JPH09202718A - Coating solution for tooth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating solution having inhibitory effects on a foul breath for many hours, useful for teeth or artificial crowns, coloring in white or in an arbitrary color, by using both a specific resin excellent in water resistance and foul breath inhibitor or a perfume. SOLUTION: This coating solution comprises N-methacryloyloxyethyl N,N- dimethylammonium/α-N-methylcarboxybetaine/butyl methacrylate copolymer, a <=4C alcohol and a deodorant, a germicide or a perfume having inhibitory effects on a foul breath. The coating solution is especially preferably obtained by blending 5-95% sthanol with 0-25% (most preferably 20-27%) of the copolymer and 0-10% of powder of a colored pigment or extender pigment. The coating solution may be mixed with chlorophyll or its derivative. The coating solution may be blended with an antienzyme such as sodium lauroylsarcosine. The coating solution may be incorporated with sodium lawrylsulfoacetate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating liquid for use in teeth or artificial crowns, which is colored white or in any color, by combining a resin having good water resistance with a breath freshener or a fragrance. The present invention relates to a tooth coating solution having a bad breath preventing effect for a long time.

[0002]

[Prior art]

Japanese Patent Application Laid-Open No. 4-82821 discloses a tooth cosmetic agent using a large amount (30 to 50%) of shellac. It is disclosed in this invention that the "original deodorant, antibacterial agent, and fragrance" can be added to clean the inside of the oral cavity. However, although shellac is not easily dissolved in water, it swells in the oral cavity, the coating becomes sparse, and the additive elutes in saliva, so even if it is added to the coating liquid (cosmetic agent). It did not stay on the coating film for a long time, but only provided a clean feeling at the time of application.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to eliminate deodorants, antibacterial agents, and fragrances (hereinafter these are collectively referred to as halitosis inhibitors).
Remains in the coating film for a long period of time, which has the effect of preventing bad breath, good pigment dispersion stability, and safe for the human body.
It is an object of the present invention to provide a tooth coating liquid having gloss and toughness equivalent to or better than conventional products.

[0004]

In order to achieve the above object, the inventors of the present invention searched for a resin having excellent water resistance and a resin that suppresses swelling of shellac and vinyl acetate in saliva, and as a result of earnest research, N- Methacryloyloxyethyl N, N
It was found that the water resistance of the coating film is improved by using the dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer, and the breath odor inhibitor remains in the coating film for a long time. Has been completed.

In this tooth coating liquid, it is essential to use N-methacryloyloxyethyl N, N.dimethylammonium.α-N-methylcarboxybetaine / butyl methacrylate copolymer and a breath freshener. Even with this minimum combination, good results can be obtained in terms of pigment dispersibility and coating adhesion, but with a resin such as shellac or vinyl acetate resin, which has good adhesion and gloss, and has a proven record of safety. It can also be used in combination. In this case, the addition amount of shellac and vinyl acetate resin is 5% to 30% in both cases.
It is. If it is less than 5%, the effect of improving stickiness cannot be obtained,
If it exceeds 30%, the viscosity of the coating solution becomes too high, and the coatability (easiness of coating) is significantly impaired. When the amount of these resins added is 15% to 30%, the coatability and stickiness are more preferable, and when the amount is 20% to 27%, the coatability, stickiness, dryness on teeth, and film thickness after drying. The most preferable result is obtained.

N-methacryloyloxyethyl N, N.
Dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is approximately 0.01%.
From the above, the effect of improving water resistance is exhibited. It is not possible to confirm whether the added amount of the breath freshener can be retained in the coating film, but it is possible to apply 0.01% of the solution on glass, dry it, and soak it in tap water for 24 hours. However, since the coating film remains, the water resistance is clear, and in principle, it is thought that the effect of preventing bad breath can be retained. O. O1%
If it is less than the above, the effect of improving water resistance is not recognized.

N-methacryloyloxyethyl N, N.
When a large amount of dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is added, the water resistance, gloss, and sedimentation stability of the pigment are excellent, but the stability over time as a coating solution is slightly inferior. Since the coating film becomes too thick, the coating film is likely to be peeled off from the coating surface, and the viscosity is high to deteriorate the coating property. Therefore, the maximum addition amount is approximately 40%.

