CN118141697A - High-temperature-resistant color-changeable fluorine-containing pit and groove sealing agent, and preparation method and application thereof - Google Patents
High-temperature-resistant color-changeable fluorine-containing pit and groove sealing agent, and preparation method and application thereof Download PDFInfo
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- CN118141697A CN118141697A CN202410272210.XA CN202410272210A CN118141697A CN 118141697 A CN118141697 A CN 118141697A CN 202410272210 A CN202410272210 A CN 202410272210A CN 118141697 A CN118141697 A CN 118141697A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 96
- 239000011737 fluorine Substances 0.000 title claims abstract description 96
- 238000007789 sealing Methods 0.000 title claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 229920005989 resin Polymers 0.000 claims abstract description 53
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- 238000000034 method Methods 0.000 claims abstract description 24
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- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 239000000565 sealant Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000068 pit and fissure sealant Substances 0.000 claims abstract description 5
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims description 30
- 229930187593 rose bengal Natural products 0.000 claims description 30
- 229940081623 rose bengal Drugs 0.000 claims description 30
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- SGJSDMIZJMFOFH-UHFFFAOYSA-N diphenyl(trifluoromethyl)-lambda3-iodane Chemical group C1(=CC=CC=C1)I(C(F)(F)F)C1=CC=CC=C1 SGJSDMIZJMFOFH-UHFFFAOYSA-N 0.000 claims description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 19
- 208000002925 dental caries Diseases 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 11
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical group CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 9
- 210000003298 dental enamel Anatomy 0.000 claims description 5
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 claims description 4
- HYQASEVIBPSPMK-UHFFFAOYSA-N 12-(2-methylprop-2-enoyloxy)dodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCOC(=O)C(C)=C HYQASEVIBPSPMK-UHFFFAOYSA-N 0.000 claims description 3
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- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 4
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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Abstract
The invention relates to the technical field of dental restoration materials, in particular to a fluorine-containing pit and groove sealing agent with high temperature resistance and color change, a preparation method and application thereof, wherein the fluorine-containing pit and groove sealing agent comprises a resin matrix and an inorganic filler; the resin matrix comprises an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant. The preparation method comprises the following steps: uniformly mixing and dispersing an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant to obtain a resin matrix; adding inorganic filler into the resin matrix, and uniformly mixing to obtain the dental pit and fissure sealant premix; and (3) defoaming the dental sulcus sealant premix to obtain the fluorine-containing sulcus sealant. The fluorine-containing pit and groove sealing agent has bright pink color before curing, is convenient for doctors to identify the sealed area when in use, turns white after curing, has certain similarity with tooth color and has certain distinction. The tooth appearance is not affected in the use process, the regular examination of doctors is easy, the high temperature resistance is realized, and the color is not reversed due to heating.
Description
Technical Field
The invention relates to a high-temperature-resistant color-changeable fluorine-containing pit and groove sealing agent, and a preparation method and application thereof, and belongs to the technical field of dental repair materials.
Background
The oral health is an important sign of the physical and mental health of residents, and the oral diseases are common diseases and frequently encountered diseases which affect the chewing, pronunciation and other physiological functions of the oral cavity, and are closely related to cerebral apoplexy, heart disease, diabetes, digestive system diseases and other systemic diseases. The fourth national oral health epidemiological investigation revealed that the 12 year old child had a caries rate of 34.5% that increased by 7.8% over ten years ago. The caries rate of children aged 5 is 70.9%, which is increased by 5.8% over ten years ago. Children have had caries conditions that have assumed an ascending situation.
