CN114796081B - Bagasse/calcium phosphate composite material, and preparation method and application thereof - Google Patents
Bagasse/calcium phosphate composite material, and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
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- A61K2800/41—Particular ingredients further characterized by their size
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Abstract
The embodiment of the invention discloses a bagasse/calcium phosphate composite material, and a preparation method and application thereof. The preparation method comprises the following steps: soaking bagasse in an aqueous solution containing a calcium ion source until the bagasse is adsorbed to reach a saturated state, adding a phosphate ion source until calcium ions in the solution are completely converted into phosphate calcium salt, and performing centrifugal separation, drying and grinding to obtain the bagasse/calcium phosphate composite material. The bagasse/calcium phosphate core-shell composite material prepared by taking bagasse as a raw material improves the cleaning performance, elasticity and anti-sensitivity performance of the calcium phosphate abrasive, and keeps excellent biocompatibility.
Description
Technical Field
The embodiment of the invention relates to the technical field of daily chemicals, oral medical treatment, nursing and cleaning products, in particular to a bagasse/calcium phosphate composite material, and a preparation method and application thereof.
Background
The calcium phosphate inorganic solid particles and the hydrate thereof are toothpaste abrasive materials with the best taste and biocompatibility, wherein the element compositions of calcium hydrophosphate dihydrate, tricalcium phosphate and hydroxyapatite are similar to the element compositions of enamel surface elements, and the toothpaste prepared by adopting the abrasive materials has unique and fine taste and outstanding performances in aspects of enamel remineralization and dentin anti-sensitivity. However, the production cost of the calcium phosphate inorganic solid particles is relatively high, and the solid particles directly prepared by a precipitation method are large in particle size, so that the cleaning effect of the calcium phosphate inorganic solid particles on tooth gaps is prevented, the calcium phosphate inorganic solid particles are prevented from entering dentinal tubules, and the anti-sensitivity performance of the calcium phosphate abrasive is reduced. In addition, the slightly soluble calcium phosphate inorganic matters can cause eutrophication pollution to water bodies.
Therefore, how to develop an alternative to calcium phosphate-based abrasive and/or tooth desensitizer is a technical challenge in the art.
Disclosure of Invention
Bagasse is a solid organic waste after sugar production of sugarcane, and is commonly used for fuel power generation, papermaking, cellulose extraction, xylitol preparation and the like, and deep processing of bagasse in the processes often causes secondary pollution, so that the requirements of energy conservation, emission reduction and carbon neutralization are difficult to realize. Bagasse mainly comprises lignin, cellulose and hemicellulose, and is harmless to human body. Lignin has certain antibacterial and antiviral properties, and edible cellulose can help digestion, and hemicellulose polysaccharide is a good prebiotic; the lignin in the bagasse wraps the cellulose and hemicellulose to form a bundle-shaped fiber structure with certain strength; the dried bagasse is easy to absorb water and swell in water at normal temperature, and the volume is increased.
The bagasse/calcium phosphate core-shell composite material prepared by taking bagasse as a raw material improves the cleaning performance, elasticity and anti-sensitivity performance of the calcium phosphate abrasive, and keeps excellent biocompatibility.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
according to a first aspect of the embodiment of the invention, the embodiment of the invention provides a preparation method of bagasse/calcium phosphate composite material, which comprises the steps of immersing bagasse in an aqueous solution containing a calcium ion source until the bagasse is adsorbed to reach a saturated state, adding a phosphate ion source until calcium ions in the solution are completely converted into phosphate calcium salt, and carrying out centrifugal separation, drying and grinding to obtain the bagasse/calcium phosphate composite material.
In the invention, the calcium ion source is selected from one or more of calcium chloride, calcium nitrate, calcium hydroxide, calcium oxide, calcium gluconate, calcium bicarbonate and calcium lactate.
