CN106074195A - A kind of toothpaste of hydroxyl apatite and calcium carbonate and preparation method thereof - Google Patents
A kind of toothpaste of hydroxyl apatite and calcium carbonate and preparation method thereof Download PDFInfo
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- CN106074195A CN106074195A CN201610539053.XA CN201610539053A CN106074195A CN 106074195 A CN106074195 A CN 106074195A CN 201610539053 A CN201610539053 A CN 201610539053A CN 106074195 A CN106074195 A CN 106074195A
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
- A61K8/21—Fluorides; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
Abstract
Hydroxyl apatite of the present invention and the toothpaste of calcium carbonate, comprise nano-grade hydroxy apatite, micron order calcium carbonate and fluoride；The particle diameter of nano-grade hydroxy apatite is less than 100 nm, the particle diameter of micron order calcium carbonate is 0.1 μm ~ 10 μm, in fluoride, fluorine element mass concentration in hydroxy agustite tooth-paste is not more than 8.0wt%, the mass content of nano-grade hydroxy apatite is not more than 20wt%, and micron order calcium carbonate is 1/10 ~ 10:1 with the mass ratio of nano-grade hydroxy apatite.When the toothpaste of described hydroxyl apatite and calcium carbonate uses, demineralization enamel and demineralization dentin sheet is helped to carry out biomineralization, repairing dental enamel surface and reduce dentin facing canaliculi dentales aperture, even blocking dentinal tubule or in dentin surface deposited hydroxyl apatite layer.Meanwhile, fluoride hydrolysis generates fluorion, promotes the mineralization process of hydroxyapatite in tooth, significantly improves described toothpaste to enamel and Dentinal repair function.
Description
Technical field
The invention belongs to daily use chemicals product technical field of living, be specifically related to one and there is reparation demineralization enamel and demineralization tooth basis
Toothpaste containing nano-grade hydroxy apatite and micron order calcium carbonate of matter and preparation method thereof.
Background technology
Toothpaste has become as the necessary in people's daily life.Along with the raising of people's living standard, bad diet is tied
The generation of structure, the absorption of sugar high-load, threaten the oral health of people.High sugar, especially sucrose, remain in oral cavity, divided
Solution becomes acid, corrodes tooth enamel and is exposed to the dentin on surface, producing enamel and Dentinal demineralization, seriously, make
Become some row diseases such as dental caries, tooth loss or sensitivity of tooth, have a strong impact on the health of people.Take off so researching and developing a can reparation
Ore deposit enamel surface and Dentinal toothpaste have very important significance.
Hydroxyapatite has good biocompatibility and a biological activity, the main component of Ye Shi dentin sclerous tissues,
Thus be widely applied in formulation of tooth-paste, promote enamel and Dentinal reparation.Micron order calcium carbonate can be then tooth
Repair and calcium ion is provided, also can improve the reparation of the pH value of microenvironment, beneficially tooth, but owing to it does not has with dental surface
There is stronger adsorption, be difficult to deposit to dental surface.
Summary of the invention
To this end, the present invention finds nano-grade hydroxy apatite and micron order calcium carbonate synergism in toothpaste, thus
There is provided one can effectively repair demineralization enamel and demineralization is Dentinal containing nano-grade hydroxy apatite with micron order calcium carbonate
Toothpaste and preparation method thereof.
For achieving the above object, the technical scheme is that
Of the present invention a kind of containing nano-grade hydroxy apatite with the toothpaste of micron order calcium carbonate, comprise micron order calcium carbonate,
Nanometer hydroxyapatite and fluoride；
The particle diameter of described nano-grade hydroxy apatite be less than 100 nm, the particle diameter of described micron order calcium carbonate be 38 μm and with
Under；
In described fluoride, fluorine element mass concentration in described hydroxy agustite tooth-paste is not more than 8.0wt%, described nanoscale
The mass content of hydroxyapatite is not more than the quality of 20wt%, described micron order calcium carbonate and described nano-grade hydroxy apatite
Ratio is 1:10 ~ 10:1.
The particle diameter of described micron order calcium carbonate is 13 μm and following, and the particle diameter of described nano-grade hydroxy apatite is
30nm~80nm。
Described micron order calcium carbonate is 1:2 ~ 4:1 with the mass ratio of described nanometer hydroxyapatite, and described micron order carbon
The mass content of acid calcium is 4wt% ~ 30wt%.
The mass content of described micron order calcium carbonate is 4wt%, and the mass content of described nano-grade hydroxy apatite is
4wt%, and calcium carbonate crystal formation is calcite phase.
Described fluoride is sodium fluoride and/or sodium monofluorophosphate, and in described fluoride, fluorine element is at described hydroxyapatite
Mass concentration in toothpaste is not more than 0.1wt%.
Preferably, also include in abrasivus, thickening agent, wetting agent, sweeting agent, antibacterial, foaming agent, essence, pigment
At least one.