Caries is generally distributed in the alveolus of teeth, and the fissure of the alveolus of teeth is easy to accumulate food residues, is not easy to clean, and bacteria are easy to grow and reproduce to cause caries. The pit and groove sealing is also called point crazing groove sealing, is the most effective method for preventing pit and groove caries recommended by world health organization, and is characterized by that it uses pit and groove sealing material to coat the pit and groove gap between occlusal surface and buccal surface of dental crown, and after it is infiltrated into pit and groove, it is gradually solidified and hardened, and reduces exposure of pit and groove point crazing groove, and establishes a layer of barrier to protect dental enamel from being corroded by bacteria, its metabolic products and food residues, in addition, because of forming local closed environment, the residual bacteria can be promoted to be apoptotic, so that it can effectively prevent pit and groove caries and secondary caries. The most widely used sealant in the market at present is a resin type pit and groove sealant, and the resin type pit and groove sealant has the advantages of good sealing property, low leakage rate and the like, can fill up gaps of teeth, is easy to clean, and prevents occurrence of dental caries.
The fluorine-containing pit and groove sealing agent can release fluorine on the basis of sealing the pit and groove, and the fluorine can directly inhibit energy metabolism required by bacterial growth in the oral cavity, inhibit adhesion of bacteria to tooth surfaces, inhibit activities of various enzymes in the bacterial metabolic process and enable the bacteria to grow, be in metabolic disorder or stop. Fluorine can bind to hydroxyapatite in tooth structure, increase hardness and acid resistance of enamel, reduce plaque formation and reduce caries incidence.
The color-changing pit and groove sealing agent has obvious color change before and after curing, is a vivid color before curing, and is opaque white after light curing. In the sealing process, the bright color is easy to see the accurate position of the smearing, so that whether the smearing is sealed in place or not is convenient to determine, and after the sealing agent is solidified, the color is white, and the color has certain similarity with the color of teeth and certain distinction. I.e. the teeth are not affected during the use, and the regular examination of doctors is easy.
The color-changing system in the prior art is sensitive to temperature, and the high temperature can catalyze the reaction of the system before curing to generate a color-changing phenomenon, namely the color-changing problem of the product before being heated. And the high temperature can also influence the cured product system, so that the product can be subjected to a color reversal phenomenon, namely the color of the cured sample is changed from white to the color before curing slowly after being heated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fluorine-containing pit and groove sealing agent with high temperature resistance and color change, a preparation method and application thereof, solves the problems of unstable color and inconvenient use of the pit and groove sealing agent, and solves the problem of fluorine release safety; the fluorine-containing pit and groove sealing agent has bright pink color before curing, is convenient for doctors to identify the sealed area when in use, turns white after curing, has similar color to teeth, is convenient for postoperative observation, is high-temperature resistant, and cannot be reversely colored due to heating; and the fluorine-containing pit and groove sealing agent can continuously and stably release fluorine in the use process, so that dental caries can be effectively prevented, and the release time is longer and safer.
The technical scheme for solving the technical problems is as follows: a high temperature resistant, color changeable fluorine-containing pit and groove sealing agent, which comprises a resin matrix and an inorganic filler;
The resin matrix comprises an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant.
Further, in the fluorine-containing pit and groove sealing agent, the resin matrix accounts for 70% -96% of the weight of the whole fluorine-containing pit and groove sealing agent; the inorganic filler accounts for 4-30% of the total weight of the fluorine-containing pit and groove sealing agent.
Further, in the resin matrix, the acrylic ester monomer accounts for 92-98.6% of the weight of the resin matrix, and the fluorine-containing cationic initiator accounts for 0.3-5% of the weight of the resin matrix; the mass ratio of the fluorine-containing cationic initiator to the co-initiator is 1: (0.5-2);
the coloring agent comprises rose bengal, and the mass ratio of the rose bengal to the fluorine-containing cationic initiator is 1: (200-800).
Further, the colorant includes rose bengal and titanium dioxide;
In the resin matrix, the titanium dioxide accounts for 0.15% -0.5% of the weight of the resin matrix.
Further, the fluorine-containing cationic initiator is diphenyl iodotrifluoromethane sulfonate.
Further, the inorganic filler is any one or more of silanized modified micron-sized or nano-sized silicon dioxide and silanized modified micron-sized or nano-sized glass powder.
