CN116650363A

CN116650363A - Tooth whitening adhesive plaster and preparation method thereof

Info

Publication number: CN116650363A
Application number: CN202310648062.2A
Authority: CN
Inventors: 李娜
Original assignee: Hainan Western Central Hospital Danzhou First People's Hospital Hainan Western Regional Medical Center
Current assignee: Hainan Western Central Hospital Danzhou First People's Hospital Hainan Western Regional Medical Center
Priority date: 2023-06-02
Filing date: 2023-06-02
Publication date: 2023-08-29
Anticipated expiration: 2043-06-02
Also published as: CN116650363B

Abstract

The application relates to the field of tooth whitening, and in particular discloses a tooth whitening adhesive plaster and a preparation method thereof, wherein the adhesive plaster comprises the following raw materials in percentage by mass: peroxide: 1 to 5 percent; and (2) an adhesive: 10-20%; humectant: 40-50%; antiallergic agent: 1 to 2 percent; catalyst: 0.01 to 0.5 percent; stabilizing agent: 0.1 to 1 percent; water: the balance; the adhesive is mainly prepared by reacting raw materials containing carbomer, hydroxyethyl cellulose and chitosan fibers at the temperature of 30-100 ℃, wherein the mass ratio of the carbomer to the hydroxyethyl cellulose to the chitosan fibers is 10: (2-4): (1-3), wherein the pH value of the reaction is 5-6. The tooth whitening adhesive tape can effectively improve the strength and reduce the fracture probability when the adhesive tape is peeled off on the premise of ensuring the flexibility and the plasticity.

Description

Tooth whitening adhesive plaster and preparation method thereof

Technical Field

The application relates to the field of tooth whitening, in particular to a tooth whitening adhesive plaster and a preparation method thereof.

Background

The tooth whitening gel paste is a cosmetic product capable of improving the beauty of teeth while protecting the health of the oral cavity. There are various tooth whitening adhesive products on the market at present, which are generally made of soft materials, have plasticity and adhesiveness, can be adhered to the surface of teeth, and realize the tooth whitening effect by releasing active ingredients.

The tooth whitening gel is required to have sufficient softness and plasticity to accommodate tooth surfaces of various shapes and to maintain adhesion on the tooth surfaces. Therefore, most of the tooth whitening stickers on the market are usually made of thinner gel materials with transparent textures, and the stickers are poor in strength, low in durability and stability, and easy to break when being attached to or peeled off, so that the stickers remain on the tooth surfaces, and the use experience of users is affected.

Disclosure of Invention

The application provides a tooth whitening adhesive and a preparation method thereof, which aim to solve the problems of low strength and easy breakage of the tooth whitening adhesive.

In a first aspect, the application provides a tooth whitening adhesive tape, which comprises the following raw materials in percentage by mass:

peroxide: 1 to 5 percent;

and (2) an adhesive: 10-20%;

humectant: 40-50%;

antiallergic agent: 1 to 2 percent;

catalyst: 0.01 to 0.5 percent;

stabilizing agent: 0.1 to 1 percent;

water: the balance;

the adhesive is mainly prepared by reacting raw materials containing carbomer, hydroxyethyl cellulose and chitosan fibers at the temperature of 30-100 ℃, wherein the mass ratio of the carbomer to the hydroxyethyl cellulose to the chitosan fibers is 10: (2-4): (1-3), wherein the pH value of the reaction is 5-6.

Optionally, the peroxide is selected from at least one of carbamide peroxide and hydrogen peroxide.

Optionally, the humectant is at least one selected from glycerol, polyethylene glycol, propylene glycol, and butylene glycol.

Optionally, the antiallergic agent is at least one selected from chloride, fluoride and sodium monofluorophosphate; strontium fluoride is preferred.

Optionally, the catalyst is a basic catalyst, more specifically sodium hydroxide.

Optionally, the stabilizer is at least one selected from sodium citrate dihydrate, disodium edetate and sodium hexametaphosphate.

