JPH09151123A - Tooth coating liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating liquid capable of coloring tooth or tooth crowns to white or any other color by using an acrylic resin prepared by neutralizing an acrylic ester-methacrylic eater-based copolymer with a specific compound. SOLUTION: This tooth coating liquid contusions ethanol and an acrylic resin prepared by neutralizing an acrylic ester-methacrylic ester-based copolymer with 2-amino-2-methyl-1,3-propanediol or 2-amino-2-methyl-1-propanol, and may also contain a color pigment or extender pigment, and furthermore, ceramic(s) and/or a vinyl acetate resin. It is preferable that this coating liquid comprises 10-94.8wt.% or more of ethanol, 0.1-30wt.% of a pigment, 0.1-20wt.% of the above acrylic resin, and 5-30wt.% of ceramic(s) and/or butyl acetate resin. The pigment is pref. titanium dioxide (optimally, <=100nm primary particle diameter on average).

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating liquid for coloring teeth or artificial crowns which is colored white or any color.

[0002]

2. Description of the Related Art A conventional tooth coating solution is made of inorganic powder (generally titanium oxide or pearl pigment) by keeping a dispersion of titanium oxide or the like in shellac or vinyl acetate resin at a relatively high viscosity. Settling was suppressed. However, both resins have poor pigment dispersibility, and the vinyl acetate resin has poor water resistance and the coating film is easily lost. In addition, shellac has poor stability over time, and even if a product in a moderately dispersed state is formed immediately after dispersion, the pigment aggregates and precipitates in about one week at room temperature.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to use a dispersion resin which is safe for human body and has good dispersion stability when it contains a pigment, excellent fixing property and water resistance. It is an object of the present invention to provide a tooth coating solution which continues stable dispersion over a long period of time and maintains a beautiful gloss for a long time even after being applied on a crown.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that an acrylic acid ester / methacrylic acid ester type copolymer is treated with 2-amino-2methyl-1.3 propanediol or 2-amino. -2 Methyl-1-propanol-neutralized acrylic resin is used to disperse fine particle titanium oxide having an average particle size of 100 nm or less in ethanol, which is a solvent for alcohol purification. Was obtained, and the present invention was completed.

In this tooth coating liquid, acrylic ester
It is essential to use an acrylic resin obtained by neutralizing a methacrylic acid ester-based copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol. Even if it is used alone or diluted, good results can be obtained in terms of dispersibility and stickiness, but it is used in combination with a resin such as shellac or vinyl acetate resin, which has good stickiness and glossiness, and has a proven safety record. It can also be used. In this case, the addition amounts of shellac and vinyl acetate resin are 5% to 30% in both cases. If it is less than 5%, the effect of improving the adhesion cannot be obtained, and if it exceeds 30%, the coating property is significantly impaired.

The amount of the acrylic resin obtained by neutralizing the acrylic acid ester / methacrylic acid ester copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol is Although depending on the type of pigment and the required amount, it is effective as a dispersant from about 0.01% or more. Below this, a stable dispersion effect cannot be obtained, or the required amount of pigment cannot be dispersed.

Acrylic resin obtained by neutralizing an acrylic ester / methacrylic ester copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol was added in a large amount. In this case, although water resistance, glossiness, and sedimentation stability of the pigment are excellent,
Since the stability with time as a coating liquid becomes slightly inferior, the coating film becomes too thick and easily peels off from the coating surface, the viscosity becomes high, and the coating property deteriorates. 40% is considered the maximum addition amount.

Amount of acrylic resin obtained by neutralizing an acrylic ester / methacrylic ester copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol Is practically 0.1% to 20%. This does not require a pigment, and when it is used as a transparent brightening agent when applied to teeth, the minimum resin blending amount that can confirm the gloss is 0.1.
%. Further, when a large amount of a pigment is dispersed in a large amount of resin, there is such an adverse effect that the viscosity becomes high, the coating property becomes poor, and the coating film becomes thick and easily peeled off from the coated surface. Excessive addition is not preferable.

Most preferred addition amount of acrylic resin obtained by neutralizing an acrylate / methacrylate copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol The range is 0.1% to 10%. Although the sticking property is insufficient with a low addition amount such as when using less than 1%, the dispersion stability of the pigment is improved, and when used in combination with shellac or vinyl acetate resin, which has a proven record in terms of safety, conventional products The same gloss and stickiness can be obtained. In addition, an acrylic acid ester / methacrylic acid ester-based copolymer is used as 2-amino-2methyl-
1.3 Propanediol or 2-amino-2methyl-
Acrylic resin neutralized with 1-propanol gives higher sticking properties than conventional products when added in an amount of 5% or more, but there is a difference in the amount of dispersed pigment, but if it exceeds 10%, applicability deteriorates. .

