JPH11335251A - Composition for oral cavity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having a proper adhesive strength to such an extent that the composition is not readily peeled by eating and drinking but readily removed if necessary. SOLUTION: This composition for the oral cavity contains (A) a polymer having one or more kinds of functional groups of formulas I to III and the like, 10,000-1,000,000 weight average molecular weight, >=1 g solubility in 100 g dehydrated ethanol at 20 deg.C, and <=10 g solubility in 100 g water at 20 deg.C, (B) a polymer having a polar functional group without the groups of formulas I to III and the like, 5,000-5,000,000 weight average molecular weight, >=1 g solubility in the dehydrated ethanol at 20 deg.C and <=10 g solubility in the water at 20 deg.C and, water and/or a lower alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an oral composition which is not easily peeled off at the level of eating and drinking, but can be easily removed when necessary, and is suitable for tooth coating.

[0002]

2. Description of the Related Art As a means for imparting aesthetics such as gloss and whiteness to teeth, a composition mainly composed of a special dental adhesive is applied to a tooth surface in a short time by irradiating ultraviolet rays or heating. What polymerizes a monomer etc. is known.
These coatings formed on the tooth surface have extremely high durability, have high adhesion strength so as not to peel off from the teeth for a long time, and it is very difficult to remove the coating from the teeth.
On the other hand, tooth makeup does not peel off easily when eating or drinking, but has an appropriate adhesive strength so that it can be easily removed when necessary. Therefore, it was very difficult to easily remove and change the coating like a nail polish while keeping the durability of the coating high. Further, in the method of polymerizing a monomer or the like in a short time using ultraviolet light or the like, it is difficult to control the adhesion strength and the degree of application.
Furthermore, the composition cannot be changed after coating, and tends to yellow over time, and the color tone and the like are insufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oral composition which does not easily peel off at the level of eating and drinking, but can be easily removed when necessary, and gives a good color tone. .

[0004]

Means for Solving the Problems The present inventors have found that an oral composition containing two kinds of polymers having specific functional groups in a molecule and water or a lower alcohol has a moderate adhesive strength. The present invention has been found to impart beauty to the teeth, such as gloss, and further has the effect of improving the acid resistance of the teeth and blocking external stimuli, and is also useful for preventing caries, hyperesthesia, etc. Was completed.

That is, the present invention provides the following (i)
~ (Vi)

[0006]

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Having a weight average molecular weight of 10,000 to 1,000,000, a solubility in 100 g of absolute ethanol at 20 ° C. of 1 g or more, and a solubility in 100 g of water at 20 ° C. of 10 g or less. (A) having a polar functional group other than (i) to (vi) in the molecule, having a weight average molecular weight of 50,000 to 5,000,000,
The present invention provides an oral composition comprising a polymer (B) having a solubility in 100 g of absolute ethanol at 100 ° C. of 1 g or more and a solubility in 100 g of water at 20 ° C. of 10 g or less, and water or / and a lower alcohol. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Polymer (A) used in the present invention
Is not particularly limited as long as it has the above functional groups (i) to (vi) in the molecule, has a film-forming property, and has the above-mentioned molecular weight, solubility in water and anhydrous ethanol.
(I) A homopolymer of the polymerizable unsaturated monomer (a) having at least one functional group of (vi), or a polymerizable unsaturated monomer (a) having these functional groups A copolymer with no polymerizable unsaturated monomer (b) is preferred.

As the polymerizable unsaturated monomer (a), the following formula (1)

[0010]

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[0011] (wherein, R ¹ represents a hydrogen atom or a methyl group, X is -COO- or -CON (R ²⁾ - (wherein R ² represents a a hydrogen atom or an alkyl group), A ¹ Represents a single bond or a hydrocarbon group which may be substituted by a halogen atom;
¹ represents a single bond, -OCO-, -COO-, -O-, -NHCO- or -CONH-, or A and B together form a polyalkyleneoxy group or a poly (alkyleneoxy) carbonyl group. And Y represents the functional group of (i) to (vi)).