The carbomer and the hydroxyethyl cellulose have good bonding effect, and the carbomer contains a large number of carboxyl groups, can perform esterification reaction with the hydroxyethyl cellulose under the conditions to form gel with a cross-linked structure, so that the strength of the adhesive plaster is effectively enhanced, and the fracture probability of the adhesive plaster in the use process is reduced.

It should be noted that the adhesive plaster prepared by crosslinking has improved rigidity, reduced plasticity and flexibility, and is unfavorable for adhesion with the tooth surface and also unfavorable for reducing the fracture probability. In order to overcome the problem, a proper amount of chitosan fibers are added, are insoluble in water, and can play a role in dispersing stress and preventing crack growth when being dispersed in aqueous gel, so that the problem of reduced flexibility caused by crosslinking is effectively compensated.

Optionally, the length of the chitosan fiber is 1-100 μm; more preferably 5 to 30. Mu.m.

In the comprehensive view, the fiber with the length has better toughening effect and does not influence the appearance quality of the adhesive tape. Nanoscale fibers are difficult to disperse and have poor toughening effect, and fibers with longer lengths affect the aesthetic properties of the adhesive tape.

Optionally, the carbomer is an epoxy modified carbomer.

Optionally, the carbomer comprises the following components in parts by weight:

acrylic acid polymerized monomer: 100-130 parts;

crosslinking agent: 1-2 parts;

and (3) an initiator: 0.5 to 1.5 parts;

the acrylic acid polymerization monomer comprises the following components in percentage by mass: 2 to 3 of acrylic acid and glycidyl methacrylate.

Optionally, the epoxy modified carbomer is prepared according to the following method:

polymerization: dissolving an acrylic acid polymerization monomer and a cross-linking agent in ethyl acetate, heating to 50-60 ℃ under a nitrogen atmosphere, and then dropwise adding an initiator solution to perform polymerization reaction;

separating: after the reaction is completed, separating out precipitate and drying to obtain the epoxy modified carbomer.

Optionally, the cross-linking agent is selected from at least one of pentaerythritol triallyl ether and allyl sucrose ether.

Alternatively, the initiator is selected from bis (2-ethylhexyl) peroxydicarbonate.

By introducing epoxy groups in the preparation process of the carbomer, the carbomer can perform ring-opening reaction with the chitosan fiber to form chemical bonding, so that the connection between the chitosan fiber and the gel main body is enhanced, the toughening effect of the carbomer is fully exerted, and the bending performance of the carbomer is ensured. Meanwhile, the strength of the adhesive tape can be improved by open-loop crosslinking, and the occurrence probability of fracture phenomenon is reduced.

It should be noted that excessive glycidyl methacrylate, an epoxy polymerization monomer, tends to cause a decrease in the hydrophilicity of carbomers, which is disadvantageous in ensuring the adhesion, water absorption and plasticity thereof.

Optionally, the raw materials of the tooth whitening adhesive also comprise 2-5 mass% of dimethyl dimethoxy silane modified silicon dioxide; the dimethyl dimethoxy silane modified silicon dioxide comprises the following components in percentage by mass: the silica of (1-5) and dimethyl dimethoxy silane are blended and modified in short chain alcohol.

Optionally, the dimethyl dimethoxy silane modified silicon dioxide is prepared according to the following steps: dissolving dimethyl dimethoxy silane in short-chain alcohol, heating to 40-50 ℃, dripping a blending liquid of the short-chain alcohol and water, heating to 85-95 ℃ after dripping, reacting for 1-2 h, and distilling under reduced pressure to recover the short-chain alcohol; then heating to 120-130 ℃ for continuous polymerization for 1-2 h, adding silicon dioxide, stirring for 0.5-1 h, and cooling to room temperature to obtain the catalyst.

Alternatively, the short chain alcohol is selected from one of methanol or ethanol.

