• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    the present invention relates to a process for preparing a particulate antimicrobial composition. the invention also relates to hygienic or personal care compositions comprising the particulate antimicrobial composition obtainable by the process according to this invention. the invention more particularly relates to a process for preparing metallic antimicrobial nanoparticles immobilized on a porous inorganic material and also incorporating these particles in the hygiene or personal care compositions. the particulate antimicrobial composition comprises 0.05% to 3% by weight of antimicrobial metal particles and 97 to 99.95% by weight of the immobilizer comprising an inorganic porous material selected from zinc oxide, magnesium hydroxide or calcium carbonate.
    公开号:BR112017002310B1
    申请号:R112017002310-5
    申请日:2015-07-16
    公开日:2020-05-12
    发明作者:Das Somnath；Gupta Satyaranjan；Mitra Rupak；Girish Muralidharan；Amitava Pramanik
    申请人:Unilever N.V.；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report
    PROCESS FOR PREPARING A PARTICULATED ANTIMICROBIAL COMPOSITION AND HYGIENE OR PERSONAL CARE COMPOSITION
    Field of the Invention [0001] The present invention relates to a process for preparing a particulate antimicrobial composition. The invention also relates to hygiene or personal care compositions comprising the particulate antimicrobial composition made by the process. The invention provides antimicrobial metallic nanoparticles immobilized in a porous inorganic material and also for incorporating the particulate antimicrobial composition in the hygiene or personal care compositions.
    Background of the Invention [0002] Any discussion of the prior art throughout the specification should not be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.
    [0003] Antimicrobial metal nanoparticles, such as silver or copper nanoparticles, are broad-spectrum antimicrobial materials used for different purposes, including water purification and other hygiene related products. However, these metallic nanoparticles are known to be toxic and cannot be used as such in compositions for human use. They also have an impact on the environment.
    [0004] Silver or copper nanoparticles have a tendency to agglomerate under certain conditions of pH and temperature, which results in the decrease of their antimicrobial activity and transmit the coloring making the product aesthetically unpleasant and difficult to be incorporated in many products, especially when the base is white or light colored.
    Petition 870190121107, of 11/21/2019, p. 13/38
    2/19 [0005] Patent document WO14052973 A1 (Stelo Technologies) discloses a method for making silver nanoparticles using an ascorbic acid derivative or an alpha-hydroxy carboxylic acid derivative as a reducing agent. Silver nanoparticles can be coated in microparticles, embedded in hydrogel particles or coated with polysaccharides. The silver nanoparticles can be used in a wound dressing, a bandage, a fungus treatment product, a deodorant, a dental floss product, a toothpick, a dietary supplement, dental X-ray, a mouthwash, a toothpaste, treatment product for acne or wounds, exfoliating and exfoliating agent for the skin. In this process, which involves mixing silver salt with reducing agent and then coprecipitating the nanoparticles formed in the microparticles, the color of the composite particles will be dark and unsuitable for personal care products, especially when they have a white base.
    [0006] Patent document KR20090018456 (Korea University Industrial and Academic Collaboration Foundation) discloses the preparation of silver zinc oxide nanocomposite by means of simultaneous mixing of sources of silver and zinc with reducing agents in ethanolic medium. The simultaneous mixing of a source of zinc and silver salt leads to unwanted dark color and decreases the effectiveness of the antimicrobial.
    [0007] Patent document RU2311804 C1 (Megrabjan) discloses a bactericidal composition containing highly dispersed metallic silver stabilized with a protective material. The material was prepared by mixing silver salt, calcium salt and a base, which would lead to unwanted dark color and less antimicrobial effectiveness.
    [0008] Patent document JP11236304 (Dowa Electronics Materials Corp.) discloses a method of preparing the silver particles incorporated into calcium carbonate by means of a process of mixing the silver salt and calcium carbonate and then calcining the material. The material obtained would have the
    Petition 870190121107, of 11/21/2019, p. 14/38
    3/19 problem of dark color and less antimicrobial efficacy.
    [0009] Patent document US2008 / 0156232 A1 (Crudden et al., 2008) discloses a process for preparing additive antimicrobial particles in which the antimicrobial agent is mixed dry with a cake-forming material and subsequently this mixture drought is added to the water. After this step, the watery paste is left to harden.
