (s) as follows: SiO2 + 2 NaOH -> Na2SiO3 + H20
    [00111] As can be seen from the reaction scheme, no NaOH will result and silica change, while at the other end, complete reaction, with 2 moles of NaOH per 1 mole of silica will result in complete conversion to Na2SiO3. In order to obtain the core particles of the invention, the reaction process must be controlled so as not to achieve complete conversion to Na2SiO3.
    [00112] The process for making the silica particles in core coating comprises etching the original silica in order to form layers of Na2SiO3, that is, the layers of Na2SiO3 are not additional layers coated on top of the silica surface.
    [00113] As the covalent bonds of the SiO2 network are transformed into ionic bonds between Na + and SiO32 ", the surface becomes polarized and adsorb water and the humectant to produce the silica particle in the core coating.
    [00114] The process may comprise an additional step after step i) and before step ii) of reacting the core-coated silica particles formed in step i) with a metal salt comprising a second metal ion, for forming silica particles in a core coating comprising silicate of the second metal ion on a surface of the silica core.
    [00115] The base can be in solid or aqueous form. The base is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, disodium phosphate, potassium phosphate, dipotassium phosphate , tetrasodium pyrophosphate and tetrapotassium pyrophosphate. A particularly preferred base is sodium hydroxide, more preferably a 50% aqueous sodium hydroxide solution.
    [00116] Step i) can be performed at a temperature in the range from 17 ° C to 90 ° C. In one embodiment, the process is carried out at room temperature, ie 20 to 26 ° C. In another embodiment, step i) is carried out at a temperature of 70 to 90 ° C. When preparing the silica particles in an industrial scale core coating, the mixer used to mix the reagents, such as a Lee mixer (Lee Industries ), preferably not heated.
    [00117] In one embodiment, in step i) the base is sodium hydroxide and the process is carried out at a temperature of 70 to 90 ° C. In another embodiment, in step i) the base is potassium hydroxide and the process is carried out at room temperature. This method is advantageous because the use of the more reactive potassium hydroxide means that heating is not necessary.
    [00118] The formation of the silica particles in the core coating in step i) is typically complete after a period of time of 2 hours.
    [00119] The weight ratio of the amount of base to the amount of silica particles in step i) can be from 1: 1 to 1:20. The weight ratio for the amount of base to the amount of silica particles can be from 1: 1 to 1: 3.
    [00120] The turbidity of the silica particles in the core coating is reduced by increasing the weight ratio to the amount of base to the amount of silica particles.
    [00121] An average depth of 1-15 nm of silica can be removed from the surface of the silica particle to form the silica core and metal silicate is formed on top of the silica core in step i). The average depth of silica removed typically increases as the weight ratio to the amount of base to the amount of silica particles increases. The d (0.5) of the silica core can be from 1 to 15 nm less than the d (0.5) of the silica particles of the starting material. The d (0.5) of the silica core can be about 2 nm, less than the d (0.5) of the silica particles of the starting material. The d (0.5) particle diameter of the silica core can be about 6 nm less than the d (0.5) of the silica particles of the retarding material. There is a greater percentage reduction in particle diameter for rigid silica particles, such as fumed silica, than for porous silica particles such as high cleaning silica. For example, for fumed silica the percentage of reduction in particle diameter (d (0.5)) may be approximately 15%, while for high-cleaning porous silica the percentage of reduction in particle diameter (d ( 0.5)) can be approximately 0.06%.
    [00122] The formation of the silica particles in the core coating of the present invention described above can be carried out by manipulating the amount of base used, the amount of humectant used, the amount of metal salt used, and variation of the reaction temperature .
    [00123] The formation of the particles in the core coating can be monitored by determining the pH of the reaction mixture. In one embodiment, step i) is complete when the pH of the reaction mixture decreases by at least 0.5 pH units from the initial mixture of the reagents. In another embodiment, step i) is complete when the pH of the reaction mixture decreases by at least 0.8 pH units from the initial mixture of the reagents. Typically, step i) is complete when the pH of the reaction mixture is about 11. The process may comprise an additional step after the step of forming the particles in the 7-8 pH adjustment coating of the reaction mixture. The pH of the reaction mixture is typically adjusted with acid. The acid can be selected from the group consisting of phosphoric acid, citric acid and lactic acid.