The adhesive adopted by the application is prepared from hydrophilic raw materials, and has strong water absorption, so that the inside active peroxide is easily diluted and dissolved out by saliva in the use process of the adhesive, and the oxidation whitening effect of the adhesive on teeth is difficult to be fully exerted. Therefore, the dimethyl dimethoxy silane modified silicon dioxide has good hydrophobicity, so that the affinity of the adhesive to saliva can be reduced to a certain extent, and the dissolution rate of active ingredients can be reduced.

Specifically, dimethyl dimethoxy silane has two methoxy groups, can generate two hydroxyl end groups after hydrolysis, and further can be polycondensed to form an Si-O-Si long chain with alkyl, and the long chain can be grafted on the surface of silicon dioxide to generate a hydrophobic effect. The long chain is easy to control the chain length, and the modified silicon dioxide with proper water-repellent capability is obtained, so that the adhesive plaster with moderate peroxide dissolution rate is realized. In addition, the Si-O-Si long chain is not easy to crosslink after grafting to increase the rigidity of the adhesive plaster, which is beneficial to reducing the fracture phenomenon in the using process.

Optionally, the stabilizer is at least one selected from sodium citrate dihydrate, tartaric acid, disodium edetate and sodium hexametaphosphate.

In a second aspect, the present application provides a method for preparing a tooth whitening strip, comprising the steps of:

preparation of an adhesive: adding carbomer, hydroxyethyl cellulose and chitosan fibers into water, uniformly stirring, adding glacial acetic acid until the pH value is 5-6, heating to 30-100 ℃ for reaction, and finishing the reaction to obtain the chitosan fiber;

gel preparation: stirring and mixing the adhesive and other raw materials under vacuum to obtain gel;

and (3) forming: and (3) coating and cutting the gel to obtain the whitening tooth paste.

The application method of the dental paste comprises the steps of cleaning an oral cavity before using, removing residues in the oral cavity, attaching the dental paste to the outer wall of a tooth, slowly diluting and dissolving peroxide stored in the dental paste by saliva in the oral cavity, enabling the peroxide to act on the surface of the tooth, degrading pigment on the surface of the tooth, and achieving a whitening effect. The tooth paste is generally used for 30-60 min, and after the tooth paste is used, the tooth paste needs to be rinsed to remove components such as residual peroxide in the oral cavity.

Preferably, the thickness of the tooth whitening paste is 0.1 to 1mm, more preferably 0.3 to 0.6mm.

In summary, the application has the following beneficial effects:

1. according to the application, carbomer, hydroxyethyl cellulose and chitosan fibers are adopted to prepare the adhesive, so that the strength of the adhesive can be effectively improved on the premise of ensuring the toughness and plasticity of the whitening tooth paste, and the fracture probability in the use process is reduced.

2. According to the application, the epoxy modified carbomer is adopted, so that the connection strength of chitosan cellulose and adhesive gel can be further improved, and the toughness and strength are improved.

3. According to the application, the dimethyl dimethoxy silane is adopted to modify the silicon dioxide, so that the dilution and dissolution speed of saliva to peroxide in the tooth paste can be effectively reduced, and the full play of the whitening effect is ensured.

Detailed Description

Carbomer preparation example

Preparation 1-1, a carbomer, was prepared as follows:

polymerization: 500ml of ethyl acetate solution is taken, 100g of acrylic acid and 1.5g of pentaerythritol triallyl ether are added, the mixture is stirred uniformly and heated to 50 ℃ under the nitrogen atmosphere, then 12g of 10wt% ethyl acetate solution of bis (2-ethylhexyl) peroxydicarbonate is dripped under the stirring condition, the reaction is carried out for 3 hours after the dripping is finished, and carbomer is precipitated from the mixed solution.

Separating: and (3) carrying out suction filtration, washing and drying on the mixed solution containing the carbomer precipitate to obtain powdery carbomer.