In the above formula (1), X is more preferably -COO-. A ¹ is a single bond or a group having 1 to 2 carbon atoms.
A linear or branched alkylene group of 0 is more preferable, and B ¹ is more preferably a single bond or -OCO-. Further, A ¹ and B ¹ together form poly (alkyleneoxy)
It is also preferable to show a carbonyl group.

Further, these polymerizable unsaturated monomers (a)
As the monomer (b) that can be copolymerized with
Monomers which may have a functional group other than (vi) are mentioned. Here, examples of the functional group other than the above (i) to (vi) include one or more groups selected from phosphoric acid, sulfonic acid, phosphonic acid, and phosphinic acid residues. Further, as the other monomer (b), in addition to such a monomer having a phosphoric acid, sulfonic acid, phosphonic acid or phosphinic acid residue,
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) T-butyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ( Dimethylaminoethyl (meth) acrylate, diethylene glycol ethoxylate (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, dimethylacrylamide, N- [3- (dimethylamino) Propyl] acrylamide, (meth) a One kind of cyclohexyl acrylate, vinyl acetate (vinyl acetate), vinyl propionate, vinyl butyrate, styrene, 2-methylstyrene, N-vinyl-2-pyrrolidone, N-phenylmaleimide, N-laurinmaleimide, N-cyclohexylmaleimide The above can also be used. Examples of the monomer having a sulfonic acid residue include 2-acrylamido-2-methylpropanesulfonic acid and sodium styrenesulfonate. The content of these monomers (b) is preferably about 20 to 100% of the total monomers.

The weight average molecular weight of the polymer (A) is from 10,000 to 1,000,000, and more preferably from 15,000 to 50,000.
It is preferably 20,000 to 200,000. When the weight average molecular weight is less than 10,000, the strength of the coating formed on the teeth is low and the durability is not sufficient.

The polymer (A) has a solubility of 1 g or more in 100 g of absolute ethanol at 20 ° C.
It is necessary that the solubility in 100 g of water at 0 ° C. is 10 g or less. If the solubility in ethanol is less than 1 g, it is difficult to formulate it as a coating agent, and if the solubility in water exceeds 10 g, the water resistance is low and the durability of the film is not sufficient. 1 g solubility in ethanol
If it is above, there is no upper limit, and it may be water-insoluble as long as its solubility in water is 10 g or less. In addition,
The solubility of the polymer in ethanol is
20 g of the polymer is added to 00 g and stirred at 20 ° C. for 1 hour. Thereafter, the remaining polymer is separated by filtration, the weight is measured, and the amount of dissolution is determined from the difference.

The solubility of the calcium salt of the polymer (A) in 100 g of water at 20 ° C. is 2 g or less, particularly 0.5 g or less, and 100 g of absolute ethanol at 20 ° C.
Is preferably 1 g or more, more preferably 2 g or more. When the oral composition of the present invention is applied to teeth, the polymer (A) reacts with calcium on the surface of teeth and in saliva to form salts in the oral cavity. Therefore, even if the polymer is soluble in water of 10 g or more, it is preferable that the water solubility is reduced and the water resistance is improved by forming a salt with calcium to improve the durability in the oral cavity. By having such solubility characteristics, the oral composition of the present invention can be imparted with appropriate durability and removability when trying to remove the composition. The solubility of the calcium salt of the polymer in ethanol is determined by adding an equimolar amount of calcium chloride to the carboxyl group or the phosphate group of the polymer to the polymer solution prepared by the above method.
After stirring at 20 ° C. for 1 hour, the precipitated polymer is separated by filtration, weighed, and the amount of dissolution is determined from the difference.

Further, the polymer (A) preferably has an acid value of 0.1 or more, particularly preferably 0.1 to 700, from the viewpoint of adhesion to teeth and durability of the coating. When the polymer (A) has phosphoric acid, sulfonic acid, phosphonic acid or phosphinic acid, the phosphorus content is preferably 0.1 to 50 mol%, particularly preferably 0.5 to 25 mol%.

The polymer (A) is contained in the oral composition in the form of 1
It is preferred that the compounding amount be from 70 to 70% by weight, especially from 5 to 40% by weight.