Preferably toothpaste comprises the component of following mass percent:
Described micron order calcium carbonate 2wt% ~ 40 wt%,
Described nano-grade hydroxy apatite 1wt% ~ 20 wt%,
Described abrasivus 2wt% ~ 40 wt%,
Described thickening agent 0.02 wt% ~ 8 wt%,
Described wetting agent 1wt% ~ 50wt%,
Described sweeting agent 0.001 wt% ~ 0.1 wt%,
Described antibacterial 0.004 wt% ~ 0.1 wt%,
Described foaming agent 0.1 wt% ~ 5 wt%,
Described fluoride 0 wt% ~ 2 wt%,
Described essence 0.6 wt% ~ 3 wt%,
Described pigment 0 wt% ~ 0.01 wt%.
Preferably, at least one during described abrasivus is silicon dioxide, calcium phosphate dibasic dihydrate or calcium carbonate；Described increasing
Thick dose is at least one in xanthan gum, carrageenan or sodium carboxymethyl cellulose；Described wetting agent is glycerol, sorbitol or poly-second
At least one in glycol 400；Described sweeting agent is at least one in saccharin, sucralose or xylitol；Described antibacterial
For at least one in zinc citrate, sodium benzoate or methyl hydroxybenzoate；Described foaming agent is sodium lauryl sulphate, cocos nucifera oil acyl
At least one in amine CAB or sodium lauroyl sarcosine；Described essence is Mint Essence；Described pigment is fruit green
At least one in element, allured red pigment, bright blue pigment or lemon yellow pigment.
Preferably formula comprises: dicalcium phosphate dehydrate 12 wt%, carrageenan 0.8 wt%, glycerol 28 wt%, sucralose
0.1 wt%, zinc citrate 0.05 wt%, sodium lauryl sulphate 2 wt%, sodium monofluorophosphate 0.76 wt%, essence 1.25 wt%,
Pigment 0.005 wt%, hydrated SiO 2 10 wt%, micron order calcium carbonate 4 wt%, nanometer hydroxyapatite 4 wt%；
Described micron order calcium carbonate, for calcite crystal formation, filters through 1200 mesh sieve, and mean diameter is 13 below m；Described
Mean diameter 60 nm of nano-grade hydroxy apatite.
The preparation method of hydroxy agustite tooth-paste of the present invention, it is characterised in that comprise the steps:
The recipe ingredient of described toothpaste is placed in 200rpm ~ 1000rpm in blender and stirs 20min ~ 60min；
Vacuum outgas becomes paste.
The technique scheme of the present invention has the advantage that compared to existing technology
1. described in the embodiment of the present invention containing nano-grade hydroxy apatite and micron order calcium carbonate toothpaste, comprise micron order carbonic acid
Calcium, nanometer hydroxyapatite and fluoride；The particle diameter of described nanometer hydroxyapatite is less than 100 nm, described micron hydroxy-apatite
The particle diameter of stone is less than 13 μm；In described fluoride, fluorine element mass concentration in described hydroxy agustite tooth-paste is not more than
8.0wt%, the mass content of described nano-grade hydroxy apatite is not more than 20wt%, described micron order calcium carbonate and described nanometer hydroxyl
The mass ratio of base apatite is 1:10 ~ 10:1.When described toothpaste uses, the micro-calcium carbonate of residual and nanometer hydroxyapatite
Synergism, it is possible to sustained release calcium ion and phosphate anion, improves microenvironment pH value, helps demineralization enamel surface and takes off
Ore deposit dentin sheet carries out biomineralization, repairing dental enamel and dentin sheet, reduces canaliculi dentales aperture, even blocks dentinal tubule
Or in dentin surface deposited hydroxyl apatite layer.