Preparation examples 1-2, an epoxy modified carbomer, were prepared as follows:

polymerization: taking 500ml of ethyl acetate solution, adding 70g of acrylic acid, 30g of glycidyl methacrylate and 1.5g of pentaerythritol triallyl ether, uniformly stirring, heating to 60 ℃ under a nitrogen atmosphere, then dropwise adding 12g of 10wt% ethyl acetate solution of bis (2-ethylhexyl) peroxydicarbonate under stirring, reacting for 3 hours after the dropwise adding is finished, and precipitating carbomer from the mixed solution.

Separating: and (3) carrying out suction filtration, washing and drying on the mixed solution containing the carbomer precipitate to obtain the powdery epoxy modified carbomer.

Preparation examples 1-3, an epoxy-modified carbomer, differ from preparation examples 1-2 in that the amount of acrylic acid used is 80g and the amount of glycidyl methacrylate used is 20g.

Preparation examples 1-4, an epoxy-modified carbomer, differ from preparation examples 1-2 in that the amount of acrylic acid used is 60g and the amount of glycidyl methacrylate used is 40g.

Preparation examples 1 to 5, an epoxy-modified carbomer, differ from preparation examples 1 to 2 in that the amount of acrylic acid used was 90g and the amount of glycidyl methacrylate used was 10g.

Preparation example of Dimethyldimethoxysilane modified silica

Preparation example 2-1, dimethyl dimethoxy silane modified silica, was prepared as follows:

dissolving 40g of dimethyl dimethoxy silane in 3.5L of methanol, heating to 40 ℃, dripping 300g of a blending liquid of short-chain alcohol and 100g of water, heating to 90 ℃ after dripping, reacting for 1h, and distilling under reduced pressure to recover methanol; then heating to 120 ℃ to continue polymerization for 1.5h, adding 1 kg of 400-mesh silicon dioxide, stirring and reacting for 0.5h, and cooling to room temperature to obtain the catalyst.

dissolving 15g of dimethyl dimethoxy silane in 3.5L of methanol, heating to 50 ℃, dripping 300g of a blending solution of short-chain alcohol and 100g of water, heating to 90 ℃ after dripping, reacting for 1h, and distilling under reduced pressure to recover methanol; then heating to 130 ℃ to continue polymerization for 1h, adding 1 kg of 400-mesh silicon dioxide, stirring and reacting for 0.5h, and cooling to room temperature to obtain the catalyst.

Preparation example 2-3 differs from preparation example 2-1 in that the same amount of methyltrimethoxysilane was used instead of dimethyldimethoxysilane.

Preparation 2-4 differs from preparation 2-1 in that an equivalent amount of trimethylmethoxysilane was used instead of dimethyldimethoxysilane.

Examples

Example 1, a tooth whitening gel patch, was prepared according to the proportions shown in table 1 and the following method:

preparation of an adhesive: adding carbomer, hydroxyethyl cellulose and chitosan fiber (average length of 20 μm) prepared in preparation example 1-1 into water, stirring, adding glacial acetic acid to pH value of 6, heating to 85deg.C, and reacting for 2 hr to obtain adhesive;

gel preparation: adding the adhesive, carbamide peroxide, glycerol, strontium fluoride, sodium hydroxide, disodium ethylenediamine tetraacetate and water into a reaction kettle, and stirring and mixing under vacuum to obtain gel;

and (3) forming: the gel is coated and cut to prepare the whitening tooth paste with the length of 10cm, the width of 3cm and the thickness of 5 mm.

Example 2, a tooth whitening gel patch, was prepared according to the proportions shown in table 1 and the following method:

gel preparation: adding an adhesive, carbamide peroxide, glycerol, strontium fluoride, sodium hydroxide, disodium ethylenediamine tetraacetate, the dimethyl dimethoxy silane modified silicon dioxide prepared in preparation example 2-1 and water into a reaction kettle, and stirring and mixing under vacuum to prepare gel;

Example 3, a tooth whitening gel patch, was prepared according to the proportions shown in table 1 and the following method:

preparation of an adhesive: adding carbomer, hydroxyethyl cellulose and chitosan fiber (average length of 15 μm) prepared in preparation examples 1-2 into water, stirring, adding glacial acetic acid to pH value of 5, heating to 90deg.C, and reacting for 2 hr to obtain adhesive;

gel preparation: adding an adhesive, carbamide peroxide, glycerol, strontium fluoride, sodium hydroxide, sodium hexametaphosphate, the dimethyl dimethoxy silane modified silicon dioxide prepared in preparation example 2-2 and water into a reaction kettle, and stirring and mixing under vacuum to prepare gel; and (3) forming: the gel is coated and cut to prepare the whitening tooth paste with the length of 10cm, the width of 3cm and the thickness of 5 mm.

