CN101343055B - Nano-hydroxyapatite hydrosol, preparation and application in toothpaste - Google Patents
Nano-hydroxyapatite hydrosol, preparation and application in toothpaste Download PDFInfo
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- CN101343055B CN101343055B CN2008100302468A CN200810030246A CN101343055B CN 101343055 B CN101343055 B CN 101343055B CN 2008100302468 A CN2008100302468 A CN 2008100302468A CN 200810030246 A CN200810030246 A CN 200810030246A CN 101343055 B CN101343055 B CN 101343055B
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Abstract
The invention discloses a preparing method of nano-hydroxyapatite hydrosol, comprising steps as follows: firstly, the milk of lime which contains 1 to 28wt% calcium hydroxide is prepared and added into a reactor; secondly, acetic acid or calcium acetate is added into the milk of lime and mixed to obtain a mixture; and the molar ratio of acetate and calcium in the mixture is 1-6:10; thirdly, the mixture is heated to 30 to 95 DEG C, 8 to 30wt% dilute phosphoric acid is gradually added and stirred at a speed > 300r/min, the dilute phosphate is added for 1 to 30min, the reaction continues for 3 to 20 hours, the pH value is adjusted by the acetic acid solution to be 7.5 to 8.5, and then the nano-hydroxyapatite hydrosol is obtained after cooling; and the mass of the added dilute phosphoric acidis that: the molar ratio of calcium and phosphorus is between 1.68-1.70:1 after the quantity of calcium of the calcium acetate in the solution is deducted. The method has advantages that the process is simple, and the nano-hydroxyapatite hydrosol prepared can be used in producing toothpastes.
Description
Technical field
The present invention relates to nano-hydroxyapatite hydrosol and preparation method thereof and the application in toothpaste.
Background technology
Hydroxyapatite is the main component of vertebrates skeleton and tooth, has good chemical stability and biocompatibility.Nanometer hydroxyapatite has characteristics such as high surface energy, high electrostatic field, strong polarization force, and enamel and cementum are had high affinity, can promote the enamel surface remineralization, improves dentium nitor face microhardness, strengthens the resistance to acid, tooth-whitening; Nanometer hydroxyapatite can also adsorb aminoacid and polysaccharide such as protein, glucosan in addition, destroys the formation of cariogenic bacteria speckle, so nanometer hydroxyapatite has the function of control dental caries and these two kinds of multiple oral diseases of periodontal disease.For the preparation of nanometer hydroxyapatite and the application in toothpaste, existing many people have carried out useful research: " nanometer hydroxyapatite and preparation method and the application in toothpaste " (number of patent application 02160058.9) employing calcium hydroxide and dalcium biphosphate as inventions such as Meng Xiangcai are raw material, by adding the nucleating agent citrate, prepared sizes add in the toothpaste less than hydroxyapatite hydrosol and the powder body of 100nm.And in another patent " application of acicular nanometer hydroxyapatite in toothpaste " (number of patent application 200410043880.7), the inventor joins the acicular nanometer hydroxyapatite of full-size less than 50nm in the toothpaste, reached repair teeth, preventing decayed tooth, desensitization effect better, but the preparation method of unexposed nanometer hydroxyapatite." a kind of preparation method of activity hydroxy agustite tooth-paste " (number of patent application 200510096305.8) of invention such as Zhang Chaowu is that feedstock production obtains hydroxy apatite powder with calcium hydroxide and phosphoric acid, joins in the toothpaste through high-temperature calcination." a kind of nanoscale toothpaste additive and synthetic method " (number of patent application 200410046143.2) of invention such as Liu Jie adopts sol-gel process to prepare a kind of strontium and replaces the nanometer hydroxyapatite toothpaste additive." method of Hydrothermal Preparation nanometer hydroxyapatite colloid " (patent No. 200610020579.3) of invention such as Xie Xingyi, adopt coprecipitation to prepare the nanometer hydroxyapatite colloid particle of aqueous phase stable dispersion by the citrate that adds 0.2～2 times of mole of calcium salt, ultrafiltration purification gets nanometer hydroxyapatite colloid then.