The polymer (B) used in the present invention has a polar functional group other than the above (i) to (vi) in the molecule and has the above-mentioned molecular weight, solubility in water and absolute ethanol. Although not particularly limited, a polymer having one or more polar groups such as phosphoric acid, carboxylic acid, and sulfonic acid residues in the molecule is preferable, and a polymer that improves coating durability by blending with polymer (A) is particularly preferable.

Specifically, methacrylic acid / methyl methacrylate copolymer, N-methacryloyloxyethyl-
N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer, methyl methacrylate / butyl methacrylate / dimethylaminoethyl methacrylate copolymer, acrylic resin,
Vinyl acetate / vinyl pyrrolidone copolymer, acrylic acid
Ethyl acrylate-Nt-butyl acrylamide copolymer, acrylic acid / methacrylic acid / ethyl acrylate /
Methyl methacrylate copolymer, acrylic acid / acrylic acid ester / octylacrylic acid copolymer, vinyl methyl ether / monoethyl maleate copolymer, acrylic acid / acrylic acid ester / methacrylic acid ester copolymer, polyvinylpyrrolidone, chloride A dimethyldiallylammonium / acrylic acid copolymer is exemplified. In addition, as these commercial products, Eudragit S-100
(Manufactured by Rohm Pharma), Yuka Former SM (manufactured by Mitsubishi Chemical), Eudragit E-100 (manufactured by Rohm Pharma), Plus Size L9948B (manufactured by Yoyo Kagaku Kogyo), Rubiset CA66 (manufactured by BASF), Ultra Hold (BASF) Amerhold DR2
5 (AMERCHOL), Amphomer (NA
TIONAL STARCH), Gantrez
ES225 (manufactured by Daicel), GK707 (manufactured by Goyo Chemical Industry), Luviskol K17 (manufactured by BASF), Marquart 280 (manufactured by CALGON)
Etc. can be used.

Of these, methacrylic acid / methyl methacrylate copolymer, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer and acrylic resin are particularly preferred. preferable.

The weight average molecular weight of the polymer (B) is 0.1.
50,000 to 5,000,000, more preferably 50,000 to 1
It is 100,000, particularly preferably 10,000 to 300,000. If the weight average molecular weight is less than 50,000 or more than 5,000,000, the effect of improving the durability of the film by blending with the polymer (A) cannot be obtained, and conversely, the strength of the film is reduced, resulting in insufficient durability.

The polymer (B) is a polymer (A)
Similarly to above, the solubility in 100 g of absolute ethanol at 20 ° C. must be 1 g or more, and the solubility in 100 g of water at 20 ° C. should be 10 g or less.

The polymer (B) contains 1
It is preferred that the compounding amount be from 70 to 70% by weight, especially from 5 to 40% by weight. The compounding weight ratio of the polymer (A) to the polymer (B) is 9.9: 0.1 to 1: 9, particularly 9.5: 0.5.
4: 6, more preferably 9.5: 0.5 to 5: 5.

The oral composition of the present invention is prepared by mixing water or a lower alcohol with the polymer (A) and the polymer (B) to form a dispersion. Here, the lower alcohol is C
_{It is} a linear or branched saturated alcohol of _1-5 , among which ethanol and isopropyl alcohol are preferable, and ethanol is particularly preferable. In addition, two or more selected from water and lower alcohols can be used in combination. Water or lower alcohols constitute 30 to 98% by weight of the total composition, especially 50 to 95%.
It is preferable to mix by weight%.

The oral composition of the present invention preferably contains titanium mica and / or titanium oxide for the purpose of imparting aesthetics and gloss to the teeth.

Titanium mica preferably has an average particle size of 1 to 200 μm from the viewpoint of aesthetics and gloss (gloss).
0 μm is particularly preferred. Titanium oxide also preferably has an average particle size of 5 nm to 5 μm, and preferably 10 nm to 0.5 μm.
m is particularly preferred. Titanium mica and titanium oxide may be used alone or in combination.

Since such mica titanium and / or titanium oxide can be uniformly dispersed in the oral composition, it is preferably added as a powder. The amount of these powders to be added to the composition for oral cavity should be set at 0.
It is preferably 1 to 10% by weight, more preferably 0.2 to 5% by weight.
% By weight.

The polymer (A) and the polymer (B)
And the mixing weight ratio of mica titanium and / or titanium oxide are 1: 0.0 from the viewpoint of gloss imparting property and uniform coating property.
1 to 1: 1 is preferred.