    [0010] Patent document WO2012 / 161603 A1 (Uniwersytet Jagiellonski) discloses yet another method. The hybrid material containing calcium carbonate microparticles with a polyelectrolyte additive and silver nanoparticles incorporated into its structure is made by means of ultrasound-assisted coprecipitation. Trisodium citrate is added to the aqueous silver nitrate solution followed by sonication at elevated temperature. A sodium carbonate solution containing polyelectrolyte and calcium nitrate is added to it, which subsequently leads to the nano-silver particles embedded in a matrix.
    [0011] Patent document WO2011 / 075855 A1 (Perlen Converting AG) discloses a method in which the composite material is made by means of pyrolysis in flaming spray.
    [0012] Patent document WO2003 / 076341 A1 (Apyron Technologies INC) also discloses a particulate material containing a carrier and an antimicrobial agent.
    [0013] Patent document WO2006 / 015317 A1 (Acrymed INC) discloses a process for making silver compounds by mixing stoichiometric amounts of solutions of a silver salt, such as a nitrate or silver acetate with a corresponding alkali or alkaline earth metal salt of an organic anionic compound. When preparing silver compounds dispersed on carrier supports, the mixing step is carried out in the presence of insoluble carrier materials.
    [0014] Patent document WO2012 / 158702 A1 (BASF) discloses a process for preparing the antimicrobial metal compound by means of
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    4/19 vaporizing an antimicrobial metal or antimicrobial metal salt, such as silver, copper or salts thereof, using a plasma and vapor cooling system formed in the presence of a fluidized gas excipient powder. Alternatively, the excipient or an excipient precursor is incorporated into the antimicrobial metal or vaporized antimicrobial metal precursor and then, after cooling, the vapor from the antimicrobial metal and the vapor from the excipient condense to form the compound.
    [0015] Patent document US2006 / 0243675 A1 (Shiue-Lian Lin) discloses a process in which the components are added to pure water and mixed and then the mixture is reserved for 3 to 5 hours to produce a homogeneous mixture ready for use in the next step. In this process, no reducing agent is used.
    [0016] Patent document WO2008 / 027950 A1 (Allen Thomas) discloses a process in which metallic particles, such as silver, copper or gold with a surfactant, such as benzalkonium chloride, are taken in a liquid medium that also has a iodine source and a substrate carrier with the same type of metal as the particles deposited in it. This leads to embedded microparticles.
    [0017] Patent document CN101999409 (Henan Huier) reveals a process in which 15 to 70% by mass of deionized water or tap water are placed for 16 to 36 hours at room temperature in a reactor. A zinc nanocarrier solution is added to the reactor, which is then dispersed and emulsified under the high speed mixture and shear for 6 to 20 minutes, while maintaining the liquid temperature at 5 to 25 degrees Celsius. Then a solution with a silver salt is added to the reactor and continuously dispersed and emulsified for 40 to 90 minutes. This is followed by spraying a solution of a reducing agent in the reactor with a flow rate of 1.5 to 9.5 kg / minute continuously dispersed and emulsified for 30 to 60 minutes to obtain the antimicrobial disinfectant.
    [0018] Patent document CN101195719B (Cao) reveals a material
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    5/19 compound containing a carrier and antibacterial metal.
    [0019] It has now been possible to solve the problems of the prior art and form a broad-spectrum, light-colored particulate antimicrobial composition with good antimicrobial properties comprising antimicrobial metal particles and porous inorganic material selected from water-insoluble inorganic materials and also providing a process for preparing this.
    [0020] It is an object of the present invention to provide a light-colored particulate antimicrobial composition that has good antimicrobial properties.
    [0021] Another objective is to provide a process for preparing a particulate antimicrobial composition that has good antimicrobial properties.
    [0022] It is yet another objective of the present invention to provide a particulate antimicrobial composition that has good antimicrobial properties and is aesthetically suitable for incorporation into hygiene or personal care compositions. It is especially beneficial for use when the basis of the hygiene or personal care composition is white or light in color.
    [0023] In addition to the elimination of bacteria, these materials are also able to act in the elimination of viruses.