Though can both prepare nanometer hydroxyapatite and contain the toothpaste of nanometer hydroxyapatite, can not satisfy simultaneously all that raw material is cheap, preparation is simple, good dispersion, add requirement easily by above-mentioned technology.Toothpaste is a kind of popular consumer goods, and is cheap, complicated preparation and dispersion technology, and use the unnecessary additive of too much toothpaste all can increase product cost, influence it and apply.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, the invention discloses a kind of preparation method of nano-hydroxyapatite hydrosol, this method technology is simple, the prices of raw and semifnished materials are cheap, and the nano-hydroxyapatite hydrosol for preparing according to this method need not carry out special dispersion treatment and just can add in the toothpaste easily.
For realizing that purpose of the present invention adopts following technical scheme: a kind of preparation method of nano-hydroxyapatite hydrosol comprises the steps:
The first step, preparation contains the lime cream of calcium hydroxide 1～28wt%, in the reactor of packing into;
Second step added acetic acid or calcium acetate in described lime cream, stir, and got mixture; The mol ratio of acetate and calcium is 1～6: 10 in the mixture;
The 3rd step, with described mixture heated to 30～95 ℃, add the dilute phosphoric acid solution of 8～30wt% then gradually and continue stirring, mixing speed〉300r/min, the time that adds dilute phosphoric acid solution is 1～30 minute, continues reaction 3～20 hours, regulates pH value to 7.5～8.5 with acetum at last, cooling gets nano-hydroxyapatite hydrosol; Wherein, the quality that adds dilute phosphoric acid solution calculates by the following method: deducting after the calcium amount of calcium acetate in the described mixture in calcium phosphorus mol ratio is that 1.68～1.70: 1 ratio adds dilute phosphoric acid solution.
In order to realize the present invention better, the content of calcium hydroxide is 10～28wt% in the lime cream of the described first step.
The mol ratio of acetate and calcium is 2～4: 10 in the mixture in described second step.
Described the 3rd step is for described mixture heated to 65～95 ℃, add the dilute phosphoric acid solution of 14～30wt% then gradually and continue stirring, mixing speed 〉=600r/min, the time that adds dilute phosphoric acid solution is 3～10 minutes, continue reaction 6～12 hours, regulate pH value to 7.5～8.5 with the acetum of 0.5～3wt% at last, cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that a kind of preparation method of above-mentioned nano-hydroxyapatite hydrosol makes comprises the nanometer hydroxyapatite of 1～18wt%, calcium acetate and the water of 1～8wt%.
Described nanometer hydroxyapatite is needle-like, and length is 60～100nm, is monodisperse status in described nano-hydroxyapatite hydrosol.
Above-mentioned nano-hydroxyapatite hydrosol is used to prepare toothpaste.
Above-mentioned nano-hydroxyapatite hydrosol is used to prepare toothpaste, earlier described nano-hydroxyapatite hydrosol is mixed with wetting agent, add the abrasivus that sodium silicate and quality are abrasivus gross mass 1/3～1/2 then, mixed 0.5～2 hour, add remaining abrasivus and other raw material again, fully mix the back and prepare toothpaste by known method.Wherein the mass ratio of nano-hydroxyapatite hydrosol and sodium silicate is 1: 0.01～0.02; The mass ratio of nano-hydroxyapatite hydrosol and wetting agent is 1: 0.5～1.1; The mass ratio of nano-hydroxyapatite hydrosol and abrasivus is 1: 1～2.2.
Wherein, the nanometer hydroxyapatite that joins in the toothpaste accounts for 2～7% of toothpaste gross mass.
Principle of the present invention is such: utilize phosphoric acid and calcium hydroxide reaction can prepare nanometer hydroxyapatite, but this course of reaction relates to the dissolving of calcium hydroxide, therefore adding phosphoric acid can not be too fast, otherwise reaction is difficult to carry out fully.And the phosphoric acid adding speed that slows down easily generates bigger particle, and the colloidal sol instability that forms, and concentration higher position is slightly reunited, precipitated.The present invention utilizes acetic acid to make reaction buffer, acetic acid can generate the solubility calcium acetate with calcium hydroxide reaction in course of reaction, go out acetic acid and phosphoric acid is replaceable, so not only can guarantee to have in the solution higher calcium ion concentration, and reaction is mainly carried out in liquid phase; In lime cream, add calcium acetate, the replaceable acetic acid that goes out in the calcium acetate of phosphoric acid during reaction, acetic acid generates the solubility calcium acetate with calcium hydroxide reaction again, therefore, utilizes calcium acetate can realize above-mentioned effect equally as reaction buffer.Acetic acid still is a kind of large fierce dog mixture, is enclosed in around the calcium hydroxide particle, can reduce the direct and solid particle reaction formation parcel of phosphoric acid.The existence of calcium acetate also can significantly increase the Zeat current potential of nanoparticle in the solution, makes colloid stable dispersion in production and storage process.
