JP5402613B2 - Dentifrice composition - Google Patents

Description

  The present invention improves the ability to remove plaque by increasing the retention in the oral cavity of glucanase enzyme having a plaque-degrading action, and has excellent enzyme stability in the dentifrice composition, moldability of the dentifrice formulation, The present invention relates to a dentifrice composition that has good foaming and liquid separation stability over time, and can impart excellent antiseptic power.

  Glucanase enzyme has an action of chemically removing plaque by enzymatic degradation of water-insoluble glucan forming plaque, and is used in oral products as an active ingredient for preventing toothworm. In order to make the degradation by enzymatic reaction work more efficiently, it is effective to lengthen the action time of the enzyme, but in the oral cavity, most of the components are removed by rinsing after tooth brushing, and the function is not necessarily maximized. There has been a demand for a dentifrice composition that does not exhibit its limit and can provide higher activity.

  An enzyme composed of a protein has a higher-order structure including an active center which is a functional expression site, but has a property of being easily deactivated by the action of a denaturant such as temperature or a surfactant. The dentifrice composition contains sodium lauryl sulfate in many dentifrice compositions in order to ensure foaming when brushing, but sodium lauryl sulfate has a strong protein denaturing action and is a nonionic surfactant or It was necessary to use a plurality of stabilizers such as amino acids in combination. In addition, a dentifrice composition containing a large amount of a nonionic polymer as a binder may deteriorate the moldability of the preparation or cause liquid separation of the preparation when the temperature changes above 40 ° C.

  Furthermore, in order to ensure the preservative power of many of the dentifrice compositions, parabens such as methylparaben and butylparaben (paraoxybenzoic acid esters), quaternary ammonium type preservatives such as benzalkonium chloride and cetylpyridinium chloride are used. In recent years, compositions that do not contain preservatives are increasing from the viewpoints of simplifying the composition and reducing environmental impact.

  In addition, many dentifrice compositions contain sodium lauryl sulfate, which is an anionic surfactant, as a foaming agent, but sodium lauryl sulfate, which has a strong denaturing action, has a bactericidal action against bacteria. It also contributes to the antiseptic effect. On the other hand, a composition that does not contain an anionic surfactant such as sodium lauryl sulfate is suitable as an enzyme compounding composition because it is difficult to inactivate the enzyme. It is desirable to secure antiseptic power.

  As a technique for retaining a glucanase enzyme that decomposes and removes plaque in the oral cavity, a liquid oral composition containing a cationic polymer and an anionic water-soluble polymer in a specific mass ratio (see Patent Document 1), cationic A liquid oral composition containing a polymer and an organic acid or a water-soluble salt thereof (see Patent Document 2) is known.

  However, in these techniques, a glucanase is used in a dentifrice composition such as a toothpaste, which contains a large amount of inorganic particles such as an abrasive and contains an anionic surfactant such as sodium lauryl sulfate for the purpose of obtaining good foaming. A sufficient oral retention effect of the enzyme cannot be obtained, and there has been a problem that sufficient foaming cannot be obtained when an anionic surfactant is not blended. Moreover, about 1 to 3 mass% of anionic polymer is normally mix | blended with dentifrice compositions, such as toothpaste, as a binder, and it is difficult to always mix | blend with the specific mass ratio of patent document 1. FIG. there were.

  As an oral composition containing a cationic polymer, a fatty acid amidopropyl betaine, and a cellulose derivative, in addition to the above-mentioned patent document, for example, for oral cavity in which phase separation does not occur even when porous calcium carbonate is blended and the rheological properties do not change. Composition (see Patent Document 3), composition for oral cavity in which phase separation does not occur even when porous calcium carbonate is blended (see Patent Document 4), shape retention, dispersibility in the oral cavity, Rheological properties that do not cause phase separation even when blended with an oral composition (see Patent Document 5) that is superior in stability over time, such as without changing the taste of the juice after dentifrice and solid-liquid separation, and porous calcium carbonate Composition for oral cavity that does not change, oral composition having a high ratio of stain removal power to polishing power (see Patent Document 6), excellent caries preventive effect without containing fluoride Such as oral care products (see Patent Document 7) with have been proposed. However, in the technologies of these patent documents, there is no description of a configuration that satisfies all the essential configuration requirements related to the present invention. From these descriptions, the composition according to the present invention improves the ability to remove plaque by increasing the retention of the glucanase enzyme in the oral cavity, improves the enzyme stability in the dentifrice composition, and moldability of the dentifrice preparation Further, it is difficult to conceive that foaming during tooth brushing and liquid separation stability over time are improved, and there is no description reminiscent of the configuration and technical idea of the present invention.