The preparation method of toothpaste the most of the present invention, technique is simple, and mastic is uniform and stable, it is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of micron order calcium carbonate in comparative example toothpaste 1, embodiment toothpaste 2 and 3；
Fig. 2 is scanning electron microscope (SEM) figure of nano-grade hydroxy apatite in embodiment toothpaste 2,3 and comparative example toothpaste 4；
Fig. 3 is the surface micro-vickers hardness change post after adamantine initial baseline in experimental example 1, acid attack and toothpaste process
Shape figure (often group 10 enamels of sample).English alphabet indicates the statistics between the micro-vickers hardness of different enamel group
Difference (indicate letter different, then p value < 0.05, there is the difference of statistical significance)；
Fig. 4 a is scanning electron microscope (SEM) figure of the enamel surface after polishing；
Fig. 4 b is scanning electron microscope (SEM) figure of the enamel surface after acid attack；
Fig. 4 c is scanning electron microscope (SEM) figure of the enamel surface after SOF processes；
Fig. 4 d is scanning electron microscope (SEM) figure of the enamel surface after toothpaste 1 processes；
Fig. 4 e is scanning electron microscope (SEM) figure of the enamel surface after toothpaste 2 processes；
Fig. 4 f is scanning electron microscope (SEM) figure of the enamel surface after toothpaste 3 processes；
Fig. 4 g is scanning electron microscope (SEM) figure of the enamel surface after toothpaste 4 processes；
Fig. 5 a is dentin sample scanning electron microscope (SEM) figure after 36wt % phosphate aqueous solution corrodes 2 min；
Fig. 5 b is that dentin sample processes the SEM picture after 6 times through Mouthsimulator saliva (SOF)；
Fig. 5 c is dentin sample SEM picture after comparative example toothpaste 1 processes 6 times；
Fig. 5 d is dentin sample SEM picture after embodiment toothpaste 2 processes 6 times；
Fig. 5 e is dentin sample SEM picture after embodiment toothpaste 3 processes 6 times；
Fig. 5 f is dentin sample SEM picture after comparative example toothpaste 4 processes 6 times；
Fig. 5 g is that dentin sample processes the SEM picture after 14 times through Mouthsimulator saliva (SOF)；
Fig. 5 h is dentin sample SEM picture after comparative example toothpaste 1 processes 14 times；
Fig. 5 i is dentin sample SEM picture after embodiment toothpaste 2 processes 14 times；
Fig. 5 j is dentin sample SEM picture after embodiment toothpaste 3 processes 14 times；
Fig. 5 k is dentin sample SEM picture after comparative example toothpaste 4 processes 14 times；
Fig. 6 a is dentin sample graph of pore diameter distribution of dentinal tubule after 36wt % phosphate aqueous solution corrodes 2 min；
Fig. 6 b is that dentin sample processes the graph of pore diameter distribution of 6 Ci Hou dentinal tubules through Mouthsimulator saliva (SOF)；
Fig. 6 c is that dentin sample processes the graph of pore diameter distribution of 6 Ci Hou dentinal tubules through comparative example toothpaste 1；
Fig. 6 d is that dentin sample processes the graph of pore diameter distribution of 6 Ci Hou dentinal tubules through embodiment toothpaste 2；
Fig. 6 e is that dentin sample processes the graph of pore diameter distribution of 6 Ci Hou dentinal tubules through embodiment toothpaste 3；
Fig. 6 f is that dentin sample processes the graph of pore diameter distribution of 6 Ci Hou dentinal tubules through comparative example toothpaste 4；
Fig. 6 g is that dentin sample processes the graph of pore diameter distribution of 14 Ci Hou dentinal tubules through Mouthsimulator saliva (SOF)；
Fig. 6 h is that dentin sample processes the graph of pore diameter distribution of 14 Ci Hou dentinal tubules through comparative example toothpaste 1；
Fig. 6 i is that dentin sample processes the graph of pore diameter distribution of 14 Ci Hou dentinal tubules through embodiment toothpaste 2；
Fig. 6 j is that dentin sample processes the graph of pore diameter distribution of 14 Ci Hou dentinal tubules through embodiment toothpaste 3；
Fig. 6 k is that dentin sample processes the graph of pore diameter distribution of 14 Ci Hou dentinal tubules through comparative example toothpaste 4；
Detailed description of the invention
In order to the object, technical solutions and advantages of the present invention are better described, below in conjunction with the drawings and specific embodiments
The present invention is described further.The present invention can be embodied in many different forms, and should not be construed as limited at this
The embodiment illustrated.On the contrary, it is provided that these embodiments so that the disclosure will be thorough and complete, and by the present invention's
Design is fully conveyed to those skilled in the art, and the present invention will only be defined by the appended claims.
Comparative example toothpaste 1
The present embodiment provides a kind of hydroxy agustite tooth-paste, by percentage to the quality, is made up of following raw materials according:
Dicalcium phosphate dehydrate 12wt%, hydrated SiO 2 10 wt%, carrageenan 2 wt%, glycerol 28 wt%, sucralose
0.1wt%, zinc citrate 0.05wt%, sodium lauryl sulphate 2wt%, sodium monofluorophosphate 0.76 wt%, Mint Essence 1.25
Wt%, lemon yellow pigment 0.005 wt%, micron order calcium carbonate 8.0 wt%, surplus are deionized water.
The preparation method of described hydroxy agustite tooth-paste, comprises the steps:
S1, said components is placed in blender 800rpm stirs 40min；
S2, vacuum outgas become paste.
Micron order calcium carbonate is 1200 mesh calcites, as shown in Figure 1.
Embodiment toothpaste 2
The present embodiment provide one containing nano-grade hydroxy apatite and micron order calcium carbonate toothpaste, by percentage to the quality, by under
Row raw material forms:
Dicalcium phosphate dehydrate 12wt%, carrageenan 2 wt%, glycerol 28 wt%, sucralose 0.1wt%, zinc citrate 0.05wt%,
Sodium lauryl sulphate 2wt%, sodium monofluorophosphate 0.76 wt%, Mint Essence 1.25 wt%, lemon yellow pigment 0.005 wt%, water
Conjunction silica 10 wt%, micron order calcium carbonate 6 wt%, nano-grade hydroxy apatite 2 wt%, surplus are deionized water.