When the nano-hydroxyapatite hydrosol that utilizes the present invention to prepare prepares toothpaste, by adding the sodium silicate component, make ionized calcium transfer water-fast afwillite fine crystals to, then can solve the compatibility problems of other raw material in nano-hydroxyapatite hydrosol and the toothpaste, above-mentioned reaction can be expressed as:
Ca(CH
3COO)
2+Na
2SiO
3→CaO?nSiO
2+CH
3COO?Na
With respect to prior art major advantage of the present invention and beneficial effect be: (1) preparation method disclosed by the invention is a raw material with phosphoric acid and calcium hydroxide, creatively utilize calcium acetate to make reaction buffer and particle dispersants prepares nano-hydroxyapatite hydrosol, not only reduced the reinforced time, and the hydroxyapatite size is tiny in the nano-hydroxyapatite hydrosol that makes; (2) utilize the size of hydroxyapatite in the nano-hydroxyapatite hydrosol that preparation method disclosed by the invention makes to reach nanoscale, can save the operation such as washing, filtration, drying of time-consuming power consumption in the nano powder preparation process, save the energy, reduced production cost; And solid content reaches 18wt% in the nano-hydroxyapatite hydrosol that makes, and stores 60 days still good dispersions, need not carry out special dispersion treatment and just can add in the toothpaste; (3) preparation method raw material disclosed by the invention is cheap and easy to get, equipment is simple, technology is easily controlled, the production efficiency height.
Description of drawings
Fig. 1 is the XRD figure of solid matter in the nano-hydroxyapatite hydrosol for preparing of embodiment 1;
Fig. 2 is the TEM figure of the nano-hydroxyapatite hydrosol for preparing of embodiment 1;
Fig. 3 is the FT-IR figure of solid matter in the nano-hydroxyapatite hydrosol for preparing of embodiment 1.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
The first step, preparation calcium hydroxide content is the lime cream 10kg of 15wt%, in the 25L reactor of packing into;
Second step added the 0.3kg glacial acetic acid in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 95 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 6kg and lasting stirring of 17wt%, mixing speed 600r/min, the time that adds phosphoric acid,diluted is 3min, continues reaction 6 hours, regulates pH value to 8.0 with the acetum of 2wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
In the nano-hydroxyapatite hydrosol that makes the XRD figure of solid matter as shown in Figure 1, by the shown characteristic of its XRD figure as can be known, the solids in the obtained colloid is the low-crystallinity hydroxyapatite; The TEM of the nano-hydroxyapatite hydrosol that makes schemes as shown in Figure 2, and Zhi Bei nanometer hydroxyapatite microscopic pattern is needle-like as can be seen from Figure 2, and is scattered; The FT-IR of solid matter figure as shown in Figure 3 in the nano-hydroxyapatite hydrosol that makes, hydroxyapatite in the nano-hydroxyapatite hydrosol that makes as can be seen from Figure 3 is a trace carbon acid group substituted hydroxy apatite, this hydroxyapatite adds better effects if in the toothpaste to more near the tooth composition.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 25, nano-hydroxyapatite hydrosol 24, sodium silicate 0.3, CMC1.0, K
121.7, calcium carbonate 46.8, saccharin sodium 0.2, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol, the calcium carbonate that adds sodium silicate and 1/3 component then mixed 0.5 hour, adds calcium carbonate and other component of remaining 2/3 component again, fully mixes;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 2.5wt% in this toothpaste.
Embodiment 2
The first step, preparation calcium hydroxide content is the lime cream 10kg of 18wt%, in the 25L reactor of packing into;
Second step added the 0.6kg calcium acetate in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 65 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 7.1kg and lasting stirring of 20wt%, mixing speed 800r/min, the time that adds phosphoric acid,diluted is 5min, continues reaction 8 hours, regulates pH value to 8.0 with the acetum of 2wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 5, sorbitol 15, the hydrosol 34, sodium silicate 0.6, CMC1.0, K
121.8, CaHPO
441.4, saccharin sodium 0.2, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol and sorbitol, the calcium carbonate that adds sodium silicate and 1/2 component then mixed 0.6 hour, adds calcium carbonate and other component of remaining 1/2 component again, fully mixes;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 4.4wt% in this toothpaste.