N-methacryloyloxyethyl N, N.
Practically, the amount of the dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer added is in the range of 0.1% to 20%. When used in a small amount such as less than 10%, it is preferably used in combination with shellac or vinyl acetate resin, but a 20% solution of shellac contains N-methacryloyloxyethyl N, N.dimethylammonium.α.
After adding -N-methylcarboxybetaine-butyl methacrylate copolymer to form a dry film on glass and then immersing it in tap water, a test was conducted. Like the above, the film becomes cloudy,
If it is added in an amount of 0.1% or more, the transparency will increase depending on the amount added. This means that the swelling of the shellac film with respect to water was suppressed, and at the same time, the possibility that the breath odor inhibitor, which is the subject matter of the present invention, remains in the film.

When it is used in an amount of 10% or more, the adhesiveness and gloss are good and the water resistance is also good even when used alone without being used in combination with other resins. Further, it can be used in combination with shellac or vinyl acetate resin in order to adjust the gloss and the flexibility of the film (which also affects the sticking property) as desired. However, 20
If it is added in excess of%, the viscosity becomes high and it is difficult to use it in combination with shellac or vinyl acetate, and it is preferable to use it alone. The film formed by N-methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine-butyl methacrylate copolymer is hard and brittle, so there is a strong possibility that it will peel off from the teeth all together. Become.

N-methacryloyloxyethyl N, N.
When dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is used alone, the preferable range of addition is 10% to 20%,
When used in combination with shellac or vinyl acetate resin, the optimum addition amount is 0.1% to 10%, which is preferable to using it alone. When the addition amount is as low as less than 1%, the fixing property is insufficient, but this can be compensated by shellac or vinyl acetate resin, and the effect of retaining the breath freshener and improving the dispersibility of the pigment can be obtained. When used in combination with shellac or vinyl acetate resin, which has a proven track record as a tooth coating solution, the same gloss and adhesion as conventional products can be obtained, and it can be used comfortably by those who have been using it for a long time. I can. Also, N
-Methacryloyloxyethyl N, N / dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer was added 10% or more, and shellac and vinyl acetate resin were added, which was slightly different from the conventional product. It has gloss and stickiness, but both are good and the water resistance is very good.

N-methacryloyloxyethyl N, N.
A film in which the properties of dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate are dominant (addition of more than 10%) and a film in which properties of shellac and vinyl acetate resin are dominant (N-methacryloyloxyethyl). N, N / dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is 1
Which is 0% or less and 20% or more of shellac and vinyl acetate resin) has excellent performance as a tooth coating liquid cannot be generally stated. Generally, the former has good water resistance and long-lasting gloss, but it is fragile and tends to peel off easily.The former is slightly swollen by saliva and the like, but the gloss is inferior, but it tends to show a natural white color and appropriate flexibility. Is the latter.

According to the principle of the present invention, all the alcohol-soluble resins having higher water resistance than shellac and vinyl acetate resins can be expected to improve the retention effect of the breath freshener. It was confirmed that phenolic resin, ketone resin, butyral resin, and rosin resin actually improve the water swelling resistance of shellac and vinyl acetate. Further, for acrylic and methacrylic resins, for example, an acrylic ester / methacrylic ester copolymer is neutralized with 2-amino-2methyl-1.3 propanediol or 2-amino-2-methyl-1-propanol. Addition of 1% to 20% of acrylic resin and the like makes pigment dispersibility good,
A sufficient effect was also observed on the ability to hold the halitosis inhibitor.
However, if the same amount is added, the water resistance is slightly inferior, and the viscosity is more likely to be increased to easily deteriorate the coating property.
The performance was inferior to that of the methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine-butyl methacrylate copolymer. Styrene acrylic acid resin and styrene maleic acid resin are also 1% to 20%
In the addition range, the water resistance was improved, the bad breath prevention effect was good, and the viscosity was also easy to handle. However, due to the dispersibility of the pigment, N-methacryloyloxyethyl N, N.dimethylammonium.alpha.-N-methyl It was inferior to the carboxybetaine / butyl methacrylate copolymer. These resins do not depart from the gist of the present invention, and can be used as a tooth coating liquid if safety is confirmed.

Ethanol is preferred as the main solvent of the tooth coating liquid of the present invention, but it is safe for humans and N-methacryloyloxyethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer is used. Any solvent may be used as long as it dissolves. However, since it is a coating liquid used in the oral cavity, a solvent that does not cause an unpleasant odor is preferable.

