JP2003221321A - At-home bleaching composition and process for using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an at-home bleaching composition comprising a novel composition exerting a photocatalytic decomposition effect and which shows an excellent safety, operability, handiness, etc. <P>SOLUTION: After applying a gel substrate (agent A) onto teeth, artificial teeth, or the like, an aqueous solution (agent B) of trivalent iron ion (Fe<SP>3+</SP>) is injected to promote dental plaque decomposition and bleaching of dental coloration. Here, the agent A comprises titanium oxide responding to UV and visible light, zirconium oxide, CMC-Na, glycerol and propylene glycol in water or a mixed system of water-alcohol. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for home bleaching for decomposing a tooth, a dental material mounted in the oral cavity, or a surface of the dental material outside the oral cavity or a deposit of a contaminant on a fiber. Regarding Specifically, titanium oxide and zirconium oxide, or a composition obtained by further adding a ferric salt to these is used to decompose and remove dental plaque and tar adhering to a tooth or a dental material by an ultraviolet light and / or a visible light system, Alternatively, it relates to home bleaching compositions that reduce discoloration or remove contaminating deposits on fibers and methods of use thereof.

[0002]

2. Description of the Related Art Aging, eating habits, and smoking cause discoloration and coloring of teeth, which intensifies the desire for white and beautiful teeth. In addition to medical treatment by a dentist, it is strong in "home-use tooth whitening method". There is interest.

In response to the demand for "white teeth", treatment by bleaching action of hydrogen peroxide is effective, and although products based on urea peroxide are sold in the United States,
This product is not approved in Japan due to problems with efficacy and side effects. However, in recent years, dentifrices using titanium oxide exhibiting a photocatalytic action have appeared as home-use whitening agents.

Toothpaste in which titanium oxide is mixed with toothpaste components such as abrasives, foaming agents and binders (Japanese Patent Publication No. 3-20363).
(Japanese Patent Laid-Open No. 9-151123) in which titanium oxide is added to a coating solution consisting of a combination of ethanol and resin or shellac to maintain gloss, but the titanium oxide used here is known. Are not visible-responsive semiconductors, but exhibit a photocatalytic action by receiving ultraviolet light.

On the other hand, a visible response type titanium oxide has been developed, and titanium oxide having a dramatically enhanced photocatalytic action by ultraviolet / visible light has come to be commercially available.
A bleaching method for teeth and the like using this visible-responsive titanium oxide has been developed.

That is, a bleaching agent for home bleaching in which titanium oxide ultrafine particles coated with calcium phosphate are mixed in a titanium oxide sol (JP-A 2000-344).
640), and a dental / oral composition (Tokukaihei 2000-220309) in which titanium oxide, a silicon compound, a silicone resin, silica, and the like are mixed with a liquid medium, are applied and adhered to a tooth, and light is applied to the portion. Products have been developed that try to remove plaque, which is mainly due to the photocatalytic decomposition effect, and bleach the discolored area by irradiating with. Thus, there is a need for a home bleaching agent that has no safety problems, is easy to handle, and is highly effective in a short time.

By the way, the present inventor first found that TiO ₂ / Fe
PCB by ³⁺ / H ₂ O ₂ / UV system, drin pesticide, DD
A low-temperature decomposition method for a persistent halogenated organic compound such as T and a haloform compound (Japanese Patent Laid-Open No. 265460/1995), ZrO ₂ / Fe ³⁺ / H ₂ O ₂ / UV system containing methanol and t-butanol. PCB by adding
A method for highly decomposing 2,4,5-T and PCT (JP-A-9-
255591) and ZrO ₂ / Fe ³⁺ / H ₂ O ₂
/ UV system for decomposing hardly biodegradable organic matter in wastewater and removing phosphorus (Japanese Patent Laid-Open No. 11-19664).