Further, the acrylic monomer comprises a main monomer and a diluent;
The main monomer is at least one of bisphenol A-glycidyl methacrylate (BisGMA) and Urethane Dimethacrylate (UDMA); the diluent is at least one of triethylene glycol dimethacrylate (TEGDMA) and 1, 12-dodecanediol dimethacrylate (D 3 MA);
the mass ratio of the main monomer to the diluent is 6: (3.5-4.5).
Further, the co-initiator is ethyl 4-dimethylaminobenzoate.
The invention also discloses a preparation method of the high-temperature-resistant and color-changeable fluorine-containing pit and groove sealing agent, which comprises the following steps:
S1, preparing a resin matrix
Uniformly mixing and dispersing an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant to obtain a resin matrix;
s2, preparation of dental pit and canal sealer premix
Adding inorganic filler into the resin matrix, and uniformly mixing to obtain the dental pit and fissure sealant premix;
S3, defoaming treatment
And (3) defoaming the dental sulcus sealant premix to obtain the fluorine-containing sulcus sealant.
The invention also discloses application of the high-temperature-resistant and color-changeable fluorine-containing pit and groove sealing agent, which is used for sealing pits and gaps on enamel to prevent dental caries.
The beneficial effects of the invention are as follows:
According to the invention, the fluorine-containing cationic initiator diphenyl iodotrifluoromethane sulfonate is added, so that the fluorine-containing pit and groove sealing agent can react with the colorant on the basis of initiating polymerization, obvious color change occurs in a system before and after curing, and the fluorine-containing pit and groove sealing agent is high-temperature resistant, strong in heat resistance and difficult to fade or color reverse before and after curing. The product has bright pink color before solidification, is convenient for doctors to identify the closed area when in use, turns white after solidification, is similar to the color of teeth, and is convenient for postoperative observation.
The fluorine-containing photoinitiator diphenyl iodotrifluoromethane sulfonate is added into the fluorine-containing pit and groove sealing agent, polymerization can be initiated after photocuring, so that a system is cured, and after the fluorine-containing cationic initiator is added, the curing performance of a fluorine-containing pit and groove sealing agent product is improved, the curing is fast, and the sensitivity of ambient light is good. Meanwhile, diphenyl iodotrifluoromethane sulfonate can interact with rose bengal, the system is pink before curing, reacts with the rose bengal during light curing, and changes color to white after curing. Namely, the light-cured compound reacts with a coloring agent rose bengal in the light-cured process, and the rose bengal is discolored to be white, so that the effect and the state of pit and groove sealing can be observed by doctors. In addition, the diphenyl iodotrifluoromethane sulfonate contains three fluoride ions in the molecule, and has polymerization reaction with double bonds in a resin matrix, so that fluorine can be continuously and slowly released in the use process, the release rate is stable, the release time is long, and dental caries can be prevented for a long time; the fluorine-containing pit and groove sealing agent disclosed by the invention has the advantages of more stable fluorine release rate, longer release time and safer release time, and does not generate sudden release phenomenon.
The fluorine-containing pit and groove sealing agent disclosed by the invention is stable in a system before curing, is stored for 7 months in a dark place at 60 ℃, keeps the color unchanged, does not fade, resists high temperature, and keeps the curing performance unchanged; the cured system is stable, the cured product turns white, and the cured sample is placed in a 60 ℃ oven for 1 month, so that the color of the cured product is kept similar to the color of teeth without the occurrence of the phenomenon of color reversal. The product system is stable, high temperature resistant before and after solidification, and is not limited by temperature conditions in the transportation, storage and use processes.
In the fluorine-containing pit and groove sealing agent, diphenyl iodide trifluoro methane sulfonate is added to enable the whole system to be more simplified, and one component has the functions of initiating polymerization, color change and fluoride ion release.