As the coloring component, carbon black, titanium white (titanium oxide), titanium black, zinc white, red iron oxide, chromium oxide, iron black, cobalt blue, alumina white, iron oxide yellow, viridian, etc. may be used, if necessary.
Zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon,
Inorganic pigments such as ultramarine, lead white, navy blue, manganese violet, aluminum powder, brass powder, CI16185, CI45430,
CI16255, CI45410, CI45440, CI45100, C.
I.19140, CI15985, CI42053, CI42090, CI
73015, CI15850, CI15585, CI15630, CI45
170, CI15800, CI15880, CI12120, CI4538
0, CI26100, CI73360, CI17200, CI12085
, CI45370, CI12075, CI21110, CI15510
, CI45425, CI45350, CI47005, CI47000
, CI21090, CI61570, CI61565, CI59040
, CI42095, CI73000, CI42052, CI69825
, CI42090, CI20170, CI60725, CI45190
, CI15865, CI26105, CI16155, CI16150
, CI14700, CI12140, CI15620, CI11725
, CI14600, CI12100, CI11680, CI18950
, CI10316, CI11380, CI11390, CI13065
, CI18820, CI10020, CI42085, CI61520
, CI74160, CI60730, CI20470 and other organic pigments and acid dye lake pigments, fish scale foil, various mica titanium,
Sericite, Muscobite, Akoya shellfish, Abalone shellfish,
Pearl pigments such as Takase shell powder can be used. Furthermore, due to its peculiarity of being used only on teeth, it has almost no coloring power and is generally called an extender pigment, barite powder, precipitated barium sulfate, barium carbonate, lime carbonate powder, precipitated calcium carbonate, gypsum, asbestos, clay, Even if silica powder, finely divided silicic acid, light algal soil, talc, basic magnesium carbonate, alumina white, gloss white, satin white, tricalcium phosphate, hydroxyapatite, etc. are used, a transparent natural white color can be obtained. Among them, hydroxyapatite, tricalcium phosphate, calcium carbonate and the like are preferable materials because they are tooth constituent components and those close thereto.

Since these coloring components are used in the oral cavity, safety for the human body must be fully considered.
It should be selected from those approved as food additives and those with low oral toxicity.

If desired, additives such as surfactants, fragrances, oils and fats, and hardly volatile hydrocarbons can be added to the tooth coating liquid of the present invention. The surfactant is expected to have favorable effects such as improving the water resistance at the interface with the gas and liquid (such as saliva) on the surface of the coating film. In addition to the breath odor prevention effect of the present invention, the fragrance can be expected to have an effect of masking an unpleasant odor when applied in the oral cavity and, conversely, improving the feeling of use. In addition, non-volatile substances such as surfactants and fragrances, fats and oils and non-volatile hydrocarbons are N-methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine-butyl methacrylate. Some of them are also useful as plasticizers for polymers and shellacs, and the coating film is flexible and has high adhesiveness and excellent durability with suppressed brittleness of the coating film.

The tooth coating solution of the present invention comprises N-methacryloyloxyethyl N, N.dimethylammonium.α-N-
Dissolve methylcarboxybetaine-butyl methacrylate copolymer in ethanol etc., and then add a pigment other than the pearl pigment to obtain the desired color and effect, and then ball mill, bead mill, sand mill, roll mill, A kneader, a homogenizer, an ultrasonic disperser, etc. are used to perform a dispersion treatment to prepare a pigment dispersion liquid, and resin and a surfactant, a fragrance, a pearl pigment and the like in consideration of the performance as a tooth coating liquid such as adhesion and hue. Basically, a dispersion or a pigment dispersed in advance is added as required, and a breath freshener is further added. Among the pigments, the reason why only the pearl pigment cannot be applied to the disperser is that the pigment breaks due to shearing due to dispersion and loses its pearl luster, so there is no need to treat it specially as long as the pigment does not break. .

【Example】

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples. The above-mentioned liquid preparation method is an industrially effective method for suppressing variations, but in this Example, a compound other than a pearl pigment is used. The ingredients were mixed at once and kneaded with a bead mill for 1 hour. Those containing the pearl pigment were added after that, and ultrasonic waves were irradiated for 15 minutes to diffuse. In addition, Example 5 containing no pigment
And Comparative Example 5 was only stirred with a magnetic stirrer. Even with such a method, there is no problem in the performance as a tooth coating solution.