    Summary of the Invention [0024] According to the present invention, there is provided a process for preparing a particulate antimicrobial composition, the process comprises the steps of:
    i. mixture of an aqueous dispersion of an immobilizer, in which the immobilizer is present in an amount of 1-5% by weight (by weight of the dispersion) and in which the immobilizer is selected from the inorganic porous material selected from oxide of zinc, magnesium hydroxide or calcium carbonate and where the immobilizer has a particle size in the range of 1-10 microns and an aqueous solution of a reducing agent, where the reducing agent is present in the aqueous solution in an amount from 10 to 30% in
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    6/19 weight of the immobilizer in the aqueous dispersion;
    ii. raising the temperature of the mixture resulting from step (i) to a temperature in the range of 70 ° C to 90 ° C;
    iii. adding a water-soluble metal salt to the mixture resulting from step (ii) in an amount equivalent to 0.05 to 3% of the metal by weight of the immobilizer being mixed.
    [0025] In accordance with yet another aspect of the present invention, a hygienic or personal care composition is provided comprising:
    i. 5% to 85% by weight of a surfactant and ii. 0.1 to 5% by weight of a particulate antimicrobial composition obtainable by the process of the invention.
    Detailed Description of the Invention [0026] These and other aspects, characteristics and advantages will become apparent to those skilled in the art from a reading of the following detailed description and attached claims. For the avoidance of doubt, any feature of one aspect of the present invention can be used in any other aspect of the invention. The word "comprising" is intended to mean "including", but not necessarily "consisting of" or "composed of". In other words, the steps or options listed need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to these examples per se. Similarly, all percentages are weight / weight percentages, unless otherwise stated. Except for comparative and operational examples, or where explicitly stated otherwise, all numbers in this specification and claims indicating material quantities or reaction conditions, physical properties of materials and / or use are to be understood as modified by the word "approximately ”. The numerical ranges expressed in the "from x to y" format are understood to include x and y. When, for a specific characteristic, multiple preferred ranges are described in the “from x to y” format, it is understood that
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    7/19 all tracks combining the different end points are also covered.
    [0027] The particulate antimicrobial composition made according to the invention comprises 0.05% to 3% by weight of antimicrobial metal particles and 97 to 99.95% by weight of the immobilizer comprising inorganic porous material selected from zinc oxide, magnesium hydroxide or calcium carbonate.
    [0028] The% by weight of the antimicrobial metal particles and the immobilizer in the particulate antimicrobial composition is by weight of the composition.
    Antimicrobial metal particles:
    [0029] It is preferred that the antimicrobial metal particles are preferably selected from the silver or copper particles, more preferably, from silver or copper nanoparticles and even more preferably they are silver nanoparticles.
    Immobilizer:
    [0030] The immobilizer is selected from a porous inorganic material selected from porous zinc oxide, magnesium hydroxide or calcium carbonate, and it is preferred that the porous inorganic materials have a nano / microstructured assembly and more preferably are aggregated of nanoplate-type structures preferably having 20-100 nm in width and more preferably 40-60 nm in width. It is preferred that the immobilizer has a particle size in the range of 1-10 microns and more preferably 2 to 5 microns. The immobilizer is preferably selected from porous zinc oxide or calcium carbonate.
    [0031] Porous inorganic materials that have nanoplate-type structures are preferably obtained from a commercial source or can be prepared using a standard precipitation process that promotes the formation of porous structures through the use of aspect modifiers crystal or through precise control of precipitation conditions. The porous calcium carbonate used is preferably
    Petition 870190121107, of 11/21/2019, p. 19/38
    8/19 polymorph vaterite, and porous zinc oxide is preferably prepared through the standard precipitation process that promotes the formation of porous structures, through the use of modifiers of the crystal aspect. Porous magnesium hydroxide is preferably obtained from the calcination of light magnesium carbonate, and such materials are also commercially available.
    [0032] The particulate antimicrobial composition comprises 0.05% to 3% by weight of metallic antimicrobial particles preferably immobilized in 97 to 99.95% by weight of an immobilizer comprising porous inorganic material selected from zinc oxide, magnesium hydroxide or calcium carbonate. Preferably, the particulate antimicrobial composition comprises 0.5% to 1.5% by weight of metallic antimicrobial particles and 98.5% to 99.5% by weight of an immobilizer. In general, when reference is made to immobilized antimicrobial particles or immobilized antimicrobial metal particles or immobilized metal nanoparticles or immobilized materials with reference to specific metals, such as silver or copper, it refers to the antimicrobial particulate composition of the invention.
