KR20060081532A - Liquid type tooth whitener with increased adhesive property - Google Patents

Abstract

The present invention relates to a liquid tooth whitening agent, and more particularly, by using an intermolecular bond between a polymer containing a carboxyl group (-COOH) and a polymer having a carbonyl group (-C = O) or an ether group (-O-). The present invention relates to a tooth whitening liquid having increased adhesiveness, and is selectively attached only to hard tissues without sticking to soft tissues in the oral cavity such as gums and lips, and characterized in that the dissolution rate of peroxide can be controlled.

Liquid, tooth whitening, tacky, peroxide, dissolution rate.

Description

Liquid type tooth whitening agent with enhanced adhesion {LIQUID TYPE TOOTH WHITENER WITH INCREASED ADHESIVE PROPERTY}

The present invention relates to a liquid tooth whitening agent, and more particularly, by using an intermolecular bond between a polymer containing a carboxyl group (-COOH) and a polymer having a carbonyl group (-C = O) or an ether group (-O-). The present invention relates to a tooth whitening liquid having increased adhesiveness, and is selectively attached only to hard tissues without sticking to soft tissues in the oral cavity such as gums and lips, and characterized in that the dissolution rate of peroxide can be controlled.

The tooth is composed of an inner dentin and an outer enamel layer. The reason why the color of teeth changes yellow is because, intrinsically, a substance having a chromophore such as a double bond due to food or the like is deposited on the enamel layer outside the tooth. In addition, externally, tartar and soft precipitates are attached to the tooth surface, resulting in discoloration of the teeth. Exogenous pigmentation among these causes can be easily removed due to brushing, but endogenous coloration cannot be removed with toothpaste or brushing. In other words, tooth whitening using toothpaste has a limit, and the tooth whitening using hydrogen peroxide solution has been developed accordingly.

In 1960, an American dentist developed a tooth whitening agent by accidentally discovering that hydrogen peroxide water whitened teeth during the treatment of a patient's gum disease. In the 1980s, a home tooth whitening device was developed. This product uses hydrogen peroxide or carbamide peroxide gel in trays, which requires the use of high concentrations of peroxide, and has many problems in oral safety due to physical irritation of the tray touching the gums.

To overcome this drawback of tray formulations, strip formulations containing low concentrations of peroxides or liquid formulations that directly apply liquids to teeth have been developed. Dual-liquid products are easy to apply to teeth and are convenient to use, and have the advantage that they can be applied to the user's desired area, but they stick easily to soft tissues in the oral cavity such as lips as well as stimulation, and are easily diluted in saliva, so that they are diluted with hydrogen peroxide. There is a disadvantage in that absorption into the inside becomes difficult to exhibit a whitening effect.

To improve this problem, several companies have developed liquid tooth whitening agents. First, a liquid tooth whitening agent using polyethylene oxide disclosed in US Pat. No. 6,770,266 of Colgate, has the characteristics of being convenient to use and less foreign matter when used. However, this formulation has a problem of low adhesion to teeth using polyethylene oxide, which is a water-soluble polymer, easily diluted by saliva, and insufficient peroxide absorption in teeth, thus making it difficult to achieve a desired whitening effect.

Liquid tooth whitening agent using organosiloxane disclosed in US Patent No. 6,569,408 of P & G Corporation can be used overnight because of its ease of use and adhesion to teeth. The disadvantage is that peroxides are not absorbed by the teeth.

Liquid tooth whitening agent using polyacrylic acid disclosed in Den-mat U.S. Patent No. 6,555,020 is also easy to dilute the tooth whitening gel by saliva, so that it does not have good adhesion to teeth. Since peroxide stabilizers such as CDTA are added to delay the whitening reaction on the tooth surface, there is a problem that it is difficult to achieve a desired tooth whitening effect.

US Patent Application Publication No. 2003/0152528 by Singh et al. Discloses a tooth whitening agent using a hydrophilic polymer and an oligomer having a molecular weight of less than 1000 Daltons that is hydrogen bonded to the hydrophilic polymer. This formulation is suitable for the formulation of solid phase by casting or extrusion. However, in the case of liquid, the kinetic energy between molecules is strong and the degree of freedom is increased, so that only the monomer having small molecular weight does not have strong hydrogen bond with the hydrophilic polymer. This makes selective attachment between the formulation and teeth impossible.