Ethanol is preferred as the main solvent for the tooth coating liquid of the present invention, but it is safe for the human body and is not
What kind of solvent can be used as long as it dissolves the acrylic resin obtained by neutralizing the methacrylic acid ester copolymer with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol I don't mind. 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, zinc sulfide, lithopone, cadmium. Yellow, vermilion, gadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, ultramarine blue, lead white,
Inorganic pigments such as navy blue, manganese violet, aluminum powder, brass powder, CI16185, CI45430, CI16255,
CI45410, CI45440, CI45100, CI19140, C.
I.15985, CI42053, CI42090, CI73015, CI
15850, CI15585, CI15630, CI45170, CI15
800, CI15880, CI12120, CI45380, CI2610
0, 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,
Pearl pigments such as mascotite, pearl oyster shell powder, abalone shell powder and Takase shell powder can be used. Furthermore, due to its peculiarity of being used only on the 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, silica powder, fine silicic acid, light algae earth, talc, basic magnesium carbonate, alumina white, gloss white, satin white, tricalcium phosphate, hydroxy Even if apatite is used, a transparent and 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.

Titanium oxide is an excellent pigment for whitening teeth because it is white and has a high concealing property, but it has a large specific gravity of about 4 and is liable to settle, and the average temporary particle diameter is 200 nm.
In the coating solution in which the general material before and after is dispersed, the pigment will settle after long-term storage, but the tooth coating solution of the present invention has excellent redispersibility and easily returns to a uniform dispersion system by shaking. To do. Further, in the present invention, even when the titanium oxide is used, the sedimentation rate of the titanium oxide can be suppressed to a minimum by selectively using fine particle titanium oxide having an average primary particle diameter of 100 nm or less.

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 necessary, 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 those improving the water resistance at the interface with the gas and liquid (such as saliva) on the surface of the coating film. The fragrance can be expected to have an effect of masking an unpleasant odor when applied in the oral cavity, or conversely improving the usability. Further, for non-volatile surfactants and fragrances, and oils and fats and non-volatile hydrocarbons, acrylic acid ester / methacrylic acid ester copolymers can be used as 2-amino-2methyl-1.3 propane. Some of them are also useful as plasticizers such as acrylic resins, shellac and vinyl acetate resins neutralized with diol or 2-amino-2methyl-1-propanol, and the coating film is formed by the plasticizer exerting its effect to an appropriate degree. The brittleness is suppressed, the coating film is flexible and has high adhesion to teeth and excellent durability.

In the tooth coating liquid of the present invention, the acrylic acid ester / methacrylic acid ester copolymer is usually prepared with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol. Dissolve the acrylic resin soaked in ethanol, etc., and then add a pigment other than the pearlescent pigment, and perform dispersion treatment with a ball mill, bead mill, sand mill, roll mill, kneader, homogenizer, ultrasonic disperser, etc. to disperse the pigment. It is basically necessary to prepare a liquid, and further add a resin and a surfactant, a fragrance, a pearl pigment and a dispersion thereof as necessary in consideration of the performance as a tooth coating liquid such as adhesion. The reason for special treatment of pearlescent pigments is that they are fragile pigments and may lose their pearly luster when subjected to strong shearing. Therefore, a pigment which loses its properties due to shearing similarly needs to be handled with care like a pearl pigment.

[0016]

EXAMPLES Next, the present invention will be described in more detail with reference to examples. Since this example is a small-scale production in the laboratory, the above-mentioned preparation method was not adopted, and all the formulations except the pearl pigment were weighed at once and then stirred with a bead mill for 1 hour. (Magnetic stirrer was used in Example 4 and Comparative Example 4) The pearl pigment was added after the bead mill was finished, and the mixture was irradiated with ultrasonic waves for 15 minutes and stirred. Such a method is not industrially suitable because it is difficult to reproduce hue and viscosity, but there is no problem in terms of performance as a tooth coating solution.

Acrylic ester / methacrylic acid ester-based copolymer in the formulation of this example was neutralized with 2-amino-2methyl-1.3 propanediol or 2-amino-2-methyl-1-propanol. Resins are "Plus size L53P" and "Plus size L53"
Supplied as a 50% ethanol solution by Mutsou Chemical under the name "D". (Example 1) Ethanol 47.5% Rack Coat 50EDS (shellac 50% ethanol solution; Nippon Shellac trade name) 50.0% Titanium oxide CR-50 (titanium oxide of normal particle size; Ishihara Sangyo trade name) 0.5 % Plus size L53P 1.0% MOUTHWASH FLAVOUR (PEPPER MINT CR) 3272-B (fragrance; ART PER FUMARY brand name) 0.5% Mica titanium SP-350 (Tayka brand name) 0.5% (Example 2) ) Ethanol 83.0% Transparent white rack dry product GBN-D (Shellac; Gifu shellac product name) 5.0% MT-500SA (Ultrafine titanium oxide (primary particle diameter 35 nm); Takeca product name) 1.5% plus Size L53D 10.0% 1-menthol (Japanese Pharmacopoeia) 0.5% (Example 3) Ethanol 63.6% Ethnyl C-3 (vinyl acetate resin; product) Chemical industry trade name) 30.0% Plus size L53D 0.2% Titanium Oxide P-25 (Ultrafine titanium oxide (primary particle size 30 nm; Nippon Aerogel brand name) 1.0% Toothpast flavor M8263 (fragrance; Takasago fragrance Trade name) 0.2% MEARLMAID OL (paste containing 20% fish scale foil; The Mearl Corporation trade name) 5.0% (Example 4) Ethanol 59.9% Rack coat 50EDS 20.0% Plus size L53P 20.0 % Methyl salicylate 0.1% (Comparative Example 1) Ethanol 46.5% Rack coat 50EDS 52.0% Titanium oxide CR-50 0.5% MOUTHWASH FLAVOUR (PEPPER MINT CR) 3272-B 0.5% Mica titanium SP -350 0.5% (Comparative Example 2) Ethanol 88.0% Transparent white rack dry product GBN-D 10.0% MT-500 A 1.5% l-menthol 0.5% (Comparative Example 3) Ethanol 63.8 Ethnyl C-3 30.0% Titanium Oxide P-25 1.0% Toothpast flavor M8263 0.2% MEAR LMAID OL (fish scale Paste containing 20% of foil; The Mearl Corporation trade name) 5.0% (Comparative example 4) Ethanol 59.9% Rack coat 50EDS 20.0% Methyl salicylate 0.1%