    [00124] The formation of the particles in the core coating in step i) can also be monitored by determining the conductivity of the reaction mixture. The end point of the process results when the conductivity of the reaction mixture decreases by at least 250 microns-Siemens / cm (pS / cm) because electrical charges transfer highly mobile ions (NaOH) to the much less mobile silica surface (mobility ~ 0). In yet another embodiment, the end point of the process results when the conductivity of the reaction mixture decreases by 250-400 pS / cm. Typically, core-coated silica particles are formed when the conductivity of the reaction mixture decreases by at least 2 milliSiemens / cm (mS / cm). Typically, core-coated silica particles are formed when the conductivity of the reaction mixture reduces by at least 5 mS / cm.
    [00125] In one embodiment, the core coated silica particles of the present invention are formed when at least 1-6% of each of the silica particle starting materials has been etched with one or more layers of silicate. In another embodiment, the core coated silica particles of the present invention are formed when at least 2.5-5% of each silica particle starting material has been etched with one or more layers of Na2SiO3. In another embodiment, the core-coated silica particles of the present invention are formed when at least 3.5-4% of each of the silica particle starting materials has been etched with one or more layers of silicate.
    [00126] It is understood that, although the general attributes of each of the preceding categories of materials may be different, there are some common attributes and any given material can have several purposes within two or more of such categories of materials. All ingredients in the compositions can have functions in addition to their primary function, and can contribute to the overall properties of the composition, including its stability, effectiveness, consistency, mouthfeel, taste, odor and so on. Preferably, the carrier is selected for compatibility with other ingredients in the composition.
    [00127] As used throughout the document, ranges are used as an abbreviation to describe each value that is within the range. Any value within the range can be selected as the end of the range. In addition, all references cited in this document are incorporated by reference in their entirety, in the event of a conflict in the definition, in the present disclosure and that of a cited reference, the present disclosure will prevail.
    [00128] Unless otherwise specified, all percentages and quantities expressed in this specification will be understood to refer to weight percentages based on the total weight of the composition. The quantities given are based on the active weight of the material. For convenience, the components of the composition of the invention are expressed in the singular; however, it is to be understood that mixtures of components are encompassed for use in the singular expression, for example, "an orally acceptable carrier polymer" may include mixtures of two or more polymers described herein.
    [00129] The invention also includes a method for whitening teeth which comprises administering the composition of the invention to the oral cavity of a patient in need. In one embodiment of the invention, the method provides a tooth whitening increase effect of at least 20% on the whiteness of the tooth surface that lasts for up to four hours.
    [00130] The modalities of the present invention are further described in the examples that follow. The examples are merely illustrative and do not limit in any way the scope of the invention as described and claimed. EXAMPLES Example 1
    [00131] It has been found that when the carrier system for a blue dye is essentially non-aqueous, the ability of the blue dye to increase teeth whiteness is improved. We have shown that the increase in teeth whiteness is greater when the blue dye is formulated in a non-aqueous solution of glycerin, compared to when the blue dye is released from an aqueous solution. Table 1

    [00132] In addition, bioadhesive materials such as Copolymer VM / MA (Gantrez) and crosslinked PVP have been shown to increase the retention of blue dye on the teeth. The inventors found, surprisingly, that when the chemistry of the silica surface is modified with a strong base the resulting particle can also increase the blue dye retention on the surface. This new material consisting of a silicate-etched silica core is referred to as and core-coated silica (CSS). Table 2


    [00133] Previous experiments found that CSS was more effective than a solution containing Gantrez of glycerin dye in releasing and retaining blue dye for teeth for an increase in teeth whitening. In addition to simple solutions, we found that CSS can be extremely effective in maintaining better tooth whitening when released from a toothpaste formula with a critical water level. Example 2 Experimental method for assessing blue dye retention in teeth and resulting tooth whiteness