  Furthermore, for example, Patent Documents 1 to 3 and 5 to 7 describe that condensed phosphate is blended in a dentifrice composition, but these techniques aim to ensure the antiseptic power of the enzyme blend composition. However, these techniques do not evoke the configuration and technical idea related to the present invention for improving the problem of antiseptic power.

  Accordingly, in a dentifrice composition containing a glucanase enzyme, the glucanase enzyme having a plaque degrading action improves the retention in the oral cavity and improves the plaque removal power, and has excellent enzyme stability in the dentifrice composition and a dentifrice formulation However, the conventional technology cannot satisfy all of these effects. However, the conventional technology cannot satisfy all of these effects.

JP 2001-240523 A JP 2001-316235 A Japanese Patent Laid-Open No. 10-330233 JP 2002-179540 A JP 2004-2476 A JP 2004-10576 A JP 2009-143874 A

  The present invention has been made in order to solve the above-mentioned problems. In a dentifrice composition containing a glucanase enzyme, the ability to remove plaque is improved by increasing the retention in the oral cavity of a glucanase enzyme having an action of degrading plaque. Another object of the present invention is to provide a dentifrice composition which is excellent in enzyme stability in a dentifrice composition and has good moldability of a dentifrice preparation, foaming at the time of toothbrushing and liquid separation stability over time. Furthermore, it aims at providing the dentifrice composition which provided the outstanding preservative power.

  As a result of diligent investigations to achieve the above object, the inventors of the present invention have added (A) a cationic polymer to 0.02 to 0.2% by mass of (B) a fatty acid in a dentifrice composition containing a glucanase enzyme. 0.4 to 1.6% by mass of fatty acid amidopropyl betaine having 12 to 14 carbon atoms, (C) 0.5 to 3% by mass of at least one selected from hydroxyethylcellulose, hydroxypropylmethylcellulose, and methylcellulose; In addition, by setting the mass ratio of component (C) / component (A) to 10 to 100, the retention of glucanase enzyme in the oral cavity is increased, the plaque removal power is improved, and the enzyme stability in the dentifrice composition In addition, the present inventors have found that moldability of dentifrice preparation, foaming at the time of tooth brushing and liquid separation stability over time can be obtained, and the present invention has been completed.

  Furthermore, by blending 0.1 to 2% by mass of (D) condensed phosphate, in addition to the above properties, the antiseptic power of the preparation is increased, leading to the completion of a dentifrice composition having an excellent antiseptic power. It was.

  More specifically, as a result of intensive studies on a dentifrice composition containing a glucanase enzyme having an excellent anti-worming function, the present inventors combined (A) to (C) in combination, and (C) By setting the ratio of component / component (A) within a specific range, the glucanase enzyme, which has the function of decomposing and removing plaque causing causative teeth, is sufficiently retained in the oral cavity to significantly improve plaque removal power. When it is collected on a toothbrush due to the high moldability of the dentifrice preparation, ensuring sufficient enzyme stability even in dentifrice compositions containing surfactants and many inorganic salts The dentifrice formulation, which is a thick emulsification dispersion system for maintaining the quality of the product, has lost its emulsification dispersion system over time. Found that even liquid separation occurs caused by Rukoto suppressed well, and have completed the present invention.

  Further, in a dentifrice composition that does not contain a preservative, it is useful to increase the amount of anionic surfactant having a bactericidal effect or to reduce the water activity of the composition. By properly blending the components (A) to (C) and blending the component (D), even if it is not based on these techniques, for example, a composition that does not blend preservatives, or sodium lauryl sulfate Sufficient antiseptic power can also be secured without blending an anionic surfactant such as.