The following tests were carried out using Examples 1 to 4 and Comparative Examples 1 to 4. Test 1--Redispersibility Test 1 (Settling Test) 10 cm of each of Examples 1 to 4 and Comparative Examples 1 to 4 was placed in a test tube with an inner diameter of 1 cm and a closed cap, and allowed to stand at room temperature for 1 month to form a precipitate and a supernatant. Measure the height of the interface. The higher the sediment, the bulkier the sediment, and the more likely it is to redisperse on shaking. Test 2--Redispersibility test 2 (actual use test over time) Examples 1 to 4 and Comparative Examples 1 to 4 were filled in the applicator of Fig. 1, left standing upward for one month, and then placed up and down. About 20 cm,
After applying vibration for about 1 minute at a speed of about 1 Hz, write on a glass plate, compare the initial drawing line with the hue and density, and visually judge the difference. {○} ... Almost unchanged. {△} ・ ・ ・ Slight change in hue or density {×} ・ ・ ・ Extremely thin or unwritable. {-} ...
Test that cannot be written from the beginning 3--Adhesion test Examples 1 to 4 and Comparative Examples 1 to 4 are filled in the applicator of FIG. 1 and applied to the upper and lower two front teeth of 20 monitors.
The change in the coating film was examined after 3 hours. {○} ... Almost no change. {△} ... There is a change but there is a coating film remaining. {X} ... Almost no coating film remains.

[0019]

[Table 1]

[0020]

As described above, according to the present invention, the dispersibility is good and the sticking property is good, and the applicability is good because it can be filled in a simple applicator.

[Brief description of the drawings]

FIG. 1 is an applicator filled with the coating liquids of Examples and Comparative Examples of the present invention.

[Explanation of symbols]

 1 coating part (brush) 2 mouthpiece (made of plastic) 3 liquid introduction part 4 outer shaft 5 valve 6 coating liquid 7 coating liquid storage pipe (inner shaft) 8 knock part 9 retaining lock 10 spring in valve 11 coating liquid storage pipe cap 12 valve seat 13 valve stem a sliding contact surface b 〃 c 〃 d 〃

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Taka Umeno Gunma Prefecture Fujioka City Tateishi 1091 Mitsubishi Pencil Stock Company Gunma Factory (72) Inventor Tomoko Hasegawa Gunma Prefecture Fujioka City Tateishi Mitsubishi Pencil Stock Company Gunma Factory (72) Inventor Kazuhiro Ami 1091 Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Stock Company Gunma Factory

Claims (7)

[Claims] 1. Ethanol and an acrylic acid ester / methacrylic acid ester type copolymer are treated with 2-amino-2methyl-
1.3 Propanediol or 2-amino-2methyl-
A tooth coating solution containing an acrylic resin neutralized with 1-propanol. 2. The tooth coating liquid according to claim 1, containing at least one kind of coloring pigment and extender pigment. 3. The tooth coating liquid according to claim 1, which contains shellac or vinyl acetate resin, or both. 4. At least 10 to 94., based on the total amount of liquid.
8% ethanol and 0.1% to 30% pigment content and 0.1
20% to 20% acrylic acid ester / methacrylic acid ester copolymer neutralized with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol % Tooth coating solution containing shellac. 5. The total amount of the liquid is at least 10 to 94.
8% ethanol and 0.1% to 30% pigment content and 0.1
20% to 20% acrylic acid ester / methacrylic acid ester copolymer neutralized with 2-amino-2methyl-1.3 propanediol or 2-amino-2methyl-1-propanol % Tooth coating solution containing butyl acetate resin. 6. The tooth coating liquid according to claim 2, wherein the pigment contains at least titanium oxide. 7. The tooth coating liquid according to claim 6, wherein the primary particle diameter of titanium oxide as a pigment is 100 nm or less on average.