In addition to these powders, fish scale foil, shell powder, etc., and various pigments and dyes for toning can also be appropriately blended.

In the present invention, various powders can be added as required. For example, α-quartz, silica, alumina, hydroxyapatite, calcium carbonate, fluoroaluminosilicate glass, barium sulfate, zirconia, glass, ultrafine silica, and an organic composite powder containing an organic component and an inorganic component can be used. Further, polymethyl methacrylate, a copolymer of methyl methacrylate and a crosslinkable monomer, a polymer powder of polystyrene, polyvinyl chloride or the like is added as required. Such glass includes silica glass,
Examples include soda quartz silicate glass, borosilicate glass, barium glass, strontium glass, zinc glass, lanthanum glass, yttria glass, barium boroaluminosilicate glass, synthetic silica, and titanium silicate glass.

The oral composition of the present invention includes various known components which can be used for the oral cavity within the range not impairing the effects of the present invention, such as sodium monofluorophosphate, tin fluoride, and sodium fluoride. Disinfectants such as chlorhexidine and its salts; pH adjusters such as sodium hydroxide; enzyme agents such as dextranase; sodium chloride;
Anti-inflammatory agents and blood circulation promoters such as crude drugs; sweeteners such as saccharin sodium; preservatives such as p-hydroxybenzoic acid; coloring agents and pigments such as titanium dioxide; and fragrances such as peppermint oil can be appropriately added.

The oral composition of the present invention can be produced by a conventional method. That is, for example, it is obtained by mixing the polymer (A), the polymer (B) and a solvent, and if necessary, the powder and a thickener such as ethyl cellulose.

The viscosity of the oral composition of the present invention when applied to teeth is preferably 2 to 500 cp, particularly preferably 5 to 200 cp. If the viscosity is less than 2 cp, the agent may drip in or out of the mouth, and if it is more than 500 cp, the agent does not spread well, making it difficult to apply the agent uniformly on the tooth surface. . Here, the viscosity of the composition is measured at 20 ° C. with a B-type viscometer.

The oral composition of the present invention is applied to teeth by a conventional method, the solvent component is evaporated, and the composition is adhered to teeth before use.
The oral composition adhered to the teeth can be easily removed using ethanol or the like.

[0036]

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Production Example 1 170.0 g of dimethoxyethane, 15.2 g of ethyl methacrylate, 20.6 g of t-butyl methacrylate were placed in a 500 ml separable flask to which a stirrer, a condenser, a dropping funnel and a nitrogen inlet were connected. 4-methacryloyloxytrimellitic anhydride (following formula (a-1)) 20.3
g, nitrogen gas is supplied at a flow rate of 1.5 L / min.
Bubble for minutes. Next, this monomer solution was heated to 60 ° C. in an oil bath with stirring, and then 2,2′-azobis (2,2
A solution of 0.10 g of 4-dimethylvaleronitrile) dissolved in 10.0 g of dimethoxyethane is put into a dropping funnel,
It was dropped into the monomer solution over 30 minutes. Then 60 ° C
For 4 hours and at 75 ° C. for 4 hours. Next, 5 L of ethanol / water = 2/1 (wt ratio) was used as a reprecipitation solvent, followed by purification twice and drying at 60 ° C. for 6 hours. The obtained polymer (polymer 1) had a weight average molecular weight (GPC, in terms of polystyrene, the same applies hereinafter) of 75,000 and an acid value of 104 KOHmg / g.
Met.

Hereinafter, the polymer 2 shown in Table 1 was prepared in the same manner.
~ Polymer 7 was produced. Table 2 shows the properties of the obtained polymer.

[0039]

[Table 1]

[0040]

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[0041]

[Table 2]

Examples 1 to 15 and Comparative Examples 1 and 2 Each component having the composition shown in Table 3 was mixed to prepare an oral composition. Table 4 shows the properties of the polymer (B).