In the invention, the phosphate ion source is selected from one or more of phosphoric acid, trisodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, phosphorus pentoxide, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and diammonium hydrogen phosphate.
In the invention, the calcium phosphate salt is selected from one or more of tricalcium phosphate, calcium hydrophosphate and hydroxyapatite.
Wherein, the bagasse is soaked in calcium salt water solution until the bagasse is sweetBagasse adsorption to saturation refers to: bagasse vs. Ca 2+ Reaching adsorption balance.
In the invention, the soaking time refers to the ratio of bagasse to Ca 2+ Preferably, the soaking time is 0.5-24 hours.
In the invention, the grain size of the bagasse/calcium phosphate composite material is 0.1-50 microns.
In the invention, the bagasse preparation method comprises the following steps: the sugar cane is squeezed, ball milled by adding water until the leaching liquid is clear and transparent, sieving with a water sieve with more than 40 meshes, removing large particles, drying the undersize and jet milling to obtain powder with the particle size of 0.1-50 microns.
According to a second aspect of embodiments of the present invention, there is provided a bagasse/calcium phosphate composite material, which is produced by the production process as described above.
According to a third aspect of embodiments of the present invention there is provided the use of a bagasse/calcium phosphate composite as described above as at least one of an abrasive, an anti-sensitization ingredient in an oral care implement.
In the present invention, the oral care product is a toothpaste, a dentifrice or a tooth desensitizing agent.
According to a fourth aspect of embodiments of the present invention there is provided a toothpaste comprising a bagasse/calcium phosphate composite as described above.
In the invention, the bagasse/calcium phosphate composite material accounts for 0.1-70% of the toothpaste by mass, and is preferably 10-70%.
In the invention, the toothpaste further comprises at least one of humectant, adhesive, abrasive, essence, preservative, sweetener, foaming agent and water.
Wherein the humectant is humectant conventionally used in the art, such as glycerin, sorbitol, sodium hyaluronate, etc.; the binder is a binder conventionally used in the art, such as xanthan gum, carrageenan, sodium carboxymethyl cellulose, sodium hydroxyethyl cellulose, carbomer, etc.; the abrasive is an abrasive conventionally used in the art, such as calcium carbonate, calcium phosphate salts, silica, and the like; the essence is of a type conventionally used in the art, such as peppermint type, spearmint type, wintergreen type, fruit type, tea type, medicinal type and the like; the preservative is a preservative conventionally used in the art, such as sodium benzoate, parabens, and the like; the sweetener is a sweetener conventionally used in the art, such as sorbitol, xylitol, sodium saccharin, and the like. The foaming agent is a foaming agent conventionally used in the art, such as sodium lauryl sulfate, sodium lauroyl sarcosinate, and the like.
In one embodiment of the present invention, when the toothpaste is abrasive to the bagasse/calcium phosphate composite, the toothpaste comprises the following components in weight percent: 1-70% of sorbitol; cellulose gum 0.3-2%; 0.1 to 2 percent of xanthan gum; 0.1 to 2 percent of carrageenan; glycerol 1-50%; 0.1 to 70 percent of bagasse/calcium phosphate composite material; essence, preservative, sweetener, foaming agent and water are added in 100%.
In another embodiment of the invention, when the toothpaste is part of the abrasive material of the bagasse/calcium phosphate composite, the toothpaste comprises the following components in weight percent: 15% -80% of humectant (glycerin, sorbitol and mixture thereof in any proportion); 0.4 to 3 percent of adhesive (xanthan gum, carrageenan, sodium carboxymethyl cellulose, hydroxyethyl cellulose sodium, carbomer and any mixture thereof); 7% -60% of abrasive (at least one of calcium carbonate, calcium phosphate and silicon dioxide is included in addition to bagasse/calcium carbonate composite material); essence, preservative, sweetener, foaming agent and water are added in 100%.