As disclosed in the above-mentioned patent publication,
The present inventor has proposed a method for decomposing an organic compound that is hard to decompose physically, chemically, and biologically using the photocatalytic action of an oxide semiconductor such as titanium oxide or zirconium oxide.
In these inventions, although ZrO ₂ was a semiconductor, it was thought that it had a large band gap and did not have a practical level of photocatalytic activity. However, depending on the system, ZrO ₂ has a higher photocatalytic activity than TiO _2. did. Also,
Regarding TiO ₂ , it is said that the anatase type has a higher photocatalytic ability than the rutile type, but it was pointed out that the rutile type has a higher photocatalytic ability for the decomposition of PCB.

[0009]

Although a bleaching agent for teeth and the like using visible-responsive titanium oxide is known in the above-mentioned prior art, it has been reported that a combination of titanium oxide and zirconium oxide improves the optical resolution. There is no.

Therefore, in view of further improving the function of the bleaching agent for teeth etc. using the visible responsive titanium oxide in the above-mentioned prior art, and in view of the results of the present inventor, TiO ₂ and ZrO ₂
Based on the idea that both photocatalytic activities could be effectively utilized synergistically for bleaching teeth, etc.

As described above, the object of the present invention is to provide a tooth surface,
Home bleaching composition with excellent safety and handling for the purpose of decomposing and removing plaque and tars adhering to the surface of dentures and other oral and dental materials, and removing contaminants such as coloring components on fibers To provide things and their uses.

[0012]

The above-mentioned objects of the present invention can be achieved by the following technical means (1) to (4).

(1) A composition for home bleaching containing titanium oxide having photocatalytic activity and zirconium oxide in the form of ultrafine particles.

(2) A composition for home bleaching containing titanium oxide having photocatalytic activity, ultrafine zirconium oxide and ferric salt.

Further, in each of the compositions (1) and (2), at least a paste / binder among a viscosity modifier and a paste / binder is added to give a composition suitable for home use. be able to.

(3) Under irradiation of ultraviolet light and / or visible light, teeth and dental materials mounted in the oral cavity, and applied to the surface of the dental material outside the oral cavity or the spots where contaminants are attached on the fibers are exposed to ultraviolet and / or visible light. A method of using the composition for home bleaching according to the above (1), wherein the composition is irradiated with light.

(4) Under irradiation of ultraviolet light and / or visible light, the tooth and the dental material mounted in the oral cavity and the ultraviolet and / or visible are applied outside the oral cavity to the surface of the dental material or the spots where the contaminants are attached on the fibers. A method of using the composition for home bleaching according to the above (3), which comprises irradiating with light.

The composition for home bleaching of the present invention comprises
Commercially available commercially available photocatalytically active titanium oxide (ultraviolet / visible light responsive titanium oxide or ultraviolet light responsive titanium oxide) and ultrafine particles (2-150 nmφ) that have activity under irradiation of ultraviolet light and / or visible light. It is used as a gel composition containing zirconium oxide as described above and dispersed in water or a water-alcohol (ethanol, glycerin, propylene glycol, etc.) mixture system, which is a viscosity modifier, CMC-Na, etc. It is preferable.

In order to remove stains on the fiber surface of clothes and the like, ultraviolet light / visible light responsive titanium oxide and ultrafine particulate zirconium oxide can be treated with the above-mentioned paste / binder without adding a ferric salt. A gel composition dispersed in water or a water-alcohol mixed system, which is a viscosity modifier and a dispersion stabilizer, such as CMC-Na is used as it is as the home bleaching composition of the present invention.

Further, even if an attempt is made to disperse the ultraviolet light / visible light responsive titanium oxide and the ultrafine particulate zirconium oxide in water or a water-ethanol mixed solution, it precipitates immediately, so that the TiO ₂ and ZrO ₂ water or water is dispersed. -CM in ethanol mixture
Stabilize the TiO 2 by adding a paste or binder such as C-Na.
A gel composition in which ₂ and ZrO ₂ are dispersed can be obtained.

Further, the obtained gel-like composition is treated with teeth,
Glycerin for viscosity adjustment and propylene glycol having both a viscosity adjusting function and an antiseptic function are mixed in order to facilitate application to a contaminated object such as a fibrous material and to maintain the form of a coating film formed by the application.