Drawings
FIG. 1 is a photograph of the color of the fluorine-containing pit and groove sealer prepared in example 1-2 before and after curing;
FIG. 2 is a graph showing the change in the amount of fluorine eluted.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A high temperature resistant, color changeable fluorine-containing pit and groove sealing agent, which comprises a resin matrix and an inorganic filler;
The resin matrix comprises an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant.
Specifically, in the fluorine-containing pit and groove sealing agent, the resin matrix accounts for 70% -96% of the weight of the whole fluorine-containing pit and groove sealing agent; the inorganic filler accounts for 4-30% of the total weight of the fluorine-containing pit and groove sealing agent.
Specifically, in the resin matrix, the acrylic ester monomer accounts for 92-98.6% of the weight of the resin matrix, and the fluorine-containing cationic initiator accounts for 0.3-5% of the weight of the resin matrix; the mass ratio of the fluorine-containing cationic initiator to the co-initiator is 1: (0.5-2);
the coloring agent comprises rose bengal, and the mass ratio of the rose bengal to the fluorine-containing cationic initiator is 1: (200-800).
Specifically, the colorant comprises rose bengal and titanium dioxide;
In the resin matrix, the titanium dioxide accounts for 0.15% -0.5% of the weight of the resin matrix. The addition of titanium dioxide can play a role in toning, so that the colorant is pink.
Specifically, the fluorine-containing cationic initiator is diphenyl iodotrifluoromethane sulfonate.
Specifically, the inorganic filler is any one or more of silanized modified micron-sized or nano-sized silicon dioxide and silanized modified micron-sized or nano-sized glass powder.
Specifically, the acrylic monomer comprises a main monomer and a diluent;
The main monomer is at least one of bisphenol A-glycidyl methacrylate and urethane dimethacrylate; the diluent is at least one of triethylene glycol dimethacrylate and 1, 12-dodecanediol dimethacrylate;
the mass ratio of the main monomer to the diluent is 6: (3.5-4.5).
Specifically, the co-initiator is ethyl 4-dimethylaminobenzoate.
A preparation method of a high-temperature-resistant color-changeable fluorine-containing pit and groove sealing agent comprises the following steps:
S1, preparing a resin matrix
Uniformly mixing and dispersing an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant to obtain a resin matrix;
s2, preparation of dental pit and canal sealer premix
Adding inorganic filler into the resin matrix, and uniformly mixing to obtain the dental pit and fissure sealant premix;
S3, defoaming treatment
And (3) defoaming the dental sulcus sealant premix to obtain the fluorine-containing sulcus sealant.
Use of a high temperature resistant variable color fluorine-containing socket sealant for sealing sockets and spots on enamel to prevent dental caries.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The preparation of the fluorine-containing pit and groove sealing agent with high temperature resistance and color change comprises the following steps:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 5.0g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 10mg of rose bengal are added into an emulsification reaction kettle, and are mechanically mixed for 24 hours, and then further dispersed by using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the dental pit and groove sealing agent premix into a rubber cup matched with a non-intervention material homogenizer, placing the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Example 2
The preparation of the fluorine-containing pit and groove sealing agent with high temperature resistance and color change comprises the following steps:
(1) Preparation of resin matrix
40G of bisphenol A-glycidyl methacrylate, 20g of urethane dimethacrylate, 40g of triethylene glycol dimethacrylate, 2g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 6mg of rose bengal are added into an emulsification reaction kettle, and are mechanically mixed for 24 hours, and then further dispersed by using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
And (3) adding 1g of micro-scale silanization modified glass powder, 1g of nano-scale silanization modified glass powder and 3g of nano-scale silanization modified silicon dioxide into the emulsification reaction kettle, and mechanically stirring for 48 hours to obtain the dental pit and groove sealing agent premix.