Micron order calcium carbonate is 1200 mesh calcites, less than 13 μm, as shown in Figure 1；The average particle of nanometer hydroxyapatite
Footpath is 60 nm, as shown in Figure 2.
The preparation method of described toothpaste, comprises the steps:
S1, said components is placed in blender 800rpm stirs 40min；
S2, vacuum outgas become paste.
Embodiment toothpaste 3
The present embodiment provide one containing nano-grade hydroxy apatite and micron order calcium carbonate toothpaste, by percentage to the quality, by under
Row raw material forms:
Dicalcium phosphate dehydrate 12wt%, carrageenan 2 wt%, glycerol 28 wt%, sucralose 0.1wt%, zinc citrate 0.05wt%,
Sodium lauryl sulphate 2wt%, sodium monofluorophosphate 0.76 wt%, Mint Essence 1.25 wt%, lemon yellow pigment 0.005 wt%, water
Conjunction silica 10 wt%, micron order calcium carbonate 4wt%, nano-grade hydroxy apatite 4 wt%, surplus are deionized water.
Micron order calcium carbonate is 1200 mesh calcites, less than 13 μm, as shown in Figure 1；The average particle of nanometer hydroxyapatite
Footpath is 60 nm, as shown in Figure 2.
The preparation method of described toothpaste, comprises the steps:
S1, said components is placed in blender 100rpm stirs 20min；
S2, vacuum outgas become paste.
Comparative example toothpaste 4
The present embodiment provides a kind of hydroxy agustite tooth-paste, by percentage to the quality, is made up of following raw materials according:
Dicalcium phosphate dehydrate 12wt%, carrageenan 2 wt%, glycerol 28 wt%, sucralose 0.1wt%, zinc citrate 0.05wt%,
Sodium lauryl sulphate 2wt%, sodium monofluorophosphate 0.76 wt%, Mint Essence 1.25 wt%, lemon yellow pigment 0.005 wt%, water
Conjunction silica 10 wt%, micron order calcium carbonate 0.0 wt%, nano-grade hydroxy apatite 8.0 wt%, surplus are deionized water.
Micron order calcium carbonate is 1200 mesh calcites, less than 13 μm, as shown in Figure 1；The average particle of nanometer hydroxyapatite
Footpath is 60 nm, as shown in Figure 2.
The preparation method of described hydroxy agustite tooth-paste, comprises the steps:
S1, said components is placed in blender 800rpm stirs 60min；
S2, vacuum outgas become paste.
The adamantine external reparative experiment of experimental example 1 demineralization
Mouthsimulator saliva (SOF), concrete composition is as follows: 137.35 mM NaCl, 4.17 mM NaHCO3,3.01 mM KCl,
7.17 mM K2HPO43H2O、1.53 mM MgCl26H2O、20.00 mM HCl、0.90 mM CaCl2、0.51 mM
Na2SO4 and Tris adjusts pH value to 7.0.
Use low-speed diamond cutting machine (SYJ-160 low-speed diamond cutting machine) cutting baurodont, prepare the tooth that thickness is 2 mm
Enamel sheet, more smooth to surface-brightening through the carborundum waterproof abrasive paper polishing grinding of 200,400,1000,2000 and 4000 mesh respectively；
Finally polish smooth with 3M polishing paper (3 microns), and at deionized water ultrasonic cleaning 3 min, standby.Use micro-vickers hardness
Instrument (HV-1000Z type, load 500gf, 15 seconds) record enamel surface micro-vickers hardness, according to hardness, select suitable dentium nitor
Quality sample, and it is randomly divided into 5 groups, often group 10.Often group enamel sheet embeds in oral cavity elastomeric material (Shanghai Columba livia board), smooth tooth
Enamel faces up, and through 1.0% aqueous citric acid solution pretreatment 10 min demineralization, then carries out micro-vickers hardness test.At toothpaste
Reason demineralization is adamantine specifically comprises the following steps that weighing 5.0 g SOF, comparative example toothpaste 1, embodiment toothpaste 2, embodiment toothpaste 3
Add 10.0 g deionized waters stirrings respectively with comparative example toothpaste 4 and make solution or toothpaste serosity, and be poured on 5 groups and be embedded with enamel sample
On the elastomeric material of product, quiet put 2 min；Then, with 20 mL deionized water rinsing 3 times, 20 ml Mouthsimulator salivas are put into
Middle immersion；Subsequently, the constant rate of speed that the container containing Mouthsimulator saliva and enamel elastomeric material is placed in 37 oC is
4 h in the constant temperature oscillator (THZ-98A) of 150 rpm.Process enamel specimen every day 3 times, in 37 oC Mouthsimulator salivas
Overnight.When processing sample number and being 14 times, take out enamel specimen, carry out micro-vickers hardness test, and often group takes out dentium nitor
Matter is a piece of, respectively takes normal teeth enamel sheet and demineralization enamel is a piece of, after all drying, preserves, for scanning electron microscope mirror SEM
(Hitachi S-3400N) phenetic analysis enamel surface repairs situation.