Meanwhile, in Korean Patent Registration No. 10-0440241, an erodible polymer composite formed by hydrogen bonding of a polymer containing a carboxyl group (-COOH) and a polymer containing a carbonyl group (-C = O) or an ether group (-O-) Tooth whitening patch comprising a tooth adhesion layer comprising a complex) and a tooth whitening component, and an erosion rate control layer comprising a mixture of a hydrophilic polymer and a film-forming polymer. This patch is characterized by the fact that it does not need to be removed and removed as it is hydrated by moisture in the oral cavity when the tooth is attached and releases the tooth whitening component and disappears after a certain time. That is, the patent relates to a patch type tooth whitening agent, in which the matrix of the tooth adhesion layer collapses due to the difference in solubility due to polymer bonding in the tooth whitening layer, thereby controlling the erosion rate.

In the present invention to compensate for the shortcomings of the prior art, by using the intermolecular bonds of the hydrophilic polymer to increase the adhesion and to selectively attach to the teeth, the rate of release of the tooth whitening component such as hydrogen peroxide according to the ratio of hydrogen bonds It is an object of the present invention to provide an adjustable liquid whitening agent.

In order to achieve the above object, in the present invention, polyvinylpi as a polymer having at least one selected from polyacrylic acid, polymethacrylic acid, carbomer (carbopol) and carbophil as a polymer containing a carboxyl group, an ether group or a carbonyl group Provided are a liquid tooth whitening agent comprising at least one selected from a group of rolidones, polyethylene oxides, polypropylene oxides and flonics, and a tooth whitening component.

The present invention is to increase the adhesion of the liquid tooth whitening agent by using the intermolecular bond between the polymer containing a carboxyl group (-COOH) and the polymer having a carbonyl group (-C = O) or ether group (-O-), selective to teeth On the other hand it is characterized in that to control the release rate of the peroxide. The difference from the patch type tooth whitening agent which controls the erosion rate by using hydrogen bonds between the aforementioned polymers is that the tooth whitening agent of the present invention is a liquid type, which increases the cohesion between polymers inside the gel, and in particular, enhances cohesion and weakens adhesion. On the other hand, it enhances the adhesion. As such, by adhering to the adhesive force is attached only to the teeth has the advantage of minimizing contamination to other tissues in the oral cavity.

Liquid tooth whitening agents according to the invention also comprise the form of gels, liquids or dispersions.

Hereinafter, the present invention will be described in detail.

In the tooth whitening agent of the present invention, a polymer containing a carboxyl group (-COOH) and a polymer having a carbonyl group (-C = O) or an ether group (-O-) are used, or a polymer composite comprising two polymers is used. These polymers are bound by intermolecular bonds (hydrogen bonds, van der Waals forces, or ionic bonds). The intermolecular hydrogen bond is a strong attraction force acting between a hydrogen atom bonded to an atom having a high electronegativity and an atom having a high electronegativity present at another molecule. When a hydrogen bond between polymers is formed, a crosslink is formed between polymer chains. Cross-linked molecular chains do not move freely. Physical crosslinking such as hydrogen bonding is reversible depending on the solvent, temperature, and hydrogen ion concentration, and the dissolution rate can be controlled according to the proportion of the polymer.

On the other hand, hydroxyapatite on the surface of the tooth has a negative charge, and consists of a porous structure. In the tooth whitening agent of the present invention, the carboxyl group is complementarily bonded to the carbonyl group or the ether group to reduce the negative charge of the carboxyl group, thereby reducing the repulsive force of the negative charge on the surface of the tooth, thereby making it possible to use the carboxyl group, the carbonyl group or the ether group alone. It can be selectively attached to the tooth surface compared to the whitening agent. After tooth attachment, it hydrates with saliva in the oral cavity, causing the release of peroxides contained therein, resulting in tooth whitening.