Titanium oxide having photocatalytic activity according to the present invention,
In the composition for home bleaching containing ultrafine particulate zirconium oxide, a sizing agent / binder, and a viscosity modifier (hereinafter sometimes referred to as agent A), the ultraviolet / visible light responsive titanium oxide and ultrafine particulate are used. Zirconium oxide and CMC-Na
A sizing agent / binder such as is a component suitable for home use, and a bleaching composition for home use containing this has an effect of removing contaminants such as teeth or fiber surfaces, but the above effect is exhibited. It takes time.

On the other hand, when a separately prepared aqueous solution of trivalent iron ions (Fe ³⁺ ) (hereinafter sometimes referred to as B agent) is added to the A agent, TiO ₂ is added as shown in FIG. , Z
Together with rO ₂ and Fe ³⁺ , the production of .OH is enhanced, so that it has the effect of promoting the discoloration of discoloration due to plaque decomposition or contaminants on the tooth surface.

Commercially available ultraviolet / visible light responsive titanium oxide (manufactured by Ecodevice Co., Ltd.) is anatase titanium oxide and has a particle size of 60 mesh or less. Center wavelength 4 including the wavelength of light from white fluorescent lamps as well as ultraviolet light
It has catalytic activity with light of 70 to 520 nm.

Further, commercially available ultraviolet light responsive titanium oxide (manufactured by Toray Industries, Inc.) is also anatase titanium oxide, and the particle size announced by the manufacturer is 15 nm. It is said that this ultraviolet light-responsive titanium oxide has photocatalytic activity only for ultraviolet light, but it was found that when it is used together with the ultrafine particulate zirconium oxide of the present invention, it exhibits photocatalytic activity even in visible light.

However, since the dispersion stability of these titanium oxides in a liquid medium is poor, it is necessary to devise them.

The compounding amount of titanium oxide in the agent A is 0.05.
Is 2.00% by weight (ratio to the total weight of the composition including water), and in order to fully exert the effect of decomposing and removing contaminants when the agents A and B are used in combination, It is preferably 0.10 to 0.20% by weight. If the compounding amount of titanium oxide is less than 0.05% by weight, the photocatalytic activity (decomposition removal effect) is extremely small, and if the compounding amount exceeds 2.00% by weight, the decomposition removal effect does not increase.

As the commercially available ultrafine particulate zirconium oxide, a product having a particle size announced by the manufacturer of 3 nm was used. However, if the particle size can exhibit photocatalytic activity by receiving ultraviolet rays, other zirconium oxide is used. It is possible to use those having a particle size of 2 to 150 nm.

The amount of zirconium oxide used is 0.3 times the amount of titanium oxide or more, and preferably 1.5 to 2 times the amount of titanium oxide in order to further improve the decomposition and removal performance of contaminants. use. If the amount of ultrafine particulate zirconium oxide used is less than 0.3 times, the effect of mixing with titanium oxide is not exerted and the decomposition and removal performance of contaminants cannot be exhibited. Also,
Even if the amount used exceeds twice that of titanium oxide, the effect is not enhanced.

Zirconium oxide in the form of ultrafine particles is added and used not only for exhibiting photocatalytic activity by receiving ultraviolet rays, but also for maintaining dispersion stability of titanium oxide in a liquid medium. In addition, since zirconium oxide in the form of ultrafine particles has a property of randomly reflecting incident light (soft hocus effect), it is possible to make agent A white by mixing it with yellow visible-responsive titanium oxide. It also has the effect of making it easier to see how dirt and the like that have been peeled off and attached to the surface of the coating float on the surface of the coating.

The water-containing liquid of titanium oxide and zirconium oxide can be made into a gel by adding a sizing agent / binder such as CMC-Na, methylcellulose, sodium alginate, etc. Has the function of peeling and removing plaque, coloring components, etc. from the teeth.

The amount of the paste / binder added is 1 to 5% by weight in the agent A. In order to keep the gel-like material on the tooth surface stably, it is preferably added at 1.0 to 4.5% by weight. The above blending amount of paste and binder such as CMC-Na is 1
When it is less than 5% by weight, the viscosity is too low and the composition of the present invention is hard to stay on the surface of an object to be contaminated such as teeth, and when it exceeds 5% by weight, the viscosity is too high and it is difficult to apply it to the surface of teeth.