Fig. 3 be the surface micro-vickers hardness change block diagram after adamantine initial baseline, acid attack and toothpaste process and
Results of statistical analysis.On initial baseline, SOF, comparative example toothpaste 1, embodiment toothpaste 2, embodiment toothpaste 3 and comparative example tooth
5 groups of adamantine average micro-vickers hardness of cream 4 be respectively 291.0 ± 9.0 HV, 285.0 ± 12.9 HV, 286.5
± 15.0 HV, 282.4 ± 13.4 HV and 281.8 ± 10.9 HV (Fig. 3), and one factor analysis of variance (Anova,
Tukey) not significant difference is shown between 5 groups of adamantine surface micro-vickers hardness.After 1% citric acid corrodes,
SOF, 5 groups of adamantine average micro-vickers hardness of toothpaste 1,2,3 and 4 reduce to be 190.2 ± 10.3 HV, 188.7 ±
10.7 HV, 186.2 ± 11.7 HV, 184.7 ± 12.2 HV and 184.9 ± 9.5 HV；One factor analysis of variance
(Anova, Tukey) shows between 5 groups of adamantine surface micro-vickers hardness not significant difference.At SOF or tooth
After cream process enamel sheet 14 times, SOF, 5 groups of adamantine average micro-vickers hardness of toothpaste 1,2,3 and 4 improve to being
199.6 ± 8.2 HV, 207.7 ± 12.6 HV, 219.6 ± 16.0 HV, 229.3 ± 17.0 HV and 210.0 ±
6.9 HV.Arranging from high to low by enamel surface micro-vickers hardness, sample sets is followed successively by 3 groups of toothpaste, 2 groups of toothpaste, toothpaste 4
Group, 1 group of toothpaste and SOF group.Each group enamel microhardness statistical analysis is as follows: between SOF group, 1 group of toothpaste and 4 groups of toothpaste not
There is significant difference；Containing 6.0 % micron order calcium carbonate and 2 groups of the toothpaste of 2.0 % nano-grade hydroxy apatites, compared with SOF group,
There is the significant difference (p value < 0.05) of statistical significance；Containing 4.0 % micron order calcium carbonate and 4.0 % nano-grade hydroxy apatites
3 groups of toothpaste, contrast one by one with SOF group, 1 group of toothpaste and 4 groups of toothpaste, all exist statistical significance significant difference (p value <
0.05).
Fig. 4 is the Electron micrographs picture of the enamel surface after initial normal, acid attack and toothpaste process.Normal throwing
Enamel surface after light is smooth, smooth (Fig. 4 a)；Enamel surface defect after acid attack, rugged, a large amount of distributions are several
The hole (Fig. 4 b) of micron size；After SOF processes 14 times, enamel surface presents fish scale-shaped, and micro-crack size is 1 ~ 2 micron
(Fig. 4 c)；After toothpaste 1 processes, enamel surface presents sand dune shape, subregion relatively flat (Fig. 4 d)；Process at toothpaste 2
After, enamel surface occurs in that a certain amount of deposit, and plane is the most smooth, distributed certain micro-hole (Fig. 4 e)；At toothpaste 3
After process, enamel surface also has certain deposit, and plane is the most smooth, and micro-hole ratio is sparse, and the size in hole is about 1 micron
(Fig. 4 f)；After toothpaste 4 processes, enamel surface also has a small amount of deposit, in sand dune shape, cheats the least 1 ~ 2 micron (Fig. 4 g).
After acid attack, enamel surface becomes rugged, in the range of surface micro-vickers hardness reduces to 180 ~ 190 HV.
Because the low ph value of citric acid causes hydroxyapatite to dissolve, forming the demineralization of enamel surface, the hydroxyapatite on surface lacks
Lose or density reduces.In hydroxyapatite course of dissolution, calcium ion, hydroxide ion and phosphate anion successively run off.