The tooth whitening agent according to the present invention may adjust the viscosity and solubility according to pH, polymer ratio, and can control the dissolution pattern of the tooth whitening material (peroxide, etc.) according to hydration. That is, as the proportion of the polymer increases, the viscosity increases, which delays the penetration of water by saliva into the matrix, thereby slowing the release of the tooth whitening material. In addition, since the viscosity of the polymer containing the carboxyl group changes depending on pH, it is possible to control the release of the tooth whitening material using the same.

Polyacrylic acid, polymethacrylic acid, carbomer (carbopol) and carbophil may be used as the polymer containing the carboxyl group in the liquid tooth whitening agent of the present invention, and the polymer having an ether group or a carbonyl group may be polyvinylpyrrolidone, Polyethylene oxide, polypropylene oxide, flonics and the like can be used. Among these polymers, polyvinylpyrrolidone and carbomer (carbopol) are most preferred because they greatly contribute to improving the safety of the peroxide, controlling the viscosity, and selective attachment to the teeth.

In the tooth whitening agent of the present invention, the carboxyl group-containing polymer may be contained in 0.1 to 5% by weight of the total composition, and the polymer having a carbonyl group or an ether group may be contained in 1 to 40% by weight of the total composition. If the amount of the polymer containing a carboxyl group, carbonyl group or ether group is lower than this, the viscosity is low and flows out of the tooth, and the two polymers do not have sufficient crosslinking and thus selective tooth attachment is impossible. On the other hand, when the content of these polymers is higher than the content range, the viscosity is excessively increased, so that the application of the tooth is poor and the feeling of use worsens.

Moreover, it is preferable that pHs of the tooth whitening agent composition of this invention are 4-9, and the thing of the pH 5-7 range is the most preferable. The viscosity is preferably 50,000 to 700,000 cps, most preferably in the range of 100,000 to 450,000 cps. If the pH is lower than 4, it can cause dental caries due to acid. If the pH is higher than 9, the peroxide, which is a tooth whitening substance, is decomposed. In addition, when the viscosity is lower than 50,000 cps flows from the tooth can not be selectively attached to the teeth, higher than 700,000 cps is not good applicability to the teeth is less feel.

In the tooth whitening agent of the present invention, the tooth whitening component may be applied to the teeth in the oral cavity to produce a whitening effect. Since the oxidizing agent is effective as a tooth whitening ingredient, it is possible to perform all these functions while being used in the oral product. For example, peroxides, perborates, percarbonates, peroxyacids, persulfates, metal chlorites, and the like can be used. Peroxides are, for example, hydrogen peroxide, carbamide peroxide, calcium peroxide, sodium percarbonate, sodium perbonate and tetrasodium pyrophosphate peroxidate It is preferable that one or more of them, and the content may comprise 1.5 to 30% by weight.

In addition, the tooth whitening agent of the present invention may further contain a condensation phosphate and / or viscosity regulators commonly used.

Condensed polyphosphates are used as an adjuvant to enhance the whitening effect and are effective in inhibiting tartar formation and removing tartar. It is also used as a chelating agent for metals and is used to remove metal ions such as iron and magnesium, which cause tooth coloring. Condensed phosphates include sodium methaphosphate, sodium hexamethaphosphate, sodium pyrophosphate, sodium pyrophosphate, sodium tripolyphosphate, and potassium metaphosphate One or more of (potassium methaphosphate) can be used.

On the other hand, in the case of carbomer acidic conditions, the intermolecular arrangement is present in a densely arranged but the viscosity of the polymer is released as the pH is increased to increase the viscosity can be used to adjust the viscosity regulator. Viscosity modifiers include one of the basic substances that can raise the pH, such as triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and phosphate buffer. The above can be used.

In addition, in the tooth whitening agent of the present invention, fluorine ions may be added to prevent tooth decay, or pigments, flavors, and sweeteners may be added.

Materials capable of supplying fluorine ions include sodium fluoride, tin fluoride, monofluorophosphate (MFP), and ammonium fluoride.

Pigments are used to make teeth look bright and include titanium dioxide, talc, hydroxyapatite, and zinc oxide, and one or more of them can be used.

Flavors include fruit flavors, mint flavors, eucalyptus flavors, sage, cinnamon flavors, and one or more of them can be used.

Sweeteners include mannitol, sorbitol, xylitol, aspartame, sugar, honey, sodium saccharin, and one or more of them may be used.