    [0033] According to the present invention, a process is provided for preparing a particulate antimicrobial composition and the process comprises the steps of:
    i. mixture of an aqueous dispersion of an immobilizer, in which the immobilizer is present in an amount of 1-5% by weight (by weight of the dispersion) and in which the immobilizer is selected from the inorganic porous material selected from oxide of zinc, magnesium hydroxide or calcium carbonate and where the immobilizer has a particle size in the range of 1-10 microns and an aqueous solution of a reducing agent, where the reducing agent is present in the aqueous solution in an amount from from 10 to 30% by weight of the immobilizer in the aqueous dispersion;
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    9/19 ii. raising the temperature of the mixture resulting from step (i) to a temperature in the range of 70 ° C to 90 ° C;
    iii. adding a water-soluble metal salt to the mixture resulting from step (ii) in an amount equivalent to 0.05 to 3% by weight of the metal by weight of the immobilizer being mixed.
    [0034] The particulate antimicrobial composition prepared by means of the process according to the invention is preferably recovered by separating the solid from the liquid medium by preferably filtration, and the particulate antimicrobial composition was preferably dried at a temperature in the range of 10-80 ° C ° C.
    [0035] A calcination step preferably not necessary for the process according to the invention and preferably the process does not comprise a calcination step.
    Immobilizer:
    [0036] The immobilizer used in the process is in the range of 1-5% and more preferably from 2 to 4% and is selected from the porous inorganic material selected from porous zinc oxide, magnesium hydroxide or calcium carbonate. The particle size is in the range of 1-10 microns and more preferably 2 to 5 microns. The immobilizer is used as an aqueous dispersion. It is preferred that the immobilizer is selected from porous zinc oxide or calcium carbonate.
    Reducing Agent:
    [0037] The reducing agent is preferably selected from the water-soluble salt of a carboxylic acid with a group of 1-4-carboxylate and most preferably it is selected from sodium acetate, sodium oxalate, trisodium citrate or diamine tetracetate disodium ethylene. It is preferred to include trisodium citrate as the reducing agent. The reducing agent is used in the range of 10-30% by weight with respect to the immobilizer and more preferably 15 to 20% by weight with respect to the immobilizer. The reducing agent is preferably provided as an aqueous solution.
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    10/19 [0038] It is essential that the aqueous dispersion of the immobilizer and the aqueous solution of the reducing agent are mixed before adding the metal salt solution. The temperature of the mixture is raised to a temperature in the range of 70 ° C to 90 ° C and more preferably 80 ° to 85 ° C.
    [0039] The pH of the reaction medium during the process is preferably maintained at a pH greater than 5 and most preferably it is in the 6-8 range.
    Water-soluble metallic salt:
    [0040] It is preferable that the water-soluble metal salt is selected from the water-soluble salt of silver or copper. It is preferable to add the water-soluble metal salt as an aqueous solution.
    [0041] It is preferable that the water-soluble silver salt is selected from silver nitrate or silver acetate. 0.05% to 3% silver by weight of an immobilizer which is preferably administered via an aqueous solution are preferably silver nitrate or silver acetate. To administer the required weight% of silver, the silver nitrate range is preferably 0.08% to 4.72% by weight or 0.078% to 4.63% by weight of silver acetate. It is preferred to use silver nitrate as the water-soluble silver salt.
    [0042] It is preferable that the water-soluble copper salt is selected from copper (II) sulfate, copper (II) nitrate, copper (II) chloride, and copper (II) acetate. 0.05% to 3% copper by weight of an immobilizer are preferably administered through an aqueous solution of copper salt in the range of 0.1% to 9%, more preferably in the range of 0.13% to 7.5 % for copper (II) sulphate, 0.15% to 8.9% for copper (II) nitrate, 0.1% to 6.4% for copper (II) chloride and 0.14% to 8, 6% for copper (II) acetate. It is preferred to use copper (II) nitrate as the water-soluble copper salt.