(3) Dental pit and canal sealing agent deaeration
Pouring the premix into a rubber cup matched with a non-intervention material homogenizer, putting the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Comparative example 1
The pit and groove sealer was prepared by the same method as in example 1, except that: the fluorine-containing cation initiator diphenyl iodotrifluoromethane sulfonate is replaced by a conventional initiator camphorquinone, and tetrabutylammonium tetrafluoroborate is added as a fluorine additive, and the specific process is as follows:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 2.0g of camphorquinone, 3.0g of ethyl 4-dimethylaminobenzoate, 0.30g of titanium dioxide, 10mg of rose bengal and 2.9g of tetrabutylammonium tetrafluoroborate were added to an emulsification reactor, and were mechanically mixed for 24 hours, followed by further dispersion using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the premix into a rubber cup matched with a non-intervention material homogenizer, putting the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Comparative example 2
The pit and groove sealer was prepared by the same method as in example 1, except that: the rose bengal in the colorant is replaced by methylene blue, and the specific process is as follows:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 5.0g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 10mg of methylene blue were added to an emulsification reactor, and the mixture was mechanically mixed for 24 hours, followed by further dispersion using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the dental pit and groove sealing agent premix into a rubber cup matched with a non-intervention material homogenizer, placing the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Comparative example 3
The pit and groove sealer was prepared by the same method as in example 1, except that: the mass ratio of the rose bengal to the fluorine-containing cationic initiator in the comparative example 3 is adjusted to be 1:125, namely increasing the use amount of rose bengal, and the specific process is as follows:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 5.0g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 40mg of rose bengal are added into an emulsification reaction kettle, and are mechanically mixed for 24 hours, and then further dispersed by using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the dental pit and groove sealing agent premix into a rubber cup matched with a non-intervention material homogenizer, placing the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Comparative example 4
The pit and groove sealer was prepared by the same method as in example 1, except that: the mass ratio of the rose bengal to the fluorine-containing cationic initiator in comparative example 4 was adjusted to be 1:1000, namely reducing the use amount of rose bengal, and specifically comprises the following steps:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 5.0g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 5mg of rose bengal are added into an emulsification reaction kettle, and are mechanically mixed for 24 hours, and then further dispersed by using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the dental pit and groove sealing agent premix into a rubber cup matched with a non-intervention material homogenizer, placing the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Comparative example 5
The pit and groove sealer was prepared by the same method as in example 1, except that: reducing the dosage of the fluorine-containing cationic initiator diphenyl iodotrifluoromethane sulfonate to ensure that the mass ratio of rose bengal to the fluorine-containing cationic initiator is 1:150, the specific process is as follows:
(1) Preparation of resin matrix
60G of bisphenol A-glycidyl methacrylate, 40g of triethylene glycol dimethacrylate, 1.5g of diphenyliodotrifluoromethane sulfonate, 3.0g of 4-dimethylaminobenzoic acid ethyl ester, 0.30g of titanium dioxide and 10mg of rose bengal are added into an emulsification reaction kettle, and are mechanically mixed for 24 hours, and then further dispersed by using a homogenizing disperser to prepare a resin matrix.
(2) Preparation of dental pit and canal sealer premix
3G of micro-scale silanization modified glass powder and 8g of nano-scale silanization modified silicon dioxide are further added into an emulsification reaction kettle, and mechanical stirring is carried out, and the dental pit and groove sealing agent premix is obtained after 48h of stirring.
(3) Dental pit and canal sealing agent deaeration
Pouring the dental pit and groove sealing agent premix into a rubber cup matched with a non-intervention material homogenizer, placing the rubber cup into non-intervention material homogenizer equipment, and operating the non-intervention material homogenizer equipment to finally obtain the bubble-free pit and groove sealing agent.
Performance testing was performed on the pit and groove blocking agents prepared in the above examples and comparative examples:
The fluorine-containing pit and groove blocking agent prepared in the above examples 1-2 was pink and white after photo-curing, as shown in FIG. 1.
Wherein, the photo-curing conditions are: the surface of the sealing agent is irradiated for 20s by a dental light curing lamp, and the light outlet and the surface of the product are kept at 1-2mm.