Method for producing a tooth whitening agent according to the present invention is as follows.

Polymers containing carboxyl groups, polyacrylic acid, polymethacrylic acid, carbomer (carbopol) and one of carbophil, polymers having ether or carbonyl groups, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, and phonics One kind of, peroxide, condensation phosphate and viscosity regulator, sweetener, and flavoring ingredients of tooth whitening are dissolved in a mixed solvent of water and ethanol to prepare a homogeneous solution. The pH of this solution is adjusted to a range of 4-9 and bubbles are removed at 40 ° C. and then filled into a container.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are only illustrative of the present invention, the scope of the present invention is not limited by these Examples.

Examples 1-9

According to the composition of Table 1, polyvinylpyrrolidone, carbomer or polyacrylic acid, hydrogen peroxide, triethanolamine, sodium pyrophosphate acid, sorbitol and fruit flavors were dissolved in a mixed solvent of water and ethanol to prepare a homogeneous solution. The liquid tooth whitening agent of the present invention was prepared by adjusting the pH of the liquid solution between 4 and 9 and removing bubbles at 40 ° C.

Examples 1 to 4 adjust the content ratio of polyvinylpyrrolidone and carbomer in the composition, and Examples 5 to 9 adjust the content ratio of polyvinylpyrrolidone and polyacrylic acid.

Composition Example (weight g) One 2 3 4 5 6 7 8 9 Polyvinylpyrrolidone 15 14.2 13.8 13.5 15 14.2 13.8 13.5 13 Carbomer 0.5 1.3 1.7 2 - - - - - Polyacrylic acid - - - - 0.5 1.3 1.7 2 2.5 Hydrogen peroxide (35%) 8 8 8 8 8 8 8 8 8 Sodium Pyrophosphate 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Triethanolamine 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Purified water 36 36 36 36 36 36 36 36 36 ethanol 36 36 36 36 36 36 36 36 36 Fruit flavor 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sorbitol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Comparative Example 1

In Example 1 above, only the hydrogen whitening component, hydrogen peroxide, was added, and the remaining components were prepared in the same manner.

Experimental Example 1 : Measurement of tooth attachment time of tooth whitening agent and measurement of elution of hydrogen peroxide

The Franz-cell modified liquid tooth whitening agent prepared in Examples 1 to 9 was attached to the same hydroxyapatite specimen as the component of the tooth, and tooth attachment time and hydrogen peroxide dissolution test were performed.

The control group 1 was a commercially available product, and was made by Colgate's Simply White containing carbomer and hydrogen peroxide.

Control 2 was a commercially available product, which was P & G's night effect containing organosilicon and hydrogen peroxide.                     

The measurement results of the tooth attachment time are shown in Table 2 below.

Time 5 minutes 10 minutes 15 minutes 30 minutes 45 minutes 60 minutes Example 1 Shape Partly lost Partly lost Complete loss - - Example 2 Shape Shape Partly lost Complete loss - - Example 3 Shape Shape Partly lost Complete loss - - Example 4 Shape Shape Partly lost Partly lost Complete loss - Example 5 Shape Partly lost Complete loss - - - Example 6 Shape Partly lost Complete loss - - - Example 7 Shape Partly lost Partly lost Complete loss - - Example 8 Shape Shape Partly lost Partly lost Complete loss - Example 9 Shape Shape Partly lost Partly lost Complete loss - Control group 1 Shape Complete loss - - - - Control 2 Shape Shape Shape Partly lost Partly lost Partly lost

Dissolution test results of hydrogen peroxide are shown in Table 3. Each value is the degree of dissolution over time.

time 5 minutes 10 minutes 15 minutes 30 minutes 45 minutes 60 minutes Example 1 15 45 77 98 98 98 Example 2 13 27 55 95 95 94 Example 3 11 28 52 92 92 90 Example 4 8 22 45 75 96 95 Example 5 35 88 98 98 96 96 Example 6 31 85 99 97 98 98 Example 7 27 55 83 98 98 96 Example 8 21 49 79 89 95 95 Example 9 25 53 79 92 95 94 Control group 1 88 99 98 98 97 99 Control 2 7 14 22 39 49 65

As shown in Tables 2 and 3, it can be seen that by varying the content ratio of carbomer and polyvinylpyrrolidone in the constituent polymer of the present invention, the adhesion time and the elution pattern of the peroxide can be controlled. In particular, it can be seen that as the content of carbomer increases, the adhesion time increases and the elution time of hydrogen peroxide increases, so that the dissolution pattern is changed into a continuous dosage form.