Accordingly, the present invention provides the following dentifrice composition.
Claim 1:
To a dentifrice composition containing a glucanase enzyme, (A) a cationic polymer in an amount of 0.02 to 0.2% by mass, and (B) fatty acid amidopropyl betaine having a fatty acid having 12 to 14 carbon atoms in an amount of 0.4 to 1.6. 0.5% by mass to 3% by mass of at least one selected from mass%, (C) hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and methyl cellulose, and the mass ratio of (C) component / (A) component is 10-100. The dentifrice composition characterized by the above-mentioned.
Claim 2:
The dentifrice composition according to claim 1, wherein the cationic polymer (A) is hydroxyethylcellulose dimethyldiallylammonium chloride and / or O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride.
Claim 3:
Furthermore, the dentifrice composition of Claim 1 or 2 which mix | blended 0.1-2 mass% of (D) condensed phosphate.

  According to the present invention, in a dentifrice composition containing a glucanase enzyme, the retention of the glucanase enzyme in the oral cavity is enhanced, so that the plaque removal power is improved, the enzyme stability in the dentifrice composition is excellent, and the dentifrice It is excellent in moldability of the preparation, foaming at the time of tooth brushing and liquid separation stability over time, and can be excellent in the effect of preventing toothworms.

  Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention is prepared as a dentifrice such as a toothpaste, a liquid dentifrice, and a moisturized dentifrice, particularly a paste-like or gel-like dentifrice. The dentifrice composition containing a glucanase enzyme includes at least one selected from (A) a cationic polymer, (B) a fatty acid amidopropyl betaine having a fatty acid having 12 to 14 carbon atoms, (C) hydroxyethylcellulose, hydroxypropylmethylcellulose, and methylcellulose. A seed is blended, and the mass ratio of component (C) / component (A) is 10 to 100.

  Glucanase is an enzyme that degrades glucan, which is a constituent component of plaque, and suppresses plaque formation. Dextranase and mutanase can be preferably used as glucanase, and dextranase is effective in removing plaque. Is more preferred.

  As the dextranase, a dextranase obtained by a known method from a known dextranase-producing bacterium belonging to the genus Ketomium, Penicillium, Aspergillus, Spicaria, Lactobacillus, Servibrio, etc. can be preferably used. However, dextranase produced from other microorganisms can also be used, and dextranase manufactured by Daiichi Sankyo Propharma Co., Ltd. can be used as a commercial product.

  The mutanase is obtained by a known method from known mutanase producing bacteria such as Pseudomonas sp., Trichoderma harzianum, Streptomyces verensis, Aspergillus nidulans, Flavobacterium sp., Bacillus sp. However, mutanases produced from other microorganisms can also be used, and commercially available products such as those produced by Amano Enzyme Co., Ltd. can be used.

These dextranases and mutanases can be used alone or in combination of two kinds, and the total blending amount thereof is 1 to 200 units / g (U / g), particularly 2 to 50 units / g in the composition. In such a range of the blending amount, the retention of the enzyme in the oral cavity, the ability to remove plaque, and the enzyme stability are improved, and it is suitable for obtaining a good preparation. If it is less than 1 unit / g, sufficient plaque removal effect may not be obtained, and if it exceeds 200 unit / g, discoloration with time may occur and appearance stability may not be sufficient.
Usually, dextranase and mutanase are preferably 10,000 to 14,000 units / g, and when 13,000 units / g are used, the blending amount is 0.0077 to 1. 54% (mass%, the same applies hereinafter) is preferable. If it is less than 0.0077%, the plaque removal effect cannot be sufficiently obtained, and if it exceeds 1.54%, discoloration with time may occur and appearance stability may be poor.

  Here, 1 unit of dextranase is the amount of dextranase that produces free reducing sugar corresponding to 1 μmol of glucose per minute when an enzyme reaction is carried out using dextran as a substrate. The amount of mutanase that produces free reducing sugar corresponding to 1 μmol of glucose per minute when an enzyme reaction is carried out using mutan as a substrate.