In SOF group, enamel surface presents fish scale-shaped, and surface micro-vickers hardness has to fraction of lifting, does not obtains sufficiently
Mineralising is repaired, and calcium ion and phosphate anion supersaturation present in SOF solution is described, is made by hydroxylapatite biology mineralising
With, repairing dental enamel surface can be helped, but repairing effect is limited to calcium ion a small amount of in solution and phosphate anion；At tooth
In cream 1 group, the micron order calcium carbonate in toothpaste can provide certain calcium concentration, help to improve environmental pH；Sodium monofluorophosphate is also
Can promote dental hydroxy apatite mineralising, so enamel surface obtains mineralising effectively, surface presents sand dune shape, part district
Territory is relatively flat, and micro-vickers hardness is highly improved；In 2 groups of toothpaste, enamel surface obtains active and effective ore deposit
Changing, compared with SOF group, micro-vickers hardness is significantly improved；In 3 groups of toothpaste, with SOF group, 1 group of toothpaste and 4 groups of toothpaste
Enamel compare, surface micro-vickers hardness obtains being obviously improved of statistical significance, and enamel surface obtains best ore deposit
Change and repair, and the deposit on surface is also most, the mutual of 4.0 % micron order calcium carbonate and 4.0 % nano-grade hydroxy apatites is described
Joining, produce synergism, optimal mass ratio is 1:1, forms the maximum amount of tosca at enamel surface, follow-up
During, sustained release calcium ion and phosphate radical, preferably repairing dental enamel surface；In 4 groups of toothpaste, enamel dimensional microstructure
Family name's hardness is greatly improved, and surface is the most relatively flat, illustrates that nanometer hydroxyapatite and single calcium monofluorophosphate. can help effectively
Demineralization enamel surface mineralising.
The Dentinal external reparative experiment of experimental example 2 demineralization
Collect the healthy third molar (patient's informed consent) extracted because of correction in stomatological hospital, fully clean up and put into 0.5
In wt% thymol aqueous solution.Using low-speed diamond cutting machine (SYJ-160 low-speed diamond cutting machine) to prepare thickness is 2
The dentin thin slice of mm, more respectively through the carborundum waterproof abrasive paper polishing grinding of 200,400,1000,2000 and 4000 mesh to surface
Light is smooth；Finally polish smooth with 3M polishing paper (3 microns), and at deionized water ultrasonic cleaning 3 min, standby.
Before using, every dentin sheet is put into demineralization in 36 wt% phosphate aqueous solutions and processes 2 min, use deionized water subsequently
Rinse 3 min, take out sample before 3 dentin do toothpaste process and, to be used as phenetic analysis, remain and be randomized into 5 groups, often organize 6
Sheet.Dentin sheet is fixed in oral cavity elastomeric material (Shanghai Columba livia board), and dentin faces up.Toothpaste processes the tool of dentin sample
Body step is as follows: weigh 5.0 g SOF, experimental group toothpaste 1,2,3 and 4 adds 10.0 g deionized water stirrings respectively and makes aqueous solution
Or toothpaste serosity, and it is poured on 5 groups of elastomeric materials being embedded with dentin sample, with soft bristle tooth brush (bright and clear jade-like stone profit toothbrush) manually
Light brush 1 min, quiet puts 1 min；Then, with 20 mL deionized water rinsing 3 times, put in 20 ml Mouthsimulator salivas and soak；
Subsequently, the constant temperature that constant rate of speed the is 150 rpm container containing Mouthsimulator saliva and dentin sheet being placed in 37 oC shakes
Swing 4 h in device (THZ-98A).Process dentin sample every day 3 times, and after third time process, 37 oC Mouthsimulator salivas
In overnight.When processing sample number and being 6,14 times, take out 3 dentin samples, after drying and processing, preserve, show for scanning electron
Micro mirror mirror SEM(Hitachi S-3400N) deposition of phenetic analysis dentin surface and the diameter situation of change (table of dentinal tubule
Before levying, dentin sample surfaces vacuum metallizing) and final dentin sample surfaces carry out X-ray elementary analysis (20 KeV).
According to sample SEM picture, measure dentinal tubule aperture (canaliculi dentales diameter measuring method: through dentinal tubule center and arrive
Reach the beeline on tubule both sides, and measurement number is more than 120, takes the meansigma methods of 3 dentin canaliculi dentaleses).
In Electron micrographs picture, the dentin surface after acid attack is smooth, and surface canaliculi dentales all comes out,
Average pore size is 3.89 ± 0.54 μm (Fig. 5 a and Fig. 6 a).Different process brings various change to the dentin of demineralization:
After SOF processes 6 times or 14 times, dentin surface is the most smooth, but canaliculi dentales aperture diminishes, respectively 3.58 ± 0.52 μm
(Fig. 5 b and Fig. 6 b) and 3.32 ± 0.52 μm (Fig. 5 g and Fig. 6 g)；After toothpaste 1 processes 6 times or 14 times, dentin surface has one
Fixed deposit, canaliculi dentales aperture also diminishes, respectively 3.44 ± 0.46 μm (Fig. 5 c and Fig. 6 c) and 3.08 ± 0.44 μm
(Fig. 5 h and Fig. 6 h)；After toothpaste 2 processes 6 times or 14 times, dentin surface has deposit, canaliculi dentales aperture also to diminish, and is respectively
3.28 ± 0.52 μm (Fig. 5 d and Fig. 6 d) and 2.76 ± 0.46 μm (Fig. 5 i and Fig. 6 i)；After toothpaste 3 processes 6 times or 14 times,
There is graininess deposit in dentin surface, and a small amount of canaliculi dentales is blocked, and canaliculi dentales aperture also diminishes, and respectively 3.10 ± 0.50
μm (Fig. 5 e and Fig. 6 e) and 2.56 ± 0.56 μm (Fig. 5 j and Fig. 6 j)；After toothpaste 4 processes 6 times or 14 times, dentin surface has
Graininess deposit, canaliculi dentales aperture also diminishes, respectively 3.31 ± 0.49 μm (Fig. 5 f and Fig. 6 f) and 2.93 ± 0.56
μm (Fig. 5 k and Fig. 6 k).Testing toothpaste and SOF from strong to weak arrangement according to the effect reducing canaliculi dentales, order is tooth respectively successively
Cream 3, toothpaste 2, toothpaste 4, toothpaste 1 and SOF.