In addition, it can be seen that even when the content ratio of polyacrylic acid and polyvinylpyrrolidone is changed, the elution pattern of the attachment time and the peroxide can be controlled. Here, as the content of polyacrylic acid increases, the adhesion time increases and the elution time of hydrogen peroxide increases.

This change in adhesion time and peroxide elution pattern due to different polymer composition is due to the hydrogen bond between carbomer and polyvinylpyrrolidone polymer, the hydrogen bond between polyacrylic acid and polyvinylpyrrolidone, and the ratio of carbomer and polyacrylic acid. Presumably due to the difference in viscosity of the formulations.

Experimental Example 2 Whitening Effect Experiment

The whitening effect of the tooth whitening agent prepared in the above Examples and Comparative Examples was evaluated by in vitro evaluation using colored hydroxyapatite tablet specimens. That is, after applying the formulations prepared in Examples and Comparative Examples, respectively, on the colored specimens, they were left at room temperature for 1 minute, dipping in water for 1 minute, and then removed and wiped lightly with a tissue three times, temperature 37 ° C., humidity 95 After standing in a thermo-hygrostat set to%, after 6 hours the formulation was removed and dried at room temperature and the L value was measured. ΔL, which is the difference in L values before and after application, was calculated. The results are summarized in Table 4 below.

ΔL (1 time use) Example 3 37.50 ± 4.50 Example 7 37.96 ± 1.98 Comparative Example 1 1.08 ± 0.55

As shown in Table 4 above, it can be seen that the tooth whitening agent of the present invention (Examples 3 and 7) including the tooth whitening component is superior to the preparation without the tooth whitening component (Comparative Example 1).

Experimental Example 3 Experiments and Results Showing the Increase in Adhesiveness

Remaining tooth whitening agent remaining on the oral mucosa when the tooth whitening agents of Example 1, Control 1 and Control 2 were respectively attached to the oral mucosa of the guinea pig, and the tooth whitening side thereof was attached to the hydroxyapatite specimen and detached after 30 minutes. Rate was evaluated. Table 5 shows the residual rates.

Survival rate Example 1 11.45 ± 7.52 Control group 1 57.96 ± 11.2 Control 2 41.08 ± 9.65

As shown in Table 5, the tooth whitening agent according to the present invention, unlike the conventional liquid formulations, it can be seen that the adhesive force is increased to increase the cohesiveness on the liquid matrix to selectively attach only to the teeth.

As described above, the liquid tooth whitening agent according to the present invention is not attached to soft tissues in the oral cavity such as gums and lips, and is selectively attached only to the teeth, and the dissolution rate of the peroxide is convenient and convenient to use.

Claims (6)

As a polymer containing a carboxyl group, at least one selected from polyacrylic acid, polymethacrylic acid, carbomer (carbopol) and carbophil, and a polymer having an ether group or a carbonyl group, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide and A liquid tooth whitening agent comprising at least one selected from flonics and a tooth whitening component. The liquid tooth whitening agent according to claim 1, wherein the polymer containing a carboxyl group is carbomer (carbopol), and the polymer having an ether group or a carbonyl group is polyvinylpyrrolidone. The liquid tooth whitening agent according to claim 1, wherein the polymer containing a carboxyl group is contained in 0.1 to 5% by weight in the total composition, and the polymer having a carbonyl group or an ether group is contained in 1 to 40% by weight in the total composition. The liquid tooth whitening agent according to claim 1, wherein the pH is 4-9. The liquid tooth whitening agent according to claim 1, wherein the viscosity is 50,000 to 700,000 cps. The tooth whitening component of claim 1, wherein the tooth whitening component is an oxidizing agent, and the peroxide, perborate, percarbonate, peroxyacids, persulfates, and metal chlorites Liquid tooth whitening agent, characterized in that at least one of.