In yet another embodiment of the present invention, when the bagasse/calcium phosphate composite is used as an abrasive and an anti-sensitivity ingredient in a dental anti-sensitivity toothpaste, the dental anti-sensitivity toothpaste comprises the following components in weight percent: 15% -80% of humectant (glycerin, sorbitol and mixture thereof in any proportion); 0.4 to 3 percent of adhesive (xanthan gum, carrageenan, sodium carboxymethyl cellulose, hydroxyethyl cellulose sodium, carbomer and any mixture thereof); 7% -60% of abrasive (at least one of calcium carbonate, calcium phosphate salt and silicon dioxide is included in addition to bagasse/calcium phosphate composite material); potassium nitrate 0.5-7%; essence, preservative, sweetener, foaming agent and water are added in 100%.
The embodiment of the invention has the following advantages:
1. the bagasse/calcium phosphate core-shell composite material prepared by taking bagasse as a raw material improves the cleaning performance, elasticity and anti-sensitivity performance of the calcium phosphate abrasive, and keeps excellent biocompatibility.
2. The bagasse is applied to the oral care products, so that the anti-inflammatory and antibacterial properties of lignin can be fully exerted, and natural and safe antibacterial and antiviral properties are provided for the oral care products; the carbon neutralization is truly realized, and other toxic chemical substances are not required to be introduced; the carbon captured by the sugarcane from the air is stored in the oral care product for a long time, so that the release period of the carbon is delayed.
3. The preparation method provided by the invention has the advantages of simple and convenient operation of steps, simple process flow, great reduction of cost and contribution to industrial production.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods used in the examples are regarded as conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
In the following examples and comparative examples, bagasse was prepared as follows: after sugar is squeezed from sugarcane, 15 times of water is added for 5 times, ball milling is carried out for 3 hours at the rotating speed of 200r/min until the leaching solution is clear and transparent, sieving is carried out through a water sieve with more than 40 meshes, large particles are removed, and the undersize is dried and crushed by air flow, thus obtaining powder with the particle size of 0.1-50 microns.
Example 1
The preparation method of the bagasse/calcium phosphate salt composite material provided by the embodiment comprises the following steps:
10g of bagasse powder is weighed and soaked in 40ml of calcium chloride aqueous solution with the concentration of 1mol/L for 2 hours, 4g of phosphoric acid is added, stirring is carried out for 20 minutes, then centrifugation is carried out for 4 minutes at the rotating speed of 1000r/min, the obtained solid phase is dried for 2 hours in a drying oven at the temperature of 80 ℃, grinding is carried out, and a 40-mesh sieve is carried out, thus obtaining the bagasse/calcium phosphate composite material.
Example 2
The preparation method of the bagasse/calcium phosphate composite material provided by the embodiment is as follows:
10g of bagasse powder is weighed and soaked in 30ml of calcium hydroxide suspension with the concentration of 1mol/L for 2 hours, 48g of trisodium phosphate is added, stirring is carried out for 1 hour, then centrifugation is carried out for 5 minutes at the rotating speed of 1000r/min, the obtained solid is dried for 2 hours in a drying oven at the temperature of 80 ℃, grinding is carried out, and a 40-mesh sieve is carried out, thus obtaining the bagasse/calcium phosphate composite material.
Example 3
The preparation method of the bagasse/calcium phosphate composite material provided by the embodiment is as follows:
weighing 50g of bagasse powder, soaking in 500ml of calcium gluconate aqueous solution with the concentration of 2mol/L for 1h, adding 12g of sodium dihydrogen phosphate, stirring for 1h, centrifuging at the rotating speed of 1000r/min for 5min, drying the obtained solid in a drying oven at 80 ℃ for 2h, grinding, and sieving with a 80-mesh sieve to obtain the bagasse/calcium phosphate composite material.