Example 4, a tooth whitening strip, was distinguished from example 2 in that carbomers prepared in preparation examples 1-3 were used in the same amount instead of carbomers prepared in preparation examples 1-1, and the respective materials were formulated as shown in Table 1.

Table 1, examples 1-4 raw material ratios

Example 5, a tooth whitening strip, differs from example 2 in that the carbomer of preparation 1-1 was replaced with the carbomer of preparation 1-4 in equal amounts.

Example 6, a tooth whitening strip, differs from example 2 in that the carbomer of preparation 1-1 was replaced with the carbomer of preparation 1-5 in equal amounts.

Example 7, a tooth whitening strip, differs from example 2 in that the same amount of dimethyl dimethoxy silane modified silica prepared in preparation 2-3 was used instead of dimethyl dimethoxy silane modified silica prepared in preparation 2-1.

Example 8, a tooth whitening strip, was distinguished from example 2 in that the same amount of the dimethyldimethoxysilane modified silica prepared in preparation 2-4 was used instead of the dimethyldimethoxysilane modified silica prepared in preparation 2-1.

Comparative example 1, a tooth whitening strip, differs from example 1 in that equal amounts of carbomer were used instead of hydroxyethyl cellulose in the raw materials of the adhesive.

Comparative example 2, a tooth whitening strip, differs from example 1 in that equal amounts of hydroxyethylcellulose were used instead of carbomers in the raw materials of the adhesive.

Comparative example 3, a tooth whitening strip, differs from example 1 in that the raw material of the adhesive agent was an equivalent amount of hydroxyethyl cellulose instead of chitosan fibers.

Performance test

Test 1: adhesive strength performance test

The experimental conditions were as follows: the measurement was performed by using a Shanghai Heng Yi tensile pressure tester (HY-0580 (DB)). At room temperature, the adhesive sample was clamped between the upper and lower clamps for tensile testing under set tensile conditions, the effective initial length between the clamps was 40mm, and the speed at which the clamps were moved was 100m/min. The determination of the tensile strength at break is determined according to the tensile tension at the final break and the size of the cross section of the initial sample, namely the tensile tension at the final break divided by the area of the cross section of the breaking place of the initial sample, the elongation at break is the maximum tensile length of the sample between clamps minus the effective initial length of the sample between clamps divided by the effective initial length of the sample between clamps, and the sample is tested three times to obtain the average value. The test results are shown in Table 2.

Test 2: fracture condition of adhesive tape

The whitening stickers prepared in the examples and the comparative examples are respectively subjected to practical application test, the stickers are attached to the surfaces of teeth, and after 5 minutes, the stickers are peeled off, and whether fracture residue exists or not is recorded. Each set of samples was tested three times and the test results are shown in table 2.

Test 3: the release rate of the whitening component of the adhesive plaster

In an indoor environment at a temperature of 25±1 ℃, the tooth whitening strip was immersed in a beaker containing 1L of deionized water, and the frosted glass should be parallel to the beaker wall. The peroxide concentration change in the water was monitored from the beginning of sample immersion and the concentration was measured with a RQflex reflectometer for 10min, 30min, 1 h.

After 1h, the whitening gel paste is dissolved in ethyl acetate, the dissolved gel paste is added into a beaker filled with 1L of deionized water, the mixture is stirred uniformly, the total concentration of the whitening component (peroxide) in the gel paste is measured, and the concentration dissolution rate (the value of the peroxide concentration in water accounting for the total concentration) at each measurement time point is calculated. The test results show that examples 1-8 all have no fracture residue during peeling, comparative examples 1-2 have fracture residue, and comparative example 3 has no fracture residue but poor plasticity and poor adhesion to tooth surfaces.