Embodiment 3
The first step, preparation calcium hydroxide content is the lime cream 10kg of 22wt%, in the 25L reactor of packing into;
Second step added the 0.8kg calcium acetate in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 90 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 5.7kg and lasting stirring of 30wt%, mixing speed 600r/min, the time that adds phosphoric acid,diluted is 10min, continues reaction 12 hours, regulates pH value to 8.0 with the acetum of 2wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 5, sorbitol 15, the hydrosol 36, sodium silicate 0.7, CMC1.0, K
121.8, SiO
239.3, saccharin sodium 0.2, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol and sorbitol, add the SiO of sodium silicate and 1/3 component then
2Mixed 1 hour, and added the SiO of remaining 2/3 component again
2With other component, fully mix;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 6.5wt% in this toothpaste.
Embodiment 4
The first step, preparation calcium hydroxide content is the lime cream 11kg of 26wt%, in the 25L reactor of packing into;
Second step added 0.7kg acetic acid in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 90 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 6.3kg and lasting stirring of 30wt%, mixing speed 600r/min, the time that adds phosphoric acid,diluted is 10min, continues reaction 20 hours, regulates pH value to 8.0 with the acetum of 2wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 5, sorbitol 5, the hydrosol 30.6, methylcellulose 0.8, hydroxyethyl-cellulose 0.4, K
121.7, a-hydrated alumina 38, colloidal silica 5.1, methyl P-hydroxybenzoic acid sodium 2.5, sodium silicate 0.6, tetrasodium pyrophosphate 6.8, allantoin 2.5, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol and sorbitol, the colloidal silica that adds sodium silicate and 1/2 component then mixed 1 hour, adds colloidal silica and other component of remaining 1/2 component again, fully mixes;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 5.0wt% in this toothpaste.
Embodiment 5
The first step, preparation calcium hydroxide content is the lime cream 5.1kg of 28wt%, in the 25L reactor of packing into;
Second step added the 0.58kg glacial acetic acid in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 95 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 10.3kg and lasting stirring of 8wt%, mixing speed 600r/min, the time that adds phosphoric acid,diluted is 30min, continues reaction 3 hours, regulates pH value to 8.5 with the acetum of 3wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 25, nano-hydroxyapatite hydrosol 24, sodium silicate 0.4, CMC1.0, K
121.7, calcium carbonate 46.7, saccharin sodium 0.2, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol, the calcium carbonate that adds sodium silicate and 1/3 component then mixed 2 hours, adds calcium carbonate and other component of remaining 2/3 component again, fully mixes;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 2.2wt% in this toothpaste.
Embodiment 6
The first step, preparation calcium hydroxide content is the lime cream 10kg of 10wt%, in the 25L reactor of packing into;
Second step added the 0.2kg calcium acetate in described lime cream, stir, and got mixture;
The 3rd step, with described mixture heated to 30 ℃, adding phosphorus acid content then gradually is phosphoric acid,diluted 9.7kg and lasting stirring of 8wt%, mixing speed 600r/min, the time that adds phosphoric acid,diluted is 1min, continues reaction 16 hours, regulates pH value to 7.5 with the acetum of 0.5wt% at last, natural cooling gets nano-hydroxyapatite hydrosol.
The nano-hydroxyapatite hydrosol that makes is used to prepare toothpaste, except that nano-hydroxyapatite hydrosol, all adopts the raw material commonly used of preparation toothpaste in the prior art in the raw material of preparation toothpaste, preparation technology also adopts prior art.
The raw material of preparation toothpaste constitutes by following mass percent: glycerol 5, sorbitol 15, the hydrosol 36, sodium silicate 0.6, CMC1.0, K
121.8, SiO
239.4, saccharin sodium 0.2, essence 1.0.
The step of preparation toothpaste is as follows:
The first step is mixed nano-hydroxyapatite hydrosol with glycerol and sorbitol, add the SiO of sodium silicate and 1/3 component then
2Mixed 1 hour, and added the SiO of remaining 2/3 component again
2With other component, fully mix;
In second step, above-mentioned raw materials is prepared toothpaste by known method.