In order to adjust the viscosity of the composition of the present invention so that it can be easily applied to the surface of teeth and the like and can maintain a thick and round film form on the surfaces of teeth formed by application, It is desirable to add water, water-ethanol, glycerin and propylene glycol as regulators.

The amount of glycerin and propylene glycol added is 3 to 10% by weight in the agent A, more preferably 3 to 5%.
Wt% is added. The addition amount of glycerin and propylene glycol is determined by adjusting the concentration so that the gel-like material does not sag when the gel-like material is applied to the tooth surface. Further, water or water-ethanol is added so that titanium oxide accounts for 0.05 to 2.00% by weight based on the total weight. When the composition of the present invention is applied to a fibrous material, the addition of glycerin or propylene glycol may be omitted.

The aqueous solution containing the trivalent iron ion of the agent B is a ferric chloride aqueous solution (Fe ³⁺ of 234 p as a food additive).
pm) or a saturated aqueous solution of ferric citrate. Since ferric citrate is poorly soluble in water, a saturated aqueous solution was obtained,
Fe ³⁺ concentration in a saturated aqueous solution of ferric citrate is 590 p
It was around pm.

The present invention is a composition for home bleaching comprising agent A or agent A and agent B, which does not require a special visible light irradiator and can be used under ordinary room light or sunlight. It can be used in general households because it has a characteristic that it can perform photocatalytic decomposition.

Further, with the composition for home bleaching of the present invention, the plaque adhered to the surface of the tooth, the denture or other oral and dental materials, the decomposition and removal of tars, and the contamination of the coloring component on the fiber, etc. Can remove things. In particular, the above composition has an excellent action and effect of bleaching discoloration or coloring of teeth caused by aging, eating habits and smoking to restore white and beautiful teeth. Further, the agent A can be used in addition to toothpaste. To remove contaminants such as coloring components on the fiber, use water or water-alcohol solution containing titanium oxide having photocatalytic activity, zirconium oxide in the form of ultrafine particles, and a paste / binder such as CMC-Na. May be.

[0038]

[Function] Large reaction force of hydroxy radical (OH)
Figure 1 shows the mechanism that causes kina radicals.
explain. (1) Ultraviolet / visible light responsive titanium oxide was exposed to ultraviolet rays
In addition to the photoactivity generated by
Electrons are excited under visible light irradiation to show photocatalytic decomposition activity.
You That is, the oxygen in the air is superposed by the conductive charge potential.
-Oxide (O_Two ⁻), And in the valence band photon is water
Reaction of direct oxidation of hydroxyl radical (OH)
Generates radicals with high power (H₂O → ・ OH +
H⁺). And any coexisting zirconium oxide
The strong diffuse reflection of light in the direction
Catalytic activity of Titanium Oxide with increased chance of visible light response
Increase, the amount of UV / visible light-responsive titanium oxide used
It is thought that it will be less.

(2) Zirconium oxide is excited by ultraviolet rays slightly contained in sunlight or artificial rays, and once excited, it has a wide band gap of 5.0 eV. Therefore, its conduction charge potential is reduced by -1.0 eV. F with trivalent power
e ³⁺ is divalent Fe ²⁺ (Fe ³⁺ → Fe ²⁺ ), and H ₂ O → · O is generated due to the strong oxidizing power of +4.0 eV potential in the valence band.
It contributes to the reaction of H + H ⁺ and partly Fe ²⁺ → Fe ³⁺
It is thought that it is also used in the oxidation reaction of Fe ²⁺ and is also involved in the rotation cycle of Fe ²⁺ ← → Fe ³⁺ .