    [0043] In accordance with yet another aspect of the present invention, a hygienic or personal care composition is provided comprising:
    i. 5% to 85% by weight of a surfactant and
    Petition 870190121107, of 11/21/2019, p. 22/38
    11/19 ii. 0.1 to 5% by weight of a particulate antimicrobial composition obtainable by a process according to the present invention.
    [0044] The level of surfactant in the personal care composition is 5% to 85% by weight of the hygiene or personal care composition and preferably 15-40% by weight.
    [0045] The surfactant is selected from the class of anionic, non-ionic, cationic or zwiterionic surfactants and preferably selected from anionic surfactants. The anionic surfactant is preferably selected from soap or non-soap surfactant.
    [0046] It is preferred that the particulate antimicrobial composition is 0.1 to 5% by weight of the personal care composition or hygiene composition and more preferably 0.25 to 4% by weight of the personal care or hygiene composition.
    [0047] The personal care or hygiene composition of the present invention can be in the form of liquid or solid compositions. Non-limiting examples of such topical compositions include lotions and creams for skin without removing, antiperspirants, deodorants, lipsticks, foundations, masks, self-tanners or sunscreen lotions, and washable products such as shampoos, conditioners, shower gels or soaps.
    [0048] It is preferable that the composition comprises conventional ingredients used in a hygiene or personal care composition and more preferably ingredients, such as fluorescent, perfumes, texture controlling agents, emollients and other antimicrobial agents.
    [0049] The invention will now be illustrated by means of the following non-limiting examples.
    Examples
    Example 1 [0050] Preparation of an antimicrobial particulate composition comprising silver nanoparticles.
    Immobilizer preparation:
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    12/19 [0051] Particles sized in microns of the immobilizer were prepared using the process described below:
    i. Porous zinc oxide:
    [0052] Porous zinc oxide was prepared using a process as described in CrystEngComm 15, 32 (2013), pp. 6349-6358. For the preparation of 100 g of porous zinc oxide, 60 g of zinc nitrate and 140 g of hexamine were mixed with trisodium citrate, in which the ratio of zinc concentration to trisodium citrate concentration was kept at 10, and the mixture was heated in a covered hydrothermal vessel at 90 ° C for 12 hours. The precipitated porous zinc oxide was filtered, washed with deionized water and air dried.
    ii. Porous Calcium Carbonate:
    [0053] 100 g of porous calcium carbonate were prepared by mixing 147 g of calcium chloride with 106 g of sodium carbonate under constant stirring at 10 ° C for 5 hours. The paste was aged for 5 hours, filtered, washed with deionized water and dried in air.
    iii. Porous Magnesium Hydroxide:
    [0054] Pure and light grade magnesium oxide was purchased from Merck. The magnesium oxide was dispersed in water to obtain the porous magnesium hydroxide that was used as an immobilizer.
    Preparation of antimicrobial particulate composition comprising silver nanoparticles:
    [0055] 400 mg of immobilizer, which were porous zinc oxide or calcium carbonate or magnesium hydroxide, were dispersed in 10 ml of water and mixed with 4 ml of 1% trisodium citrate solution. The mixture was heated to 80 ° C followed by the addition of 0.25 ml of 2% freshly prepared silver nitrate. The mixture was stirred for 20 minutes at 300 rpm. The sample was filtered and dried at room temperature. The size of the silver nanoparticles formed in the above process varied between 5-50 nm, and the silver nanoparticles were immobilized in the respective immobilizer.
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    13/19
    Evidence for incorporating silver in the immobilizer:
    [0056] The energy dispersive X-ray spectroscopic analysis of the antimicrobial particulate composition comprising silver nanoparticles and porous zinc oxide prepared using the process described in Example 1 was performed using a FESEM (ZEISS) instrument operated at 10 kV of voltage electron to determine the presence of silver in the antimicrobial particulate composition. The analyzed weight% of different ingredients is shown in Table 1 below:
    Table 1
    Element Weight (%) Oxygen 23.60 Zinc 73.09 Silver 3.31 Total 100.00
    [0057] The results in Table 1 show that the particulate antimicrobial composition contains zinc, oxygen and silver as constituents.