Example 4
The preparation method of the bagasse/calcium phosphate composite material provided by the embodiment is as follows:
weighing 20g of bagasse powder, soaking in 60ml of calcium bicarbonate suspension with the concentration of 2mol/L for 1h, adding 15g of diammonium hydrogen phosphate, stirring for 40min, centrifuging at the rotating speed of 1000r/min for 10min, drying the obtained solid in a drying oven at 80 ℃ for 2h, grinding, and sieving with a 80-mesh sieve to obtain the bagasse/calcium phosphate composite material.
Example 5
The embodiment provides toothpaste, which comprises the following components in percentage by weight:
20% of bagasse/calcium phosphate composite material of example 1, 5% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 0.3% of xanthan gum, 0.5% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate and the balance of water.
The preparation method of the toothpaste comprises the following steps:
1) Adding water, sodium benzoate, saccharin sodium and sorbitol into water phase pot of homogenizing emulsifying equipment, stirring to dissolve;
2) Adding glycerol into an oil phase pot of homogenizing emulsifying equipment, starting stirring at a rotation speed of 100r/min, and adding xanthan gum, carrageenan and sodium carboxymethylcellulose into the oil phase pot until the mixture is uniformly dispersed for later use;
3) Sucking the materials in the oil phase pot into the homogenizing pot through negative pressure, starting wall-mounted stirring (rotating speed of 100 r/min), sucking the materials in the water phase pot into the homogenizing pot through negative pressure, starting homogenizing stirring rotating speed (2000 r/min), stirring for 5min until the materials are uniformly dispersed, and fully swelling;
4) Sucking bagasse/calcium phosphate composite material and silicon dioxide into a homogenizing pot under negative pressure, and stirring for 30 minutes until the system is uniform;
5) Adding peppermint essence into a homogenizing pot, stirring uniformly, and starting vacuum until the negative pressure is less than-0.06 Mp;
6) Sucking sodium laurylsulfate into the homogenizing pot under negative pressure, stirring for 10min, vacuum-starting until negative pressure is less than-0.08 MP, stirring until the system is uniform, and discharging.
Example 6
The embodiment provides a tooth anti-sensitive toothpaste, which comprises the following components in percentage by weight:
10% of bagasse/calcium phosphate composite material of example 2, 10% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 0.4% of xanthan gum, 0.4% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate, 3% of potassium nitrate and the balance of water.
The preparation method of the tooth anti-sensitive toothpaste provided in the embodiment is basically the same as that in embodiment 5, wherein potassium nitrate is added in step 1).
Example 7
The embodiment provides toothpaste, which comprises the following components in percentage by weight:
5% of bagasse/calcium phosphate composite material of example 4, 15% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 5% of silicon dioxide, 0.5% of xanthan gum, 0.3% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate and the balance of water.
The toothpaste provided in this example was prepared in the same manner as in example 5.
Comparative example 1
This comparative example provides a toothpaste that differs from example 5 only in that the bagasse/calcium phosphate composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.
The toothpaste provided in this comparative example was prepared in the same manner as in example 5.
Comparative example 2
This comparative example provides a dental anti-sensitivity toothpaste which differs from example 6 only in that the bagasse/calcium phosphate composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.
The preparation method of the tooth anti-sensitive toothpaste provided in the comparative example is the same as that in example 5.
Comparative example 3
This comparative example provides a toothpaste that differs from example 7 in that the bagasse/calcium phosphate composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.
The toothpaste provided in this comparative example was prepared in the same manner as in example 5.
Test example 1
Whiteness detection
The whiteness of the toothpaste was tested using a WSD-III type automatic whiteness meter. The whiteness test results of the toothpastes of example 5 and comparative example 1 are shown in Table 1.
TABLE 1
Toothpaste sample | Whiteness degree |
Example 5 | 93 |
Comparative example 1 | 95 |
The results show that: the whiteness of the toothpastes of example 5 and comparative example 1 are substantially identical, demonstrating that the bagasse/calcium phosphate composite of the present invention, as an abrasive for toothpastes, is capable of achieving substantially the same paste appearance properties as the abrasive monocalcium phosphate.