This is because the particle size of zirconium oxide is about 3 nm.
Since it is ultra-fine particles, the photocatalytic activity was improved by increasing the specific surface area, and it is considered that the photocatalytic function could be exhibited by capturing weak ultraviolet rays. In fact, when the composition A containing only zirconium oxide was used as the photocatalyst in the agent A of the present invention and only zirconium oxide having a particle size of 60 μm was used, bacterial growth was observed within one week. On the other hand, in the case of using zirconium oxide having a particle size of about 3 nm, no bacterial growth was observed even after 1.5 months. Therefore, when a zirconium oxide having a particle size of about 3 nm was used, the bacteria would undergo a photocatalytic decomposition reaction. It was understood that it was received and sterilized. The reason why a small amount of Fe ³⁺ may be added is that Fe ²⁺ ←
→ It is considered that the mutual exchange reaction of Fe ³⁺ occurs.

(3) H generated by oxidative decomposition of water by photons in the valence band of titanium oxide and zirconium oxide
⁺ Reacts with O ₂ ⁻ to become an · OOH radical, and this radical causes Fe ²⁺ → Fe ³⁺ to proceed, whereby · OH is generated.

(4) Then, .OH generated by the series of reactions decomposes / removes pollutants on the surface of the polluted object such as teeth or fibers such as dental plaque or coloring matter contacting the photocatalyst.

In using the composition of the present invention, sunlight and room light are sufficient as a light source for causing a photocatalytic reaction, and it is a great feature of the present invention that a special visible light irradiation device is not required. is there.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The following examples of the present invention show preferred examples, and the present invention is not limited to these examples.

(1) Preparation of bleaching composition A agent for home use: 1.95 g of carboxymethyl cellulose sodium (CMC-Na) is added to 40 g of distilled water or 5% aqueous ethanol solution and stirred to dissolve uniformly.
To this transparent gel, 0.1 g of ultraviolet light / visible light responsive titanium oxide (manufactured by Ecodevice Co., Ltd.) or ultraviolet light responsive titanium oxide (manufactured by Toray Co., Ltd.) and the announced particle size of 3 nm were previously oxidized. When 0.2 g of zirconium was well mixed with stirring, the mixture was uniformly dispersed, and further 2.3 g of glycerin and 4.0 g of propylene glycol were added and mixed with stirring to obtain a white opaque gel. After being applied to teeth or dentures, distilled water or a 5% ethanol aqueous solution was adjusted in the range of 39 to 42 g so that the viscosity of this product would not drop. The addition amounts of CMC-Na, glycerin and propylene glycol were tested unchanged.

Agent B: A saturated aqueous solution of ferric citrate is prepared, and the supernatant is used. The Fe ³⁺ concentration in this saturated aqueous solution was 592 ppm, and the pH was 2.96.

(2) Preparation of Decomposition Target (a) Cigarette Consume Containing a filter, a cigarette tobacco, and a filter part of a small plastic pipe were collected to obtain an ethanol extract. The dark brown ethanol solution was concentrated under reduced pressure to obtain a tar-like substance, which was used as a tobacco tar concentrate.

(B) Preparation of Black Tea Concentrate Two commercially available black tea bags were dipped in 150 mL of distilled water, subjected to hot water extraction for 20 minutes in boiling water, and then concentrated under reduced pressure to 40 mL to obtain a black tea concentrate.

(C) Methylene blue solution Methylene blue 0.015 g / 15 mL ethanol solution was prepared.

(D) Humic acid solution and lignin solution The humic acid solution was 0.015 g / 15 mL ethanol solution, and the lignin solution was 0.015 g / 15 mL ethanol solution.

[0051]

Example 1 10 mL of a diluted solution of methylene blue diluted with 28 times the above methylene blue with 10 mL of the concentrated solution of black tea and 5B filter paper were separately spotted, and TiO _{2 was} added.
(0.08 wt%), ZrO ₂ (0.16 wt%), T
iO ₂ / ZrO ₂ (0.08 wt% / 0.16 wt%,)
The gel-like substance was applied, and after 5 minutes, the change in color after 10 minutes was visually observed.

[0052]

[Table 1] In the table, TiO ₂ is anatase type ultraviolet light / visible light responsive titanium oxide manufactured by Eco Device Co., Ltd., and TiO ₂ ^* is anatase type ultraviolet light responsive type manufactured by Toray Industries, Inc. Titanium oxide.