    Reflectance of the antimicrobial particulate composition comprising silver nanoparticles:
    [0058] The reflectance of the antimicrobial particulate composition comprising silver nanoparticles in which the immobilizer used was zinc oxide, calcium carbonate or magnesium hydroxide and prepared as described in Example 1 was measured.
    [0059] In the comparative example (Example 5) where commercial non-porous zinc oxide was used to immobilize the silver nanoparticles, otherwise using the same process. In another comparative example (Example 6), a process according to the prior art was used, in which the immobilization of the silver particles was done through calcination. In this process, porous zinc oxide was used without using the reducing agent and at the end of the process the material was calcined by heating to a temperature of 500 ° C.
    [0060] The reflectance of the materials described above was measured using the
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    14/19 Gretag Macbeth reflectometer at 460 nm in SCI, SAV mode, UV condition excluded. A film of the dispersion of the immobilized silver nanoparticles was prepared on a glass slide with an area of 4 cm X 4 cm. The film was dried, and the reflectance was measured. The measured b * values indicated the opacity index. The negative b * values indicated the proximity to the whitish color, and the b * values less than -0.5 indicate the approximately white color. The data are presented in Table 2.
    Table 2
    Examples Material B* Example 2 Silver nanoparticles immobilized on porous zinc oxide -1.1 Example 3 Silver nanoparticles immobilized on porous calcium carbonate -8.0 Example 4 Silver nanoparticles immobilized in porous magnesium hydroxide -1.9 Example 5 Silver nanoparticles immobilized on zinc oxide in a non-porous rod shape 5.0 Example 6 Silver nanoparticles immobilized on porous zinc oxide by means of a calcination process 3.6
    [0061] The data presented in Table 2 show that the particulate antimicrobial composition prepared according to the invention has a negative b * value indicating a desired color profile that can best be used in formulations without affecting the aesthetics of the product. In the comparative examples in which the immobilizer used was non-porous zinc oxide and had a rod-shaped structure or where the immobilization process of the silver particles was carried out using a calcination process, the immobilized materials had b * values relatively high indicating a dark color.
    Variation in process efficiency parameters:
    [0062] The preparation of the particulate antimicrobial composition comprising silver nanoparticles was done by changing the concentration of the immobilizer, silver nitrate or trisodium citrate. For all
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    15/19 In these experiments, zinc oxide was used as an immobilizer.
    [0063] The reflectance of the antimicrobial particulate composition comprising silver nanoparticles obtained was measured as described above to assess the b * value to indicate the color of the material and the results are shown in Table 3. In Table 3, in the process condition column , the weight% of porous zinc oxide is in relation to the volume of water, while the percentages of silver and trisodium citrate are in relation to porous zinc oxide. All percentage values mentioned in Table 3 correspond to the amount of ingredients used during the preparation of the particulate antimicrobial composition comprising silver nanoparticles. The product composition column indicates the weight% of silver and porous zinc oxide after the immobilization of the silver nanoparticles.
    Table 3
    Ex. No. Variation ofProcess Process Condition Product Composition B* Oxideporous zinc Silver Trisodium citrate Ag%inWeight ZnO% inWeight mg % inWeight mg % by weight mg % by weight 7 Variation in porous zinc oxide concentration 250 2.5 6.35 2.5 40 16 2.5 97.5 -5.92 8 400 4 6.35 1.6 40 10 1.6 98.4 -5.36 9 1000 10 6.35 0.6 40 4 0.6 99.4 -0.45 10 Variation of silver concentration 400 4 1.27 0.3 40 10 0.3 99.7 -12.3 8 400 4 6.35 1.6 40 10 1.6 98.4 -5.36 11 400 4 25.41 6.0 40 10 6.0 94.0 +13.9 12 400 4 63.53 13.7 40 10 13.7 86.3 +1.1 13 Variation of citrate concentrationtrisodium 400 4 6.35 1.6 20 5 1.6 98.4 +3.84 8 400 4 6.35 1.6 40 10 1.6 98.4 -5.36 14 400 4 6.35 1.6 120 30 1.6 98.4 -10.9
    0064] The data presented in Table 3 show this variation in the
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    16/19 process parameters during the preparation of the particulate antimicrobial composition using silver nanoparticles and porous zinc oxide. The b * value becomes more positive with the increase in weight% porous zinc oxide (Example 9), while the increase in silver weight% leads to the positive b * value (Example 11 and 12). Alternatively, decreasing the weight% of the trisodium citrate below 10 leads to a positive b * value (Example 13). Generally for the best result as shown in Table 3 to obtain the b * value less than 0.5, the percentage in aqueous weight of porous zinc oxide is in the range of 1-5, and the percentage in weight of citrate and silver with relation to porous zinc oxide is in the range of 10-30 and 0.05-3, respectively.