[0043]

[Table 3]

[0044]

[Table 4]

Test Example 1 A test for peelability by eating and drinking was performed. The panelists were divided into groups of seven, and at 9 am the oral composition was applied to the entire surface of the six upper front teeth and a photograph of the front teeth was taken. At 10 am, ingest 200 ml of water, and at 0 pm eat and drink 1 commercial hamburger, 1 commercial fried chicken, 100 g of lettuce and tomato salad, 1 steamed potato, and 200 ml of commercial oolong tea. Sometimes 200 ml of water
Was ingested. Then, a photograph of the front teeth was taken at 6:00 pm, and the degree of the remaining of the oral composition on the teeth was determined based on the following criteria by comparing with a photograph taken at 9:00 am. The results are shown in Table 5 as average points.

(Evaluation criteria) 3 points: no peeling at all 2 points: only the tip of the tooth peeled 1 point: less than 1/4 peeled 0 point: 1/4 or more peeled

[0047]

[Table 5]

From Table 5, it was found that the oral composition of the present invention was hardly peeled off even after eating and drinking.

Test Example 2 Panavia EX (manufactured by Kuraray Co., Ltd.) as a dental adhesive was applied to bovine teeth according to a conventional method, and the compositions of Examples 1 to 15 were similarly applied to bovine teeth. Thereafter, the sample was immersed in artificial saliva (Salibate, manufactured by Teijin Limited) at 36 ° C. for 24 hours, and then subjected to a removal test using absorbent cotton containing ethanol. The dental adhesive could not be removed at all by ethanol, but all the oral compositions 1 to 15 of the present invention could be completely removed.

Test Example 3 In the demineralization of a tooth by an acid, hydroxyapatite (HAP) is eluted from enamel on the tooth surface. Therefore, the presence or absence of demineralization of teeth by acid can be determined by quantifying the eluted phosphate ions. After closing the pulp cavity of bovine teeth with Panavia EX (manufactured by Kuraray), which is a dental adhesive, the oral compositions 1 to 15 of the present invention were applied to the entire bovine teeth. After coating and drying, the coating was immersed in artificial saliva (Salibate, Teijin) at 36 ° C. for 6 hours, and brushed 10 times with a commercially available toothbrush under a load of 400 g.
Next, each bovine tooth was treated with 0.1 M lactate buffer (pH 4) 5
After immersion in 0 ml at 36 ° C., the phosphate ions in the lactate buffer were colorimetrically measured using P-test Wako (manufactured by Wako Pure Chemical Industries, Ltd.) for measuring inorganic phosphorus. Comparative Examples were the bovine teeth (untreated) whose pulp cavity was merely closed and Comparative Examples 1 and 2. Table 6 shows the results. As a result, Examples 1 to 1
No phosphate ion was detected in any of the lactate buffers in which the bovine teeth coated with No. 5 were immersed. Therefore, it was found that the oral composition of the present invention can impart acid resistance to teeth.

[0051]

[Table 6]

[0052]

The oral composition of the present invention is suitably used for coating teeth, does not peel off easily by eating or drinking, but has an appropriate adhesive strength which can be easily removed when necessary. It has the effect of imparting the beauty of gloss and the like, and also has the effect of improving the acid resistance of teeth and blocking external stimuli, and is also useful for preventing caries, hyperesthesia, and the like.

Claims (4)

[Claims] 1. The following (i) to (vi) in a molecule: Having at least one kind of functional group represented by the formula, having a weight average molecular weight of 10,000 to 1,000,000,
(A) having a solubility in water of 1 g or more and a solubility in water of 100 g at 20 ° C. of 10 g or less, having a polar functional group other than (i) to (vi) in the molecule and having a weight average molecular weight of 0.1 g. Oral cavity containing a polymer (B) having a solubility in 100 g of anhydrous ethanol at 20 ° C. of 1 g or more and 10 g or less in 100 g of water at 20 ° C., and water or / and a lower alcohol. Composition. 2. The oral composition according to claim 1, wherein the blending weight ratio of the polymer (A) and the polymer (B) is from 9.9: 0.1 to 1: 9. 3. The oral composition according to claim 1, further comprising titanium mica and / or titanium oxide. 4. A polymer (A) and a polymer (B),
The mixing weight ratio with mica titanium and / or titanium oxide is
The oral composition according to claim 3, wherein the ratio is 1: 0.01 to 1: 1.