As is clear from Table 1, the case of using only TiO ₂ , the case of using only ZrO _2, and the case of TiO ₂ / Zr
Comparing the cases of using O ₂ , it is clear that TiO ₂ and Zr
It can be seen that there is a synergistic effect of O ₂ . In addition, TiO ₂ -Fe
^{Even if the 3+} system and the TiO ₂ —ZrO ₂ —Fe ³⁺ system are compared, it is clear that there is a synergistic effect of TiO ₂ and ZrO ₂ . Ti
Even when TiO ₂ ^* is used instead of O ₂ , TiO ₂ ^* and Zr
It can be seen that there is a synergistic effect of O ₂ .

Also, is there no response to visible light?
It has been found that when ultraviolet light-responsive titanium oxide (TiO ₂ ^* ), which is said to be almost absent, coexists with zirconium oxide in the form of ultrafine particles, a photocatalytic activity also occurs with respect to visible light as shown by the above experimental results.

An experiment was carried out with a methylene blue diluting solution at a concentration at which the color change of the solution was large. However, since the black tea concentrate is hardly decomposed, it takes time for the composition of the present invention to remove contaminants. Takes. However, as is apparent from the result after 20 minutes, the composition of the present invention showed that TiO ₂ and Zr
It was found that the coexistence of O ₂ synergistically increased the photocatalytic activity.

[0056]

[Example 2] In a room under the illumination of a fluorescent lamp, about 0.1 g of the above-mentioned agent A was applied on a transparent glass plate, 5 μL of a methylene blue solution was placed on this, and the tip of the microspatel was set up and lightly touched. The mixture was mixed with the agent A so as to be cut off. Then, 10 μL of a saturated aqueous solution of ferric citrate, which is the above-mentioned agent B, was added to this, and the tip of the microspatel was stood up and lightly patted and mixed for 5 minutes, and then the absorption at 580 nm was measured by a densitometer. It was measured. as a result,
The color tone of methylene blue was fading by 77 to 82%. From this result, it can be seen that methylene blue was decomposed.
As a control product, a gel-like material not containing TiO ₂ and ZrO ₂ in the agent A was added to 5 μL of a methylene blue solution for measurement, but the color tone of methylene blue did not change.

[0057]

Example 3 In order to find an appropriate ratio of the photocatalyst of titanium oxide and zirconium oxide contained in the agent A, zirconium oxide (particle size 3 nm) was added to ultraviolet / visible light responsive titanium oxide in an amount of 0. 3x, 0.5x, 1x, 1.7
When the agent A of (1) in Example 2 was prepared by adding twice, twice and three times the weight, when the amount of zirconium oxide added was 0.5 times or less, precipitation of ultraviolet / visible responsive titanium oxide was observed. Was recognized. When the amount of zirconium oxide added is more than 1 time, the dispersion stability of titanium oxide in the liquid medium and the soft-hocus effect of zirconium oxide make it possible to mix it with yellow ultraviolet / visible light responsive titanium oxide. In order to make the agent A white, and to make it easier to visually see the appearance of dirt or the like that has been peeled off / desorbed when it is applied to teeth, etc., on the coated surface of agent A, It is preferably 7 to 2 times. In addition, precipitation of ultraviolet / visible light responsive titanium oxide was observed in both cases of using 1 time and 1.5 times the amount of zirconium oxide having a particle size of 60 μm with respect to the above titanium oxide.

[0058]

Example 4 In order to find out the concentration of titanium oxide and zirconium oxide contained in the agent A, which shows the decomposition action of the photocatalyst, a test was conducted using a black tea concentrate as an object to be decomposed.
The weight ratio of ultraviolet light / visible light responsive titanium oxide and zirconium oxide (particle size 3 nm) in the agent A was set to 1: 2 according to the test result of the above-mentioned Example 3.