In dentin semiquantitative surface elemental analysis result (voltage 20 eKv), acid attack dentin, SOF group, toothpaste 1
Group, 2 groups of toothpaste, 3 groups of toothpaste and 4 groups of toothpaste process 14 Ci Hou dentin surface calcium-phosphorus ratios respectively may be about 0.2,0.7,1.1,2,
1.8 and 1.5.
In actual processing procedure, reducing of demineralization dentin surface canaliculi dentales aperture is the result of biomineralization, is
In toothpaste, active matter provides calcium ion, phosphate anion, under fluorion and pH environmental effect, forms hydroxyapatite phase material
Result.Here active matter comprises SOF solution, calcium carbonate and hydroxyapatite.After acid attack, dentin surface or its surface
In the canaliculi dentales exposed, easily the micron order in deposition toothpaste and nano-scale particle thing, help to repair demineralization dentin.Finally
In result, 1,2,3 and 4 pairs of Dentinal remineralization efficacy of demineralization of toothpaste will be better than SOF solution, shows the micron order in toothpaste
Calcium carbonate, nano-grade hydroxy apatite and single calcium monofluorophosphate. have played effect, can bring mineralising repairing effect significantly.Toothpaste 1,
2, in 3 and 4 groups, find that the toothpaste 3 containing 4.0 % micron order calcium carbonate and 4.0 % nano-grade hydroxy apatites is to demineralization dentin
Remineralization efficacy best, than 1 group of the toothpaste containing 8.0% micron order calcium carbonate and 4 groups of the toothpaste containing 8.0% nano-grade hydroxy apatite
Will get well, hint is in toothpaste 3, and 4% micron order calcium carbonate and 4% nano-grade hydroxy apatite can exist synergism, on surface
Advantage deposits, and during follow-up, adjusts solution environmental pH value, and also the mineralising for tooth provides more calcium ions and phosphoric acid
Radical ion.The best in quality ratio of its micro-calcium carbonate and nano-grade hydroxy apatite is 1:1.Toothpaste processes dentin after 14 times
Semi-quantitative elemental analysis result shows the tooth that the toothpaste 2 and 3 containing micron order calcium carbonate and nano-grade hydroxy apatite processed
The calcium-phosphorus ratio on essence surface, higher than what other were organized, also high than the calcium-phosphorus ratio numerical value 1.67 of hydroxyapatite, illustrate to there is micron order
The deposition of calcium carbonate, and the deposition of these calcium carbonate be under the collaborative help of nanometer hydroxyapatite produce.Study carefully
Its reason is probably the different charge adsorption effect of micron order calcium carbonate and nano-grade hydroxy apatite particle surface.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. one kind contains nano-grade hydroxy apatite and the toothpaste of micron order calcium carbonate, it is characterised in that comprise nano-grade hydroxy phosphorus
Lime stone, micron order calcium carbonate and fluoride；
The particle diameter of described nano-grade hydroxy apatite be less than 100 nm, the particle diameter of described micron order calcium carbonate be 38 μm and with
Under；
In described fluoride, fluorine element mass concentration in described hydroxy agustite tooth-paste is not more than 8.0wt%, described nanoscale
The mass content of hydroxyapatite is not more than the quality of 20wt%, described micron order calcium carbonate and described nano-grade hydroxy apatite
Ratio is 1:10 ~ 10:1.
Toothpaste the most according to claim 1, it is characterised in that the particle diameter of described micron order calcium carbonate be 13 μm and with
Under, the particle diameter of described nano-grade hydroxy apatite is 30nm ~ 80nm.
Toothpaste the most according to claim 1 and 2, it is characterised in that described micron order calcium carbonate and described nano hydroxyapatite
The mass ratio of lime stone is 1:2 ~ 4:1, and the mass content of described micron order calcium carbonate is 4wt% ~ 30wt%.
Toothpaste the most according to claim 3, it is characterised in that the mass content of described micron order calcium carbonate is 4wt%, institute
The mass content stating nano-grade hydroxy apatite is 4wt%, and calcium carbonate crystal formation is calcite phase.