After measured, nanometer hydroxyapatite content is 2.4wt% in this toothpaste.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a nano-hydroxyapatite hydrosol is characterized in that, comprises
Following steps:
The first step, preparation contains the lime cream of calcium hydroxide 1～28wt%, in the reactor of packing into;
Second step added acetic acid or calcium acetate in described lime cream, stir, and got mixture; The mol ratio of acetate and calcium is 1～6: 10 in the mixture;
The 3rd step, with described mixture heated to 30～95 ℃, add the dilute phosphoric acid solution of 8～30wt% then gradually and continue stirring, mixing speed＞300r/min, the time that adds dilute phosphoric acid solution is 1～30 minute, continues reaction 3～20 hours, regulates pH value to 7.5～8.5 with acetum at last, cooling gets nano-hydroxyapatite hydrosol; Wherein, the quality that adds dilute phosphoric acid solution calculates by the following method: deducting after the calcium amount of calcium acetate in the described mixture in calcium phosphorus mol ratio is that 1.68～1.70: 1 ratio adds dilute phosphoric acid solution.
2. according to the preparation method of the described nano-hydroxyapatite hydrosol of claim 1, it is characterized in that the calcium hydroxide content of lime cream is 10～28wt% in the described first step.
3. according to the preparation method of the described nano-hydroxyapatite hydrosol of claim 1, it is characterized in that the mol ratio of acetate and calcium is 2～4: 10 in the mixture in described second step.
4. according to the preparation method of the described nano-hydroxyapatite hydrosol of claim 1, it is characterized in that, described the 3rd step is for described mixture heated to 65～95 ℃, add the dilute phosphoric acid solution of 14～30wt% then gradually and continue stirring, mixing speed 〉=600r/min, the time that adds dilute phosphoric acid solution is 3～10 minutes, continue reaction 6～12 hours, regulate pH value to 7.5～8.5 with the acetum of 0.5～3wt% at last, cooling gets nano-hydroxyapatite hydrosol.
5. the nano-hydroxyapatite hydrosol that makes of the preparation method of the described nano-hydroxyapatite hydrosol of claim 1 comprises the nanometer hydroxyapatite of 1～18wt%, calcium acetate and the water of 1～8wt%.
6. according to the described nano-hydroxyapatite hydrosol of claim 5, it is characterized in that described nanometer hydroxyapatite is needle-like, length is 60～100nm, is monodisperse status in described nano-hydroxyapatite hydrosol.
7. application that the described nano-hydroxyapatite hydrosol of claim 5 is used to prepare toothpaste.
8. application according to claim 7, it is characterized in that, earlier described nano-hydroxyapatite hydrosol is mixed with wetting agent, add the abrasivus that sodium silicate and quality are abrasivus gross mass 1/3～1/2 then, mixed 0.5～2 hour, add remaining abrasivus and other raw material again, fully mix the back and prepare toothpaste by known method; Wherein the mass ratio of nano-hydroxyapatite hydrosol and sodium silicate is 1: 0.01～0.02; The mass ratio of nano-hydroxyapatite hydrosol and wetting agent is 1: 0.5～1.1; The mass ratio of nano-hydroxyapatite hydrosol and abrasivus is 1: 1～2.2.
9. application according to claim 7 is characterized in that, the nanometer hydroxyapatite that joins in the toothpaste accounts for 2～7% of toothpaste gross mass.
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| CN103030125B (en) * | 2011-09-29 | 2016-01-06 | 深圳兰度生物材料有限公司 | A kind of medical fortifying fibre and preparation method thereof |
| CN102502907B (en) * | 2011-10-14 | 2013-06-26 | 江苏永冠给排水设备有限公司 | Production method of attapulgite loaded hydroxyapatite composite defluorination filter bulb |
| EA033695B1 (en) * | 2015-07-03 | 2019-11-18 | Unilever Nv | Oral care composition |
| CN108609593B (en) * | 2018-04-27 | 2020-09-08 | 武汉亚洲生物材料有限公司 | Hydroxyapatite and preparation method and application thereof |
| CN111634897B (en) * | 2020-05-27 | 2023-11-07 | 天宝动物营养科技股份有限公司 | Nanoscale calcium hydroxy phosphate/calcium hydrophosphate and preparation method thereof |
| CN111591969B (en) * | 2020-06-03 | 2021-01-05 | 连云港东泰食品配料有限公司 | Preparation method of hydroxyapatite with high suspension degree |
| CN114886782B (en) * | 2022-05-07 | 2023-06-16 | 深圳市博威凯特科技有限公司 | Active calcium compound based on nano hydroxyapatite and preparation method and application thereof |
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