Test 4: adhesive skin whitening effect test

The maxillary premolars removed by orthodontic treatment within 30 days were selected, and tooth surface color differences (L x values) were measured with a spectrocolorimeter. The teeth were then wrapped with a whitening strip and immersed in a beaker containing 100ml of deionized water, immersed for 2 hours at 37±1 ℃ and then removed, and the tooth surface color difference (L x value) was measured with a spectrocolorimeter. The whitening effect was evaluated based on the change in L values (Δl) before and after the immersion treatment. The test results are shown in Table 2.

TABLE 2 results of tooth whitening gel paste Performance test

Analysis of test results:

(1) By combining examples 1-8 and comparative examples 1-3 and combining Table 2, the application can remarkably improve the strength of teeth and reduce the problem of fracture residues in the use process or peeling process under the condition of ensuring the plasticity and bending performance of the adhesive by adopting carbomer, hydroxyethyl cellulose and chitosan fibers as the adhesive of the adhesive.

(2) As can be seen from the combination of the embodiment 1 and the embodiments 2-4 and the combination of the table 2, the application can effectively reduce the dilution and dissolution rate of the active substances in the adhesive plaster by doping the dimethyl dimethoxy silane modified silicon dioxide, ensure the matching of the transmission rate of the active substances to the tooth surface and the oxidative degradation rate, and ensure the full play of the whitening effect.

The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims

1. The tooth whitening adhesive tape is characterized by comprising the following raw materials in percentage by mass:

peroxide: 1 to 5 percent;

and (2) an adhesive: 10-20%;

humectant: 40-50%;

antiallergic agent: 1 to 2 percent;

catalyst: 0.01 to 0.5 percent;

stabilizing agent: 0.1 to 1 percent;

water: the balance;

2. The tooth whitening strip as set forth in claim 1, wherein the length of the chitosan fiber is 1 to 100 μm.

3. The tooth whitening strip of claim 1, wherein the carbomer is an epoxy modified carbomer.

4. A tooth whitening strip according to claim 3, wherein the raw materials of the carbomer comprise the following components in parts by weight:

acrylic acid polymerized monomer: 100-130 parts;

crosslinking agent: 1-2 parts;

and (3) an initiator: 0.5 to 1.5 parts;

5. The tooth whitening strip of claim 4, wherein the epoxy modified carbomer is prepared by the following method:

6. The tooth whitening strip according to claim 1, wherein the raw materials of the tooth whitening strip further comprise 2 to 5 mass% of dimethyl dimethoxy silane modified silica; the dimethyl dimethoxy silane modified silicon dioxide comprises the following components in percentage by mass: the silica of (1-5) and dimethyl dimethoxy silane are blended and modified in short chain alcohol.

7. The tooth whitening strip of claim 6 wherein said dimethyldimethoxysilane modified silica is prepared by the steps of:

dissolving dimethyl dimethoxy silane in short-chain alcohol, heating to 40-50 ℃, dripping a blending liquid of the short-chain alcohol and water, heating to 85-95 ℃ after dripping, reacting for 1-2 h, and distilling under reduced pressure to recover the short-chain alcohol; then heating to 120-130 ℃ for continuous polymerization for 1-2 h, adding silicon dioxide, stirring for 0.5-1 h, and cooling to room temperature to obtain the catalyst.

8. The tooth whitening strip as in claim 1, wherein the peroxide is at least one selected from the group consisting of carbamide peroxide and hydrogen peroxide.

9. The tooth whitening strip as in claim 1, wherein the stabilizing agent is selected from at least one of sodium citrate dihydrate, tartaric acid, disodium edetate and sodium hexametaphosphate.

10. The method for preparing a tooth whitening strip according to any one of claims 1 to 9, comprising the steps of: