JPH05139943A - Composition for oral cavity for suppressing coloring of tooth - Google Patents

Abstract

PURPOSE:To obtain a composition for oral cavity effective for suppressing coloring of teeth, containing a composite material prepared by coating the surface of a water-insoluble substrate with a quaternary nitrogen-containing water-insoluble polymer. CONSTITUTION:The surface of a water-insoluble substrate such as calcium hydrogenphosphate or polystyrene is coated with a quaternary nitrogen- containing water-insoluble polymer (e.g. poly[vinylbenzyldimethyllalurylammonium chloride]) having about 1,000-1,000,000 molecular weight to give a composite material. A composition for oral cavity comprising 0.01-50wt.% based on the whole amount of the composition of the composite material as an active ingredient is prepared. This composition can be prepared into a dosage form such as dentifrice (e.g. toothpaste, tooth powder, liquid dentifrice or mouthwash), a pasty composition (e.g. ointment or gingiva massaging cream), chewing gum, froth or coating for toothbrush. The composition can remove colored deposit without damaging cement and dentine on the surface of root.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oral composition which is effective in suppressing tooth coloring.

[0002]

2. Description of the Related Art Tooth coloring is caused by adhesion of colored deposits to teeth, and removal and inhibition of the colored deposits can be achieved by physically abrading the teeth with an abrasive compound conventionally used in toothpaste. The method of removal is the main one.

[0003]

However, although an abrasive having a high polishing power has a high ability to remove colored deposits, it may cause cement root or dentin on the root surface depending on the wrong brushing method such as horizontal polishing. On the other hand, it may promote damage.
Therefore, there is a demand for a method capable of removing colored deposits regardless of the polishing power. As such, it has been proposed to add polyvinylpyrrolidone, polyethylene glycol and the like to the oral composition, but the effect of removing the colored deposits is not sufficient.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of such circumstances, the mechanism of action is not clear, but the surface of a water-insoluble substrate is a water-insoluble polymer having a quaternary nitrogen. It has been found that the composite coated with (1) extremely effectively removes the colored deposits on the teeth and suppresses the coloring of the teeth, thus completing the present invention.

That is, the present invention provides an oral composition for suppressing tooth coloring, which comprises, as an active ingredient, a complex in which the surface of a water-insoluble substrate is coated with a water-insoluble polymer having a quaternary nitrogen. Is provided.

In the present invention, the water-insoluble polymer having a quaternary nitrogen used for coating the surface of the water-insoluble substrate has a molecular weight of about 1,000 to 1,000,000, preferably
The thing of about 5000 to 800,000 is mentioned. Examples of the water-insoluble polymer having quaternary nitrogen include those represented by the general formula:

[0007]

[Chemical 1]

[Wherein A is

[0009]

[Chemical 2]

Where l is 20 to 2000, and n is 100
An integer of 0 or more, X and Y are the same or different anions, R is an alkyl group having 6 to 18 carbon atoms, m is an integer of 2 to 10], quaternary ammonium type, betaine type, pyridyl Examples include water-insoluble polymers having quaternary nitrogen of pyridinium type, diamine type or ether type.

Specific examples of such a polymer include poly
[Vinylbenzyl dimethyl lauryl ammonium chloride], poly [vinyl benzyl stearyl betaine], poly [vinyl benzyl lauryl pyridyl pyridinium chloride], poly [vinyl benzyl lauryl diammonium chloride] and poly [vinyl benzyl cetyl ammonyl hexyl ether] ..

The water-insoluble substrate coated with the water-insoluble polymer having quaternary nitrogen is not particularly limited, but inorganic powders such as calcium hydrogen phosphate, calcium carbonate, alumina, silicic acid anhydride, zeolite and polystyrene, Granules such as organic powders of polyethylene, polymethylmethacrylate, etc., or fibrous forms such as nylon floss can be used.

To coat the surface of these water-insoluble substrates with the water-insoluble polymer having quaternary nitrogen, for example, the following method is adopted.

[0014]

[Chemical 3]

First, the product (B) is obtained by the reaction represented by the reaction formula (1). The compound (H) is usually about 1.0 to 2.5 times mol, preferably about 1.1 to 2.1 times the compound (P).
It is better to carry out a double molar reaction. The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60 to 110 ° C. being suitable. The product (B) can be purified by a method such as concentration, distillation and recrystallization.

Next, by the reaction represented by the reaction formula (2),
A product (PCS) and a product (PCSDB) are obtained.
The polymerization of reaction formula (2) can be carried out by a usual method such as suspension polymerization, solution polymerization or bulk polymerization, and the obtained polymer can be purified by a method such as reprecipitation or washing.

Next, the reaction represented by the reaction formula (3) is carried out on the surface of the water-insoluble substrate to obtain the target complex.
In the reaction formula (3), the compound (PCS) or (P
Compound (B) is usually used in an amount of about 0.02 to 0.15 equivalent, preferably about 0.05 to 0.10 per 1 equivalent of chlorine in CSDB).
Equivalent reaction is preferred. The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60-100 ° C. being suitable.

When a water-insoluble polymer in which the substituent represented by A in Chemical Formula 1 is other than the substituent represented by Chemical Formula 3 is used, coating can be performed in the same manner.

The oral composition of the present invention comprises the composite thus obtained, in which the surface of the water-insoluble substrate is coated with the water-insoluble polymer having a quaternary nitrogen, based on the total amount of the composition. 01 to 50% by weight, preferably 0.1 to 10% by weight
Compound.

The oral composition of the present invention may be prepared by a conventional method such as toothpaste (eg toothpaste, powder toothpaste, water toothpaste, mouthwash, etc.), paste composition (eg ointment, gingival massage cream, etc.), chewing gum. It may be in the form of coating such as floss or toothbrush, and in addition to the above-mentioned components, the following components may be appropriately added depending on the form of the composition.

For example, as the nonionic surfactant, a fatty acid ester of sugar or sugar alcohol, wherein the fatty acid residue has 12 to 18 carbon atoms and the average degree of esterification is 1.1 to 2.5, preferably Can use 1.2 to 1.9. Examples of the fatty acid ester of sugar or sugar alcohol include sucrose fatty acid ester, maltose fatty acid ester, maltitol fatty acid ester, maltotriitol fatty acid ester, maltotetriitol fatty acid ester, maltotetriitol fatty acid ester, maltopentay. Examples thereof include tall fatty acid ester, maltohexaitol fatty acid ester, maltoheptitol fatty acid ester, sorbitan fatty acid ester, lactose fatty acid ester, and lactitol fatty acid ester.

As the nonionic surfactant, polyoxyethylene sorbitan monolaurate,
Polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil such as polyoxyethylene fatty acid ester, lauric acid mono- or diethanolamide and other fatty acid diethanolamide, fatty acid monoglyceride, polyoxyethylene higher grade Alcohol ethers, polyoxyethylene polyoxypropylene fatty acid esters and the like can also be used.

As the anionic surfactant, for example, a water-soluble salt of a higher alkyl sulfate ester whose alkyl group has 8 to 18 carbon atoms such as sodium lauryl sulfate, lauroyl sarcosinate, sodium myristyl sulfate, and α-olefin. Carbon number of fatty acid group such as sulfonate, sodium lauryl monoglyceride sulfonate is 1
Water-soluble salts of higher fatty acid monoglyceride sulfonates of 0-18, higher fatty acid sodium monoglyceride monosulfate, sodium-N-methyl-N-palmityl taurate, sodium-N-lauroyl-β-alanine, sodium-N-long chain An acyl basic amino acid or the like is used.

Further, as the amphoteric surfactant, for example,
2-Alkyl-N-carboxymethyl-N-hydroxylethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, lauryldimethylaminoacetic acid betaine and the like are used.

These surfactants may be used alone or in combination of two or more. Also,
The content of the surfactant is usually 0.0 based on the entire composition.
It is 1 to 5% by weight, preferably 0.05 to 3% by weight.