    [00134] The roots of human third molars were removed and the teeth were cut from the crown through the root. Each half of the tooth was mounted on methacrylate resin and then fixed on a brushing tray, the enamel side facing out using a thermal printing compound. Four teeth were mounted per tray. The teeth were brushed for 10 minutes with a 1: 2 (w / w) silica toothpaste suspension to remove any extrinsic surface stains, rinsed with deionized water, dried with fresh air, and CIELAB baseline measurements were recorded with a spectrophotometer (Spectroshade Micro, MHT Technologies). The teeth were submerged in saliva (9 mL / tray), aged at 37 ° C with gentle agitation for 15 minutes. The test toothpaste (6 g) was then added to the tray already containing 9 ml of saliva, the teeth were brushed for 2 minutes, rinsed with 100 ml deionized water, dried with fresh air and CIELAB measurements were recorded. The teeth were aged in saliva for 10 minutes or 30 minutes. The teeth were rinsed and dried with cold air before CIELAB measurements were recorded at each time point during the immersion cycle. Δb * is reported and is the change in the yellow-blue axis in the CIELAB color space. This is the metric by which the deposition of the blue dye can be quantified. The reported Δb * is the difference between the b * values of the tooth after surface stains are removed from that after brushing with the product containing the blue dye. A change in the whiteness index (WIO) can also be reported to show that the deposition of blue dyes results in an increased whiteness of a tooth. Table 3: Composition of the formula with bands


    [00135] Silica in core coating and blue dye versus corresponding formula without silica in core coating. Both formulas contain 7% water and 0.05% dye, 0.05% FD&C Blue # 1. Table 4:

    [00136] The data in Table 4 demonstrate that the addition of CSS to the formula results in similar deposition of the blue dye, but an increase in the dye retention time on the teeth. Table 5: CSS vs. Gantrez

    [00137] At 2% load in toothpaste with low water content (7%), CSS provides superior blue dye release and retention compared to Gantrez. Table 6: 2% xPVP with 0.05%, 0.10% and 0.15% FD&C Blue # 1

    [00138] It can be seen from the data in Table 6 that 2% silica in core coating provides a dose response in bleaching efficacy with various levels of blue dye.
    [00139] In a toothpaste formula with low water content (approximately 7%) and CSS, the increase in the amount of blue dye will also increase the amount of dye deposited on the teeth and the perceived whiteness of the teeth. Only 0.05% of FD&C Blue # 1 promotes a significant change in the whiteness of the teeth from the deposition of the blue dye.
    [00140] In summary, we demonstrate that a low water formula containing CSS can improve the retention of blue dye on teeth. For optimal release of the blue dye, a minimum amount of water is required to activate the CSS.
    [00141] As those skilled in the art will appreciate, countless changes and modifications can be made to the modalities described in this document, without departing from the spirit of the invention. All such variations are intended to fall within the scope of the appended claims.
    权利要求:
    Claims (15)
    [0001]
    1. Oral hygiene composition for teeth whitening, characterized by the fact that it comprises: (i) a dye showing a blue to violet blue color with an angle of shade in the CIELAB system ranging from 200 to 320 degrees, optionally from 200 to 290 degrees ; (ii) core coated silica particles, wherein each core coated silica particle comprises a silica core and a surface of the silica core is etched with the metal silicate; (iii) an orally acceptable carrier vehicle comprising a non-aqueous solvent; wherein the composition comprises water in an amount of between 3% by weight and 30% by weight and in which the metal silicate for each silica particle is: (iv) a monovalent metal ion metal silicate, optionally a group I metal ion; or (v) a monovalent metal ion metal silicate, optionally a group I metal ion and one or more of a divalent metal ion, a trivalent metal ion, and a tetravalent metal ion.
    [0002]
    2. Composition according to claim 1, characterized by the fact that the metal silicate comprises the formula M12SiO3.xH2O wherein M1 is a monovalent metal ion, optionally a group I metal ion, still optionally Na or K ex is 0 to 10.
    [0003]
    3. Composition according to claim 1 or 2, characterized by the fact that the external depth of 10 nm of a silica particle in core coating comprises from 0.1 to 10% by weight of MúSiOa.xJúO, optionally in which the external depth of 10 nm of a silica particle in a core coating has the general formula: (SiO2) p [Oo * N + nH + hOH-j]. qH2O where O * is oxygen in the form of silicate; N is a Group I metal ion; p, o, n, h, j and q are the atomic percentages of each component, and the total charge of each silica particle in the core coating is zero.