The above pit and groove sealing agent curing time was measured by the following method: the mixed sealant was put into a sample tank (cylindrical mold having a height of 4mm and a diameter of 4 mm), the temperature of the sample tank was maintained at (37.+ -. 1) ℃ and air bubbles were carefully discharged to cause the sealant in the sample tank to slightly overflow, and a film was covered. The output window of the light curing lamp was aligned with the center of the sample and placed against the film, and the light was irradiated for 20s, and the time required from the start of irradiation to the maximum temperature was recorded.
The above pit blocking agent was tested for ambient light sensitivity by the following method: in the dark room, the light source was placed vertically at the opening of the sample cell (cylindrical mold having a height of 2mm and a diameter of 4 mm), and the light source was adjusted so that the illuminance at the opening of the sample cell reached (8 000.+ -. 500) lx. A blocking agent was added to the (23.+ -. 1) C sample cell, and the cell was placed under a light source, and the time required from the onset of illumination to the occurrence of deviation in the linear increase in temperature was recorded. The thickness of the above pit blocking agent uncured film was also measured by: the slide was placed horizontally on the stage of an optical microscope, a blocking agent was dropped onto the slide, and a cover slip was placed before polymerization began. The sealer should be formed in a circular shape or a nearly circular shape, irradiated with a light for 20 seconds, after 5 minutes, the edge of the sealer wafer was inspected, and the distance from the parting line between the cured and uncured sealer to the outer edge of the sealer wafer was measured to an accuracy of 5 μm.
Meanwhile, the stability of the pit and groove blocking agent is also measured, and the measuring method comprises the following steps: the cured pit and groove sealing agent is placed at 60 ℃ for 30 days, the color change of the cured pit and groove sealing agent is observed, if the pit and groove sealing agent still keeps white, the stability is good, and if the pit and groove sealing agent has a color reversal phenomenon, the stability is poor. Specific measurement data are shown in table 1 below.
TABLE 1 pit and groove sealer performance data for examples 1-2 and comparative examples 1-5
As can be seen from the data of example 1 and example 2 in Table 1, the fluorine-containing pit and groove sealing agent prepared by the method of the invention has the advantages of quick solidification, reduced use time of a light curing lamp and reduced discomfort of users; insensitivity to ambient light gives the operator more time to perform the closing operation. And the cured product is pink before curing, so that a doctor can conveniently identify a closed area when using the cured product, the cured product becomes white, and the cured product has certain similarity and distinction with tooth colors, does not influence the tooth beauty, and is easy for the doctor to check regularly. In addition, the cured heat stability is better, and the phenomenon of inverse color after heating can not occur, so that the tooth-shaped coating has better service performance, and the influence of inverse color of the pit-groove sealing agent on aesthetic feeling caused by the fact that teeth are contacted with hotter foods is avoided.
From the comparison of the data of example 1 and comparative example 1, it can be seen that: compared with the conventional initiator camphorquinone, the fluorine-containing cationic initiator diphenyl iodotrifluoromethane sulfonate has better photocuring performance, and if the conventional initiator camphorquinone is adopted, the color change before and after curing does not occur, so that the observation convenience can not be brought to the use process.
From the comparison of the data of example 1 and comparative example 2, it can be seen that: the system is more stable after the rose bengal and the diphenyl iodotrifluoromethane sulfonate are adopted for reaction, and the problem of color reversal does not occur after the rose bengal and the diphenyl iodotrifluoromethane sulfonate are heated. .
From the comparison of the data of example 1 and comparative examples 3, 4, 5, it can be seen that: the mass ratio of the coloring agent to the fluorine-containing cationic initiator can influence the use effect of the pit and groove sealing agent, and the pit and groove sealing agent with excellent use effect can be obtained more conveniently by adopting the dosage ratio defined by the invention, because the fluorine-containing photoinitiator diphenyl iodotrifluoromethane sulfonate can initiate polymerization after photo-curing, the curing performance of a system is improved, and the fluorine-containing pit and groove sealing agent product is fast to cure and insensitive to environmental light. Meanwhile, the diphenyl iodotrifluoro methane sulfonate can interact with rose bengal to enable the system to be pink before solidification, and react with the colorant rose bengal in the photo-solidification process, so that the rose bengal is discolored to be white, and the effect and the state of pit and groove sealing can be observed by doctors.