In a room under the illumination of a fluorescent lamp, 0.06 of ultraviolet / visible light responsive titanium oxide in agent A was applied on a transparent glass plate.
%, 0.21%, 0.65%, 0.72%, 1.25%
And about 1.45% each of the agent A containing 1.45% (both by weight), and 10 μm of the black tea concentrate
L was put on it, the tip of the microspatel was stood up, and it was lightly tapped to mix with agent A. Then, 10 μL of a saturated aqueous solution of ferric citrate having a concentration of 592 ppm%
Was added, the tip of the microspatel was stood up, and the mixture was lightly beaten and mixed.

Immediately after the addition of a saturated aqueous solution of ferric citrate having a concentration of 592 ppm, the black tea concentrate gradually changed from brown to black, and after 5 minutes at any concentration of the ultraviolet light / ray visible responsive titanium oxide. It was completely blackened.

Since the blackening means that the black tea concentrate is carbonized and decomposed, an agent A having an ultraviolet / visible light responsive titanium oxide concentration of 0.08 mg / 0.1 g was prepared to obtain a transparent glass plate. When applied to the above, 2 parts of the saturated aqueous solution of ferric citrate was added to determine the quantitative relationship between TiO ₂ and ferric citrate.
μL, 5 μL and 10 μL were respectively added to observe the decomposition reaction of the black tea concentrate in the room under the illumination of the fluorescent lamp.

When the amount of the saturated aqueous ferric citrate solution added was 2 μL, the color of the target substance to be decomposed was brown, and when 5 μL, blackening was observed, and when 10 μL, blackening was immediately observed. It was From this result, it is considered that when 10 μL of a saturated aqueous solution of ferric citrate is used, the minimum concentration of ultraviolet / visible light responsive titanium oxide necessary for causing photocatalytic decomposition is about 0.08 mg / 100 mg. .

[0063]

[Embodiment 5] An ultraviolet / visible light responsive titanium oxide is 1.2.
30 μL each of the humic acid infusion solution and the lignin solution prepared by the above-mentioned procedure using the same agent A as in Example 4 containing 5 wt%
In addition, the same test as in Example 4 was performed, but the brown color of these solutions immediately disappeared.

[0064]

[Example 6] In a room illuminated by a fluorescent lamp, a tar-shaped cigarette tar concentrate was applied to one surface of a denture, allowed to stand at room temperature for one week and dried, and then an ultraviolet / visible light-responsive titanium oxide 0.1 g of agent A with a minimum concentration of about 0.08 mg / 100 mg
Was top-coated, the tip of the microspatel was stood up, and the mixture was lightly patted and mixed with the tar concentrate. Further, 10 μL of a saturated aqueous solution of ferric citrate of the agent B having a concentration of 592 ppm was added to the mixture to stir the tip of the microspatel, and the mixture was gently tapped to mix. Five minutes after the addition of the saturated aqueous solution of ferric citrate, the denture was held under running tap water to wash off the applied material.

In FIG. 2A, the denture not subjected to the home bleaching operation is shown on the left side, and the denture subjected to the home bleaching operation is shown on the right side. Most of the residue was removed, although the tar concentrate remained along the linear depression on the denture. 30 μL of each of the black tea concentrate, the humic acid solution and the lignin solution was applied on the denture and dried for 1 day, and then the composition A for home bleaching was used in the same manner as the tobacco tar concentrate.
Agent and B agent. These three objects to be decomposed are 2.
Degradation was visually observed within 5 minutes, and as shown in the black tea concentrate (Fig. 2 (b)) and the lignin solution (Fig. 2 (c)), the denture returned to its original color after being completely washed away with running tap water. did.

[0066]

Example 7 For example, when coffee is spilled on clothes and is bleached and removed by the agent A and the agent B, an iron salt produced by the reaction of tannin in the fiber and the iron citrate of the agent B is formed into the fiber. It remains as black spots on the top.
In order to prevent this, without adding the iron citrate solution of the agent B, titanium oxide, zirconium oxide, CMC-Na, and a mixture of water and ethanol (for example, TiO ₂ / ZrO ₂ ) in which the compounding amounts of titanium oxide and zirconium oxide are increased. ₂ /
CMC-Na / purified water / ethanol = 0.030 g /
0.054 g / 0.400 g / 15 mL / 15 mL) was prepared and applied to coffee stains (dry) on white fibers under room light and after 15-20 minutes wipe the application with a tissue. gone.