    [0004]
    4. Composition according to claim 3, characterized by the fact that the external depth of 10 nm of each particle has one of the following compositions: (SiOp) 3 0.3 oNa 0.41. 8, VOHpO (SiO2) 30.6 - No, 36.7, 63H2O (SiO2) 23.25 [dll, 73. H10.2 6N13.20]. 5.33 H2O.
    [0005]
    5. Composition according to claim 1, characterized by the fact that the metal silicate comprises a Group 2 metal ion silicate, a transition metal ion, a Group 13 metal ion, a metal ion Group 14 or mixtures thereof, optionally in which the metal silicate comprises a silicate of Ca2 +, Mg2 +, Zn2 +, Sn2 +, Sr2 +, Al3 +, Zr4 +, Ti4 +, Fe3 +, Fe2 +, Mo2 +, Co2 +, Ni2 +, Mn2 +, Cu2 +, Pd2 +, Mo2 +, Ru2 + or their mixtures.
    [0006]
    6. Composition according to claim 5, characterized by the fact that the metal silicate comprises the formula M2SiO3.xH2O in which M2 is a divalent metal ion and x is 0 to 10, optionally in which M2 is selected from the group consisting of in Zn, Ca, Mg, Sn and Sr, still optionally where M2 is Zn.
    [0007]
    7. Composition according to claim 5 or 6, characterized by the fact that the external depth of 10 nm of each silica particle in the core coating has the general formula: (SiO2) p [0 * oN + nM2 + mU3 + uV4 + vH + h0H-j]. qH20 where O * is oxygen in the form of silicate; N is a monovalent metal ion; M is a divalent metal ion; U is a trivalent metal ion, V is a tetravalent metal ion; Vp, o, n, m, u, v, h, j and q are the atomic percentages of each component; and the total charge of each core-coated silica particle is zero, optionally where the 10 nm outer depth of each core-coated silica particle has the following composition: (SiO2) 26. s2 [0 * 7. asNas. igZn4. esCli. 49H3.73] • 3.7 7H2O.
    [0008]
    8. Composition according to any one of claims 1 to 7, characterized in that the silica is selected from the group consisting of precipitated silica, fumed silica and fused silica.
    [0009]
    Composition according to any one of claims 1 to 8, characterized in that the d (0.5) value of the silica particles in the core coating is from 5 nm to 50 pm, optionally from 26 pm at 40 pm or from 18 pm to 25 pm or from 10 pm to 15 pm or from 5 nm to 12 nm.
    [0010]
    10. Composition according to any one of claims 1 to 9, characterized by the fact that the amount of water is 5; δ by weight to 15% by weight or from 5% by weight to less than 10% by weight, of 10% by weight to 17% by weight or about 7% by weight.
    [0011]
    11. Composition according to any one of claims 1 to 10, characterized by the fact that the amount of silica particles in the core coating is 0.001 to 10 t by weight or 0.01 to 5% by weight, or 0, 05 to 5 r by weight, or 0.1 to 5 t by weight, or 0.5 to 5% by weight, or 0.5 to 3% by weight, or 1 to 2% by weight, or about 1% by weight of the composition.
    [0012]
    12. Composition according to any one of claims 1 to 11, characterized by the fact that the dye is a blue dye, such as such as FD&C Blue # 1, FD&C Blue # 2, FD&C Blue # 4, Food blue Cl 5, Acid Blue 1, or mixtures thereof.
    [0013]
    13. Composition according to any one of claims 1 to 12, characterized by the fact that the dye comprises a mixture of one or more blue dyes and one or more red dyes.
    [0014]
    14. Composition according to any one of claims 1 to 13, characterized by the fact that the non-aqueous solvent is glycerol.
    [0015]
    15. Composition according to any one of claims 1 to 14, characterized by the fact that it is in the form of a toothpaste, optionally in which the composition is a toothpaste comprising one or more of an abrasive, surfactant, foaming agent , vitamin, polymer, enzyme, humectant, thickener, antimicrobial agent, preservative, flavoring and / or a combination of two or more of them.
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