In addition, fluorine content was measured for the fluorine-containing pit and groove sealer prepared in example 1 and comparative example 1 according to the method for measuring soluble fluorine of YY0623-2008 dental materials. The specific results are shown in fig. 2, and it is found from the comparison of fig. 2 that the fluorine release rate of the fluorine-containing pit and groove sealing agent of example 1 is more stable, the phenomenon of abrupt release does not occur, and the release time is longer and safer.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. The high-temperature-resistant color-changeable fluorine-containing pit and groove sealing agent is characterized by comprising a resin matrix and an inorganic filler;
The resin matrix comprises an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant.
2. The high temperature resistant and color changeable fluorine-containing pit and groove sealing agent according to claim 1, wherein the resin matrix accounts for 70-96% of the total weight of the fluorine-containing pit and groove sealing agent; the inorganic filler accounts for 4-30% of the total weight of the fluorine-containing pit and groove sealing agent.
3. The high temperature resistant and color changeable fluorine-containing pit and groove sealing agent according to claim 1, wherein the acrylic monomer accounts for 92-98.6% of the weight of the resin matrix, and the fluorine-containing cationic initiator accounts for 0.3-5% of the weight of the resin matrix; the mass ratio of the fluorine-containing cationic initiator to the co-initiator is 1: (0.5-2);
the coloring agent comprises rose bengal, and the mass ratio of the rose bengal to the fluorine-containing cationic initiator is 1: (200-800).
4. A high temperature resistant, color changeable fluorine-containing pit and groove sealer according to claim 3 wherein said colorants comprise rose bengal and titanium dioxide;
In the resin matrix, the titanium dioxide accounts for 0.15% -0.5% of the weight of the resin matrix.
5. A high temperature resistant, color changeable fluorine-containing pit and groove sealer according to any one of claims 1-4 wherein said fluorine-containing cationic initiator is diphenyl iodotrifluoromethane sulfonate.
6. The high temperature resistant and color changeable fluorine-containing pit and groove sealing agent according to any one of claims 1 to 4, wherein the inorganic filler is any one or more of silanized modified micron-sized or nanometer-sized silicon dioxide and silanized modified micron-sized or nanometer-sized glass powder.
7. The high temperature resistant, color changeable fluorine-containing pit and groove sealer according to any one of claims 1-4, wherein the acrylic monomer comprises a main monomer and a diluent;
The main monomer is at least one of bisphenol A-glycidyl methacrylate and urethane dimethacrylate; the diluent is at least one of triethylene glycol dimethacrylate and 1, 12-dodecanediol dimethacrylate;
the mass ratio of the main monomer to the diluent is 6: (3.5-4.5).
8. A high temperature resistant, color changeable fluorine-containing pit and groove sealer according to any one of claims 1-4 wherein said co-initiator is ethyl 4-dimethylaminobenzoate.
9. A method for preparing a fluorine-containing pit and groove sealing agent with high temperature resistance and color change according to any one of claims 1 to 8, which is characterized in that the preparation method comprises the following steps:
S1, preparing a resin matrix
Uniformly mixing and dispersing an acrylic monomer, a fluorine-containing cationic initiator, a co-initiator and a colorant to obtain a resin matrix;
s2, preparation of dental pit and canal sealer premix
Adding inorganic filler into the resin matrix, and uniformly mixing to obtain the dental pit and fissure sealant premix;
S3, defoaming treatment
And (3) defoaming the dental sulcus sealant premix to obtain the fluorine-containing sulcus sealant.
10. Use of a fluorine-containing pit and fissure sealant according to any of claims 1-8 for sealing pits and fissures in dental enamel to prevent dental caries.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118141697A true CN118141697A (en) | 2024-06-07 |
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