5. according to the toothpaste described in any one of claim 1-4, it is characterised in that described fluoride is sodium fluoride and/or single fluorine
Sodium phosphate, in described fluoride, fluorine element mass concentration in described hydroxy agustite tooth-paste is not more than 0.1wt%.
6. according to the toothpaste described in any one of claim 1-5, it is characterised in that also include abrasivus, thickening agent, wetting agent,
At least one in sweeting agent, antibacterial, foaming agent, essence, pigment.
Toothpaste the most according to claim 6, it is characterised in that comprise the component of following mass percent:
Described micron order calcium carbonate 2wt% ~ 40 wt%,
Described nano-grade hydroxy apatite 1wt% ~ 20 wt%,
Described abrasivus 2wt% ~ 40 wt%,
Described thickening agent 0.02 wt% ~ 8 wt%,
Described wetting agent 1wt% ~ 50wt%,
Described sweeting agent 0.001 wt% ~ 0.1 wt%,
Described antibacterial 0.004 wt% ~ 0.1 wt%,
Described foaming agent 0.1 wt% ~ 5 wt%,
Described fluoride 0 wt% ~ 2 wt%,
Described essence 0.6 wt% ~ 3 wt%,
Described pigment 0 wt% ~ 0.01 wt%.
Toothpaste the most according to claim 7, it is characterised in that described abrasivus is silicon dioxide, calcium phosphate dibasic dihydrate
Or at least one in calcium carbonate；Described thickening agent is at least one in xanthan gum, carrageenan or sodium carboxymethyl cellulose；Institute
Stating wetting agent is at least one in glycerol, sorbitol or PEG400；Described sweeting agent is saccharin, sucralose or wood
At least one in sugar alcohol；Described antibacterial is at least one in zinc citrate, sodium benzoate or methyl hydroxybenzoate；Described
Infusion is at least one in sodium lauryl sulphate, cocamido propyl betaine or sodium lauroyl sarcosine；Described essence
For Mint Essence；Described pigment is at least one in light green pigment, allured red pigment, bright blue pigment or lemon yellow pigment.
Toothpaste the most according to claim 8, it is characterised in that comprise: dicalcium phosphate dehydrate 12 wt%, carrageenan 0.8
Wt%, glycerol 28 wt%, sucralose 0.1 wt%, zinc citrate 0.05 wt%, sodium lauryl sulphate 2 wt%, single fluorophosphoric acid
Sodium 0.76 wt%, essence 1.25 wt%, pigment 0.005 wt%, hydrated SiO 2 10 wt%, micron order calcium carbonate 4 wt%, receive
Rice hydroxyapatite 4 wt%；
Described micron order calcium carbonate, for calcite crystal formation, filters through 1200 mesh sieve, and mean diameter is 13 below m；Described
Mean diameter 60 nm of nano-grade hydroxy apatite.
10. the preparation method of the toothpaste described in an any one of claim 1-9, it is characterised in that comprise the steps:
The recipe ingredient of described toothpaste is placed in 200rpm ~ 1000rpm in blender and stirs 20min ~ 60min；
Vacuum outgas becomes paste.
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| CN106511105A (en) * | 2017-01-10 | 2017-03-22 | 杭州皎洁口腔保健用品有限公司 | Anhydrous toothpaste repairing demineralized enamel and dentin and preparation method thereof |
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| CN107625659A (en) * | 2017-09-04 | 2018-01-26 | 美晨集团股份有限公司 | A kind of whitening toothpaste and preparation method thereof |
| CN108272646A (en) * | 2018-04-11 | 2018-07-13 | 佳木斯大学 | A kind of antibacterial toothpaste and preparation method thereof of hydroxyl apatite |
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| CN112891234A (en) * | 2019-12-03 | 2021-06-04 | 谭生龙 | Biphase calcium-phosphorus material and toothpaste containing biphase calcium-phosphorus material |
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| CN111481453A (en) * | 2020-04-30 | 2020-08-04 | 扬州倍加洁日化有限公司 | Desensitizing oral composition, preparation method and application thereof |
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| CN113425610A (en) * | 2021-07-19 | 2021-09-24 | 厦门金特康生物科技有限公司 | Toothpaste and preparation method thereof |
| CN114886782A (en) * | 2022-05-07 | 2022-08-12 | 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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Address after: 311305 building 3, 268 Dakang Road, Qingshanhu science and Technology City, Lin'an District, Hangzhou City, Zhejiang Province Patentee after: HANGZHOU JIAOJIE ORAL HEALTH CARE PRODUCTS Co.,Ltd. Address before: Building 15, No. 2, Huafeng Road, Shiqiao Street, Xiacheng District, Hangzhou, Zhejiang 310022 Patentee before: HANGZHOU JIAOJIE ORAL HEALTH CARE PRODUCTS Co.,Ltd. |