The oral composition of the present invention further includes menthol carboxylic acid, anethole, eugenol, methyl salicylate, limonene, ocimene, n-decyl alcohol, citronellol, α-terbineol, methyl acetate, citronellyl acetate, methyl. Eugenol, cineole, linalool, ethyl linalool, wanilin, thymol, spearmint oil, peppermint oil, lemon oil, orange oil, sage oil, rosemary oil, cinnamon oil, pimento oil, cinnamon oil, perilla oil, wintergreen oil, cloves Fragrances such as oil and eucalyptus oil, individually or in combination, are 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the whole composition.
Can be mixed to some extent. Further, 0.01 to 1% by weight, and preferably 0.05 to 5% by weight of a sweetener such as saccharin sodium, stevioside, neoheshelidyl dihydrochalcone, glycyrrhizin, perillartine, thaumatin, asparatyl phenylalanine methyl ester and p-methoxycinnamic aldehyde. 0.5% by weight can be added.

For example, in the case of a paste composition such as an ointment, as a binding agent, carrageenan, sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, cellulose derivatives such as sodium carboxymethylhydroxylethylcellulose, and alkali metal alginates such as sodium alginate. , Propylene glycol alginate, xanthan gum, gums such as tragacanth gum, karaya gum, and arabic gum, polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer, synthetic binders such as polyvinylpyrrolidone, silica gel, aluminum silica gel, bee gum, inorganic such as lavonite One or two or more binders and the like may be blended. The compounding amount thereof is usually 0.3 to 5% by weight.

Further, in the production of a paste-like or liquid oral composition, sorbit, glycerin,
Ethylene glycol, propylene glycol, 1,3-
One kind or two or more kinds of butylene glycol, polyethylene glycol, polypropylene glycol, xylit, maltite, lactit and the like may be blended. The blending amount of these is usually 10 to 70% by weight.

In the case of toothpaste, dicalcium phosphate dihydrate and anhydride, monobasic calcium phosphate, tribasic calcium phosphate, calcium carbonate, calcium pyrophosphate, aluminum hydroxide, alumina, silicic acid anhydride, silica gel, One or more of aluminum silicate, insoluble sodium metaphosphate, tribasic magnesium phosphate, magnesium carbonate, calcium sulfate, polymethylmethacrylate, bentonite, zirconium silicate, synthetic resin and the like can be blended, and can be blended. The amount is usually 5.0
˜90% by weight, and in the case of toothpaste 5 to 60% by weight.

In the present invention, as the active ingredient, further, cetylpyridinium chloride, chlorhexidine salts, bactericides such as triclosan, dextranase,
Amylase, protease, mutanase, lysozyme,
Enzymes such as lytic enzymes (Litech Enzyme), alkali metal monofluorophosphates such as sodium monofluorophosphate, potassium monofluorophosphate, sodium fluoride, fluorides such as stannous fluoride, tranexamic acid and epsilon aminocaproic acid, aluminum Chlorhydroxy allantoin, dihydrocholesterol, glycyrrhizin salts, glycyrrhetinic acid, glycerophosphate, chlorophyll, sodium chloride, caropeptide,
One type or two or more types of active ingredients such as a water-soluble inorganic phosphate compound may be blended.

[0031]

EXAMPLES Next, the present invention will be described more specifically by showing experimental examples and examples, but the present invention is not limited thereto. All "%" are% by weight. Experimental Example 1 A person's tooth enamel was etched with 0.1N hydrochloric acid for 2 minutes,
Rinse with water, then stir with a dilute solution of stannous fluoride,
It was wiped dry and finally exposed to a stream of hydrogen sulfide gas to deposit a stannous sulfide brown deposit. Gardner Automatic Color Difference Meter (Gardner Automatic Color Di)
fference meter). Next, apply a dispersion liquid of the following composition on this surface, and use a mechanical brushing machine to obtain 3.0
00 back-and-forth polishing, and the remaining stain was measured with a measuring instrument. Finally, dental pumice was used to completely remove the remaining stains and the reflectance of the surface was read. The dirt removing ability is expressed by the following equation. % Of dirt removed = {(Rd 3,000 strokes-Rd in
itial) / (Rd pumiced-Rd initial)} × 100 Rd initial, Rd 3,000 strokes and Rd pumiced
Is the reflectance value measured on the first dirty surface,
It is the value after 3,000 round trips and the value after removing the remaining dirt with pumice stone. The compositions of the composites used in the experiment are shown in Tables 1 and 2, and the results are shown in Table 3.