    Sequence of process steps:
    [0065] The sequence of addition of materials according to the present invention in which the aqueous dispersion of the immobilizer is mixed with the aqueous solution of a reducing agent, such as trisodium citrate followed by the addition of antimicrobial silver nitrate, has been compared to process in which antimicrobial silver nitrate was added prior to the addition of the reducing agent or in which the process for preparing porous zinc oxide as described previously in Example 1 was carried out in the presence of silver nitrate, despite using the same process. In the processes, the levels of the different materials were as in Example 8.
    [0066] The reflectance of the immobilized material obtained was measured as described above to assess the b * value to indicate the color of the material, and the results are shown in Table 4.
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    17/19
    Table 4
    Example Process B* Example 8 Addition of trisodium citrate to porous zinc oxide followed by silver nitrate -5.4 Example 15 Addition of silver nitrate to porous zinc oxide followed by trisodium citrate +13.5 Example 16 Hydrothermal treatment of zinc nitrate and hexamine in the presence of trisodium citrate and silver nitrate +12.6
    [0067] The data presented in Table 4 show that the addition of trisodium citrate to zinc oxide followed by silver nitrate produces the antimicrobial particulate composition according to the invention with a negative b * value (Example 8), while the addition of nitrate silver to zinc oxide followed by trisodium citrate produces a positive b * value (Example 15). Also, the formation of porous zinc oxide in the presence of silver nitrate again produces the positive b * value (Example 16).
    Antimicrobial efficacy:
    [0068] The antimicrobial efficacy was tested using the gram positive bacterium Staphylococcus aureus and the gram negative bacterium Escherichia coli using the Time kill test, according to the BS EN1040 protocol.
    [0069] 10 g of soap were dissolved in 90 ml of water at 50 ° C. It was left for equilibrium at a temperature of 45 ° C in a water bath. The particulate antimicrobial composition comprising silver nanoparticles was added to the soap solution to obtain an effective silver charge of 1 ppm, and this was calculated using the ICP-OES analysis. 1 ml of bacterial suspension of Staphylococcus aureus (10 8 cells / ml) and E. coli (10 8 cells / ml), respectively, was added to the tubes containing 1 ml of sterile water and left for equilibration at 45 ° C for 2 minutes. 8 ml of 10% solution of
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    18/19 soap containing particulate antimicrobial composition comprising silver nanoparticles were added to these bacterial suspensions respectively and were left to act for 30 seconds and 60 seconds, respectively. At these respective time points, 1 ml of the suspension was taken and added to 9 ml of neutralizer (Dey-Engley Neutralizing Broth) to inactivate the action of the antimicrobial. The neutralized samples were then transferred to plates after serial dilution in Soy Agar Tripticase (nutrient medium) to enumerate residual bacteria. The effectiveness of the particulate antimicrobial composition comprising silver nanoparticles was also assessed with methicillin-resistant Staphylococcus aureus (MRSA) in 60 and 300 seconds, respectively. The results are shown in Table 5.