The N-methacryloyloxyethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer in the formulation of this example is 30% by weight from Mitsubishi Chemical under the name "Yukaformer AM75". Supplied as a 40% ethanol solution. (Example 1) Ethanol 46.5% rack coat 50EDS (shellac 50% ethanol solution; trade name of Nippon Shellac Co., Ltd.) 50.0% titanium oxide CR-50 (titanium oxide of ordinary particle size; Ishihara Sangyo Co., Ltd.) Product name) 0.5% Yukafoamer AM75 201 (40% ethanol solution) 1.0% MOUTHWASH FLAVOUR (PEPPER MINT CR) 3272-B (fragrance; Art Perfumery Co., Ltd. product name) 0.5% chlorone ( Copper chlorophyllin sodium; Nippon Chlorophyll Co., Ltd. trade name 1.0% Mica titanium SP-350 (Taika Co., Ltd. trade name) 0.5% (Example 2) Ethanol 82.5% Transparent white rack dry product GBN- D (Shellac; Gifu Shellac Co., Ltd. product name) 5.0% MT-500SA (Ultrafine titanium oxide (primary particle diameter 35 nm); Teika Co., Ltd. product name) 1.5% Yu CAFAMOR AM75 202 (30% ethanol solution) 10.0% l-menthol (Japanese Pharmacopoeia) 0.5% Lauroyl sarcosine sodium (Wako Pure Chemical Industries, Ltd. reagent) 0.5% (Example 3) Ethanol 63 0.0% Ethnyl C-3 (vinyl acetate resin; product name of Sekisui Chemical Co., Ltd.) 30.0% Yucaformer AM75 204 (40% ethanol solution) 0.3% Titanium Oxide P-25 (Ultrafine titanium oxide ( Primary particle size 30 nm; Nippon Aerogel Co., Ltd. product name 1.0% Toothpast flavor M8263 (fragrance; Takasago Fragrance Co., Ltd. product name) 0.2% NIKKOL LSA (sodium lauryl sulfoacetate; Nikko Chemical Co., Ltd. product) Name) 0.5% MEARLMAID OL (paste containing 20% fish scale foil; The Mearl Corporation trade name) 5.0% (Example 4) Ethanol 88.8% Transparent white rack dried product Z-GBN (Serac; Gifu Shellac Co., Ltd. trade name) 6.0% Yucaformer AM75 R205S (30% ethanol solution) 5.0% Thymol (Shiso) Family plant extract, fragrance, bactericide; manufactured by Osaka Kasei Co., Ltd. 0.2% (Example 5) Ethanol 59.8% Rack Coat 50EDS 20.0% Yucaformer AM75 206 (30% ethanol solution) 20. 0% Methyl salicylate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 0.1% Nicotinic acid amide (manufactured by Organic Synthetic Chemical Industry Co., Ltd.) 0.1% (Comparative Example 1) Ethanol 45.5% Rack Coat 50EDS 52. 0% Titanium oxide CR-50 0.5% MOUTHWASH FLAVOUR (PEPPER MINT CR) 3272-B 0.5% Chlorone 1.0% Mica titanium SP-350 0.5% (Comparative example ) Ethanol 88.0% Clear white rack dry product GBN-D 10.0% MT-500SA 1.5% l-menthol 0.5% lauroyl sarcosine sodium 0.5% (Comparative Example 3) Ethanol 63.3% Ethnyl C-3 30.0% Titanium Oxide P-25 1.0% Toothpast flavor M8263 0.2% NIKKOL LSA 0.5% MERLMAID OL 5.0% (Comparative Example 4) Ethanol 92.3% Transparent white rack dry Product Z-GBN 7.5% Thymol 0.2% (Comparative Example 5) Ethanol 59.8% Rackcoat 50EDS 20.0% Yucaformer AM75 206 20.0% Methyl salicylate 0.1% Nicotinic acid amide 0.1 % (Comparative Example 6) Ethanol 46.5% Rack coat 50EDS 50.0% Titanium oxide CR-5 0.5% plus size L53D (50% ethanol solution of acrylic resin obtained by neutralizing acrylic acid / methacrylic acid ester copolymer with 2-amino-2methyl-1.3 propanediol; ) Trade name) 1.0% MOUTHWASH FLAVOUR (PEPPER MINT CR) 3272-B 0.5% Chlorone 1.0% Mica titanium SP-350 0.5% Using Examples 1-5 and Comparative Examples 1-6 The following tests were conducted. Test 1-Sensory test by monitor Eleven people who are usually healthy and do not feel bad breath were collected, and after brushing their teeth well, Examples 1 to 5 and Comparative Examples 1 to 6 were applied, and 2
The teeth were smelled each other without brushing the teeth for 4 hours, and the presence or absence thereof was judged. (Tests were conducted in random order,
Since it is a day-long test, there are no special dietary restrictions other than having the monitor eat normal food. Judgment was made on the following three levels: {O} No odor, {△} Slight odor, {×} Unpleasant odor, {○} = 2 points, {△} = 1
Points, {x} = 0 points, and the larger the total score of 10 people other than the person himself, the better the sustainability of the halitosis prevention effect. Test 1-Adhesion Test by Monitor In Test 1-, the residual state of the coating film 24 hours after coating was examined. {◎} ... Almost no change. Although there are changes such as {○} white turbidity, they remain. {△} ... The coating film was lost in some areas, but the coating film was mostly left. {X} ... Almost no coating film remains. Test 2 Water resistance / water swelling resistance test Examples 1 to 5 and Comparative Examples 1 to 6 were applied to a glass plate with a doctor blade of 8 mil, and dried to obtain a pencil hardness of the film as it is and a glass plate in tap water. After soaking each for 24 hours, the pencil hardness of the coating film in which rough water was removed with soft paper was measured. Pencil hardness is JIS K540
It was judged according to 0-6.14 "Pencil scratch test".
In order to make it easy to understand the difference between the two, the rank difference is expressed as a numerical value, with the dry film strength as the "initial" hardness and the film strength after immersion in water as the "test" film strength. did.
For example, if the "initial" coating strength is "HB" and the "post-test" coating strength is "B", the "rank difference" is 1. Rank difference is 4 if "initial" is "HB" and "after test" is "4B".
It was judged that the larger the value, the larger the swelling due to water (= the lower the water swelling resistance).