[0032]

[Table 1]

[Table 2]

[0033]

[Table 3]

Example 1 In the composite 1 of Table 1, the polystyrene powder was replaced with a nylon thread, and the compound (B) and the compound (PCS) were polymerized on the surface of the nylon thread to obtain a coated nylon floss.

Example 2 A toothpaste was produced according to a conventional method according to the following formulation. Dicalcium phosphate dihydrate 50% Glycerin 20 Sodium carboxymethylcellulose 1.0 Fragrance 1.0 Sodium lauryl sulfate 1.0 Complex 9 (Table 2) 1.0 Sodium saccharin 1.0 Sodium fluoride 1.0 Allantoin 1.0 Water adjusted to 100%

Example 3 A toothpaste was produced according to a conventional method according to the following formulation. Methylcellulose 3.0% Glycerin 30.0 Saccharin sodium 0.1 Fragrance 1.0 Chlorhexidine gluconate 0.01 Ethanol 3.0 Complex 5 (Table 1) 0.5 Methyl paraoxybenzoate 0.06 Prepared to 100% water.

Example 4 A gingival massage cream was produced according to a conventional method according to the following formulation. White petrolatum 8.0% Propylene glycol 4.0 Dextranase 1.0 Stearyl alcohol 8.0 Polyethylene glycol 4,000 25.0 Polyethylene glycol 400 37.0 Sucrose stearate 0.5 Complex 3 (Table 1) ) 2.0 Methyl paraoxybenzoate 0.1 Water Prepared to 100%

Example 5 A mouthwash was produced according to a conventional method according to the following formulation. Ethanol 10% Sodium saccharin 0.05 Perfume 1.0 Sodium monofluorophosphate 0.1 Chlorhexidine hydrochloride 0.01 Complex 8 (Table 2) 0.5 Sucrose palmitate 0.5 Methyl paraoxybenzoate 0.06 Prepared to 100% water

Example 6 A chewing gum was produced according to a conventional method according to the following formulation. Gum base Natural chicle 20 Vinyl acetate resin 30 Ester gum 10 Wax 15 Emulsifier 5 Complex 7 (Table 2) 20 100 g

[0040]

EFFECTS OF THE INVENTION According to the present invention, there is provided an oral composition for suppressing tooth coloring, which is capable of extremely effectively removing colored deposits on teeth without depending on the polishing force.

[Procedure amendment]

[Submission date] March 4, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

As the nonionic surfactant, polyoxyethylene sorbitan monolaurate,
Polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, fatty acid ethanolamide such as lauric acid mono- or diethanolamide, fatty acid monoglyceride, polyoxyethylene higher alcohol ether , Polyoxyethylene polyoxypropylene fatty acid ester and the like can also be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

As the anionic surfactant, for example, a water-soluble salt of a higher alkyl sulfate ester having an alkyl group having 8 to 18 carbon atoms such as sodium lauryl sulfate and sodium myristyl sulfate, an α-olefin sulfonate, and a higher fatty acid salt. Sodium monoglyceride monosulfate, sodium-N-methyl-N-palmityl tauride, sodium-N-lauroyl-β-alanine, lauroyl sarcosinate, sodium-N-long-chain acyl basic amino acid and the like are used.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

For example, in the case of a paste composition such as an ointment, as a binding agent, carrageenan, sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, cellulose derivatives such as sodium carboxymethylhydroxylethylcellulose, and alkali metal alginates such as sodium alginate. , Alginic acid propylene glycol ester, xanthan gum, gums such as tragacanth gum, karaya gum, arabic gum, polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer, synthetic binders such as polyvinylpyrrolidone, silica gel, aluminum silica gel, bee gum, inorganic such as laponite One or two or more binders and the like may be blended. The compounding amount thereof is usually 0.3 to 5% by weight.

Claims (1)

[Claims] 1. A composition for oral cavity for suppressing tooth coloring, which comprises a complex in which the surface of a water-insoluble substrate is coated with a water-insoluble polymer having quaternary nitrogen.