Test example 2
Cleaning force test
1.0g of toothpaste sample is weighed and placed on a white organic glass plate attached with special dirt on a cleaning value tester, a nose with a soft bristle toothbrush is put down, so that the bristles are in close contact with the organic glass plate, the instrument is started, and the toothbrush moves back and forth immediately to rub the organic glass plate. After rubbing for 20 times, 50 times, 100 times, 150 times, 200 times and 300 times in sequence, the organic glass plate is taken out and put into a whiteness meter to measure corresponding data. The 6 data are converted into a cleaning value CV. Higher CV values indicate more cleaning power of the toothpaste. The results of the test of the cleaning values of the toothpastes of example 5 and comparative example 1 are shown in Table 2.
TABLE 2
Toothpaste sample | CV value |
Example 5 | 22 |
Comparative example 1 | 18 |
The results show that: when 20% of the abrasive monocalcium phosphate in the toothpaste is replaced by the bagasse/calcium carbonate composite material of the embodiment of the invention, the cleaning value of the toothpaste is increased from 18 to 22, and the cleaning value of the toothpaste is improved by more than 20%, which shows that compared with the abrasive monocalcium phosphate, the bagasse/calcium phosphate composite material of the embodiment of the invention has excellent tooth cleaning performance as the abrasive for the toothpaste.
Test example 3
In vitro dentin tubule experiment
Cutting dentin sheet with thickness of about 3mm at 1-4mm position under enamel dentin boundary perpendicular to long axis direction of dentin with hard tissue cutter, sequentially grinding with sand paper on horizontal grinder, polishing to obtain dentin sheet with thickness of about 2mm, ultrasonic cleaning, etching with 6% citric acid for 2min, washing with distilled water for 30S, and blow drying to obtain sensitive dentin. The tooth brushing experiment was performed on sensitive dentin with the same toothbrush using the same concentration of the toothpaste slurry, and then SEM observation was performed on the surface and longitudinal section of the isolated dentin, and the occlusion rate (PR) of the isolated dentin tubule was calculated. The results of the tests for the clogging rate of the tooth anti-sensitive toothpaste of example 6 and comparative example 2 are shown in Table 3.
TABLE 3 Table 3
Toothpaste sample | PR value |
Example 6 | 96% |
Comparative example 2 | 20% |
The results show that: when 10% of abrasive monocalcium phosphate in the tooth anti-sensitive toothpaste is used for replacing the bagasse/calcium phosphate composite material in the embodiment of the invention, the in-vitro dentinal tubule blocking rate of the tooth anti-sensitive toothpaste is obviously increased, and the blocking rate reaches more than 95%, which shows that compared with the abrasive monocalcium phosphate, the bagasse/calcium phosphate composite material in the embodiment of the invention has more excellent desensitizing effect when being used as the abrasive and anti-sensitive component for the tooth anti-sensitive toothpaste.
Test example 4
Taste test brush
60 volunteers with healthy oral cavity were randomly selected and grouped into experiments 1-4, each group being 15. Among them, the volunteer of experiment 1 used the toothpaste of example 6, the volunteer of experiment 2 used the toothpaste of comparative example 2, the volunteer of experiment 3 used the toothpaste of example 7, and the volunteer of experiment 4 used the toothpaste of comparative example 3. All volunteers used the personal habit brushing regimen in a unified manner using a toothbrush provided by Yunnan white drug group Co., ltd. Filling out a questionnaire for the mouth feel of the toothpaste after 3 days, and obtaining a result through statistics. Wherein:
like: the taste is fine and smooth, and no granular feel exists;
generally: the taste is rough, and the friction feeling of particles is obvious;
dislike: has a rough taste and obvious granular friction feeling.
The test results are shown in Table 4.