[0020]

[Table 1]

[0021]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to obtain a cosmetic coating solution for teeth which has good dispersibility, good adhesion, and good durability after application.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyokazu Sakurai 1091 Tateishi, Gunma Prefecture Fujioka City R & D Center (72) Inventor Tetsuo Takasaka 1091 Tateishi Fujioka City Gunma Research, Mitsubishi Pencil Stock Company In the development center (72) Inventor Taka Umeno 1091, Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd.R & D center (72) Inventor Tomoko Hasegawa 1091, Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd. 72) Inventor Kazuhiro Ami 1091 Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd.

Claims (7)

[Claims] 1. A deodorant containing an alcohol having at least 4 carbon atoms and N-methacryloyloxyethyl N, N.dimethylammonium.alpha.-N-methylcarboxybetaine.butyl methacrylate copolymer, which has an effect of preventing bad breath. A tooth coating solution containing an agent, a germicide or a fragrance. 2. The tooth coating liquid according to claim 1, which contains chlorophyll or a derivative thereof. 3. The tooth coating liquid according to claim 1, which contains an anti-enzyme agent. 4. The tooth coating solution according to claim 3, wherein the anti-enzyme agent is lauroyl sarcosine sodium. 5. The tooth coating solution according to claim 1, which contains sodium lauryl sulfoacetate or sodium lauryl sulfate. 6. The alcohol having 4 or less carbon atoms is ethanol, and in addition to N-methacryloyloxyethyl N, N.dimethylammonium.α-N-methylcarboxybetaine / butyl methacrylate copolymer, shellac or vinyl acetate. The tooth coating liquid according to claim 1, claim 2, claim 3, claim 4 or claim 5, containing one or both of the resins. 7. 5-95% ethanol and N-methacryloyloxyethyl N, N.dimethylammonium.alpha.
7. The tooth coating liquid according to claim 6, wherein the N-methylcarboxybetaine / butyl methacrylate copolymer is contained in an amount of 0 to 25% and the powder such as a coloring pigment or an extender pigment is included in an amount of 0 to 10%.