    Table 5
    Example Material Bacterial reduction (log CFU / ml) E. coli S. aureus MRSA 30 sec 60 s 30 sec 60 s 60 s 300 s Example17 Soap 3.4 3.5 0.0 0.1 0.3 1.2 Example18 Soap + Porous zinc oxide 3.9 6.3 0.0 0.2 - - Example19 Soap + silver nitrate 6.3 7.7 4.2 5.2 - - Example20 Soap +nanoparticles ofsilver 3.7 7.0 4.8 6.0 - - Example21 Soap +Nanoparticles ofsilver immobilized on zinc oxide 7.6 6.7 5.1 6.7 2.0 4.6 Example22 Soap +Nanoparticles ofsilver immobilized on calcium carbonate 8.1 8.1 4.8 6.8 1.8 4.9
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    19/19
    Example23 Soap +Nanoparticles ofsilver immobilized in magnesium hydroxide 5.2 7.8 3.9 5.4 - -
    [0070] The data in Table 5 shows that immobilized silver nanoparticles (Example 21-23) have superior bacterial reduction against both E. coli and S. aureus when compared to any of their individual constituents. Although silver nitrate and silver nanoparticles with soap show comparative antimicrobial action, their use is limited, since silver nitrate is unstable and cannot be formulated in products, while the use of nanoparticles alone has problems related to agglomeration, instability after storage and environmental risks. The data also show that the immobilized silver nanoparticles have antimicrobial action against MRSA with 5 log reduction in 300 s.
    [0071] No effectiveness validation tests have been performed on immobilizers per se used in Example 22 and Example 23, since there is no evidence in the literature on antimicrobial activity, calcium carbonate (immobilizer in Example 22) or magnesium hydroxide (immobilizer in Example 23).
    权利要求:
    Claims (8)
    [1]
    Claims
    1. Process for preparing a particulate antimicrobial composition, the process being characterized by comprising the steps of:
    1. mixing an aqueous dispersion of an immobilizer, in which the immobilizer is present in an amount of 1-5% by weight of the dispersion and in which the immobilizer is selected from the inorganic porous material selected from zinc oxide, hydroxide magnesium or calcium carbonate and where the immobilizer has a particle size in the range of 1-10 pm and an aqueous solution of a reducing agent, where the reducing agent is present in the aqueous solution in an amount from 10 to 30% by weight of the immobilizer in the aqueous dispersion;
    ii. raising the temperature of the mixture resulting from step (i) to a temperature in the range of 70 ° C to 90 ° C;
    iii. adding a water-soluble metal salt to the mixture resulting from step (ii) in an amount equivalent to 0.05 to 3% of the metal by weight of the immobilizer being mixed.
    [2]
    2. Process for preparing a particulate antimicrobial composition according to claim 1, characterized in that the water-soluble metal salt is selected from the silver or water-soluble copper salt.
    [3]
    Process for preparing a particulate antimicrobial composition according to claim 1 or 2, characterized in that the water-soluble metal salt is water-soluble silver salt.
    [4]
    4. Process for preparing a particulate antimicrobial composition according to claim 3, characterized in that the water-soluble silver salt is selected from silver nitrate or silver acetate.
    Petition 870190121107, of 11/21/2019, p. 32/38
    2/2
    [5]
    5. Process for preparing a particulate antimicrobial composition, according to claim 4, characterized in that the water-soluble copper salt is selected from copper (II) sulfate, copper (II) nitrate, copper (II) chloride ), or copper (II) acetate.
    [6]
    Process for preparing a particulate antimicrobial composition according to any one of claims 1 to 5, characterized in that the reducing agent is selected from a water-soluble salt of a carboxylic acid with a group of 1-4-carboxylate.
    [7]
    Process for preparing a particulate antimicrobial composition according to claim 1 or 6, characterized in that the reducing agent is selected from sodium acetate, sodium oxalate, trisodium citrate or disodium ethylene diamine tetracetate.
    [8]
    8. Hygiene or personal care composition, characterized by comprising:
    i. 5% to 85% by weight of a surfactant and ii. 0.1 to 5% by weight of a particulate antimicrobial composition obtainable by a process as defined in claim 1.
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    CN106572949A|2017-04-19|
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    WO2016020168A1|2016-02-11|
    US20170209347A1|2017-07-27|
    US20190262243A1|2019-08-29|
    CN106572949B|2021-01-26|
    EA030761B1|2018-09-28|
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    EP3354134A1|2018-08-01|
    US10682298B2|2020-06-16|
    EA201790319A1|2017-06-30|
    EP3177142A1|2017-06-14|
    BR112017002310A2|2018-01-16|
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    法律状态:
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-02-23| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    优先权:
    申请号 | 申请日 | 专利标题
    EP14180010.2|2014-08-06|
    EP14180010|2014-08-06|
    PCT/EP2015/066298|WO2016020168A1|2014-08-06|2015-07-16|A process for preparing an antimicrobial particulate composition|
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