As a result, although it took time, the stain did not spread on the cloth, the stain on the coffee disappeared, and the state was restored to the original state. When the cloth was washed with water and dried, a faint brown color remained on the edges where the chemical was not applied.

[0068]

[Embodiment 8] The same titanium oxide, zirconium oxide, and CMC as those in the above-mentioned Embodiment 7 are added to the black tea concentrate or tobacco tar on the denture without adding the iron citrate solution of B agent.
-Na and a mixture of water and ethanol (eg TiO 2
₂ / ZrO ₂ / CMC-Na / purified water / ethanol = 0.
030g / 0.054g / 0.400g / 15mL / 1
5 mL) was applied. After 5 to 10 minutes, stains had floated up on the surface of the applied material, and when wiped off with a tissue paper, the adhered black tea concentrate or tobacco tar was removed.

From the results of Examples 7 and 8 above,
It was considered that only the .OH radicals generated by titanium oxide and zirconium oxide in the state shown in FIG. 1 in which iron ions were not involved acted on the stain.

[0070]

Industrial Applicability The composition for home bleaching of the present invention has a function of decomposing and removing plaque, tars, or fibers adhering to the surface of teeth, dentures or other surfaces of oral and dental materials, or coloring of objects to be decomposed such as fibers. The effect of fading can be achieved within a short time. Moreover, the composition for home bleaching is excellent in safety and handling. Moreover, since the composition for home bleaching does not require a special visible light irradiation device, it can be easily used at home.

[Brief description of drawings]

FIG. 1 shows the photocatalytic decomposition action of the tooth etc. of the present invention.
It is a figure explaining the mechanism which causes a radical.

FIG. 2 is a diagram showing the results of a photocatalytic decomposition treatment of black tea concentrate, lignin and tobacco tar according to the present invention. In tobacco tar (Fig. 2 (a)), black tea concentrate (Fig. 2 (b)) and lignin (Fig. 2 (c)), the left side is not decomposed and the right side is denture after the decomposition process. Is.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06L 3/04 D06L 3/04 F term (reference) 4C052 AA20 FF10 4C083 AB211 AB212 AB241 AB242 AC102 AC302 AD272 CC41 EE35 4G069 AA08 BA04A BA04B BA05A BA05B BA21A BA21B BA48A BC66B BC66C BE08B CD10 DA06 EA08 EB19 FA01 FA03 FB06 FB23 4H003 BA10 DA03 DB01 DC04 EE11 FA30

Claims (7)

[Claims] 1. A composition for home bleaching containing titanium oxide having photocatalytic activity and zirconium oxide in the form of ultrafine particles. 2. The composition for home bleaching according to claim 1, comprising at least a paste / binder among a viscosity modifier and a paste / binder. 3. A dentifrice containing the composition for home bleaching according to claim 2. 4. A composition for home bleaching containing titanium oxide having photocatalytic activity, zirconium oxide in the form of ultrafine particles, and ferric salt. 5. The composition for home bleaching according to claim 4, wherein the composition comprises at least a paste / binder among a viscosity modifier and a paste / binder. 6. A tooth and a dental material mounted in the oral cavity under the irradiation of ultraviolet light and / or visible light, and is applied to the surface of the dental material on the surface of the dental material or the spot where contaminants are attached on the fiber outside the oral cavity, and then ultraviolet and / or ultraviolet light is applied.
Alternatively, the method for using the composition for home bleaching according to claim 1, wherein the composition is irradiated with visible light. 7. Ultraviolet and / or visible light is applied by irradiating with ultraviolet light and / or visible light to a tooth, a dental material mounted in the oral cavity, and a surface of the dental material outside the oral cavity or a spot where contaminants are attached on fibers. The method of using the composition for home bleaching according to claim 4, wherein the composition is irradiated with.