TABLE 4 Table 4
Group of | Toothpaste sample | Xi Huan | In general | Dislike | Preference degree |
Experiment 1 group | Example 6 | 13 | 2 | 0 | 86.7% |
Experiment 2 group | Comparative example 2 | 8 | 2 | 5 | 53.3% |
Experiment 3 group | Example 7 | 9 | 3 | 3 | 60% |
Experiment 4 group | Comparative example 3 | 8 | 3 | 4 | 53.3% |
The results show that: when 5% of the abrasive monocalcium phosphate in the toothpaste was replaced with the bagasse/calcium phosphate composite material of the present examples, the brushing mouthfeel of the toothpaste was substantially unchanged (see experiments 3-4); when 10% of the abrasive monocalcium phosphate in the toothpaste is used for replacing the bagasse/calcium phosphate composite material in the embodiment of the invention, the taste preference of the toothpaste in a brushing test is increased by more than 30% (see experiment 1-2 groups), and the above shows that compared with the abrasive monocalcium phosphate, the bagasse/calcium phosphate composite material in the embodiment of the invention can be accepted and favored by the public when being added into the toothpaste.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. A preparation method of a composite material for oral care is characterized in that bagasse is soaked in an aqueous solution of a calcium ion source until the bagasse is adsorbed to reach a saturated state, then a phosphate ion source is added until calcium ions in the solution are completely converted into phosphate calcium salt, and centrifugal separation, drying and grinding are carried out to obtain the composite material; the preparation method of the bagasse comprises the following steps: after sugar is squeezed from sugarcane, water is added for ball milling until the leaching solution is clear and transparent, a water sieve with more than 40 meshes is used for removing large particles, and undersize materials are dried and crushed by air flow to obtain powder with the particle size of 0.1-50 microns; the particle size of the composite material is 0.1-50 microns.
2. The method of claim 1, wherein the source of calcium ions is selected from one or more of calcium chloride, calcium nitrate, calcium hydroxide, calcium oxide, calcium gluconate, calcium bicarbonate, and calcium lactate.
3. The method of claim 1, wherein the phosphate ion source is selected from one or more of phosphoric acid, trisodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, phosphorus pentoxide, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and diammonium hydrogen phosphate.
4. The method of claim 1, wherein the calcium phosphate salt is selected from one or more of tricalcium phosphate, calcium hydrogen phosphate, and hydroxyapatite.
5. The method of preparing an oral care composite according to claim 1, wherein the soaking time is 0.5-24 hours.
6. Composite material for oral care, characterized in that it is produced by the production method according to any one of claims 1 to 5.
7. Use of the composite material of claim 6 as at least one of an abrasive, an anti-sensitization component in the manufacture of an oral care implement.
8. The use of claim 7 wherein the oral care implement is a toothpaste, a dentifrice or a tooth desensitizing agent.
9. A toothpaste comprising the composite material of claim 6, wherein the composite material comprises 0.1-70% of the toothpaste by mass;
the toothpaste also comprises at least one of humectant, binder, abrasive, essence, antiseptic, sweetener, foaming agent and water.
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CN109627827A (en) * | 2018-12-18 | 2019-04-16 | 厦门双瑞船舶涂料有限公司 | A kind of calcium zinc orthophosphate activated by thallium/bagasse composite anti-corrosive pigment and preparation method thereof |
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WO2016011978A1 (en) * | 2014-07-24 | 2016-01-28 | 北京大清生物技术有限公司 | Composition with multiple oral treatment and healthcare functions and preparation method therefor |
CN112154014A (en) * | 2018-05-21 | 2020-12-29 | 荷兰联合利华有限公司 | Oral care compositions based on calcium phosphate polyion clusters |
CN109627827A (en) * | 2018-12-18 | 2019-04-16 | 厦门双瑞船舶涂料有限公司 | A kind of calcium zinc orthophosphate activated by thallium/bagasse composite anti-corrosive pigment and preparation method thereof |
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