  Examples of the cationic polymer (A) compounded in the dentifrice composition containing the glucanase enzyme include dimethyldiallylammonium, 2-hydroxy-3 (trimethylammonio) propyl as the cationic group, cellulose, dextran and the like. Examples include those added to derivatives, homopolymers of dimethyldiallylammonium chloride, and copolymers of dimethyldiallylammonium chloride and a polymerizable monomer having at least one ethylenically unsaturated hydrocarbon.

  Examples of such cationic polymers include hydroxyethyl cellulose dimethyl diallylammonium chloride, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose, and O- [2-hydroxy-3- (trimethylammonio) chloride. ) Propyl] dextran, homopolymer of dimethyldiallylammonium chloride, copolymer of dimethyldiallylammonium chloride and acrylic acid, copolymer of dimethyldiallylammonium chloride and acrylamide, ternary copolymer of dimethyldiallylammonium chloride, acrylic acid and acrylamide, etc. The nitrogen content is preferably 0.1 to 3%.

  Specifically, hydroxyethyl cellulose dimethyl diallylammonium chloride is obtained by graft polymerization of dimethyl diallylammonium salt to hydroxyethyl cellulose, and the viscosity of a 2% (mass%, hereinafter the same) aqueous solution is 50 to 2,000 mPa · s (BH Brook). Field type viscometer, rotor No. 2, 20 rotations, 21 ° C.) can be used, for example, Cellcoat L-200 (2% aqueous solution viscosity: 35 to 350 mPa · s, BH type Brookfield viscosity manufactured by Akzo Novell) Meter, rotor No. 2, 20 revolutions, 21 ° C., measurement time 1 minute), Cellcoat H-100 (2% aqueous solution viscosity: 500-2750 mPa · s, BH type Brookfield viscometer, rotor No. 2, 20 revolutions, 21 ° C., measurement time 1 minute) and the like.

  As O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride, viscosity can be measured with a 1% or 2% aqueous solution, and a viscosity of 5 to 800 mPa · s (BL viscometer, 2% aqueous solution). For example, Leogard KGP (2% aqueous solution viscosity: 5 to 50 mPa · s), Leogard G (2% aqueous solution viscosity: 100 to 600 mPa · s) manufactured by Lion Co., Ltd. ), Leoguard GP (2% aqueous solution viscosity: 100-600 mPa · s), Leoguard LP (2% aqueous solution viscosity: 300-800 mPa · s), etc., 1% aqueous solution with a viscosity of 500-2,600 mPa · s (BH Brookfield type) Viscometer, rotor No. 2, 20 revolutions, 25 ° C.), for example, Leo Guard MG manufactured by Lion Corporation (1% aqueous solution viscosity: 500~1,200mPa · s), Reogado MLP (1% aqueous solution viscosity: 1,000~2,600mPa · s) and the like can be used.

  In addition, as O- [2-hydroxy-3- (trimethylammonio) propyl] dextran chloride, the viscosity of a 2% aqueous solution is 1 to 1,000 mPa · s (BL viscometer, rotor No. 2, 30 rotations, 25 ° C), for example, those commercially available under the trade names of CDC, CDC-L, CDC-H, and CDC-NK from Meisho Sangyo Co., Ltd. can be used.

  The homopolymer of dimethyldiallylammonium chloride is trade name Marcoat 100, the copolymer of dimethyldiallylammonium chloride and acrylic acid is tradename Marcoat 280, the copolymer of dimethyldiallylammonium chloride and acrylamide is tradename Marcoat 550, and dimethyldiallylammonium chloride. As the three-component copolymer of acrylic acid and acrylamide, those available from Nalco Japan Co., Ltd. can be used as the trade name Marcote 3330.

  Among these cationic polymers, hydroxyethyl cellulose dimethyl diallylammonium chloride and O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose are particularly preferable because of their excellent plaque removal power. Can be used for

  (A) The compounding quantity of a cationic polymer is 0.02-0.2% of the whole composition, Preferably it is 0.05-0.10%. If it is less than 0.02%, the plaque removing power and the moldability of the dentifrice preparation may be lowered. If it exceeds 0.2%, the enzyme stability and the plaque removing power may be lowered.

The fatty acid amidopropyl betaine of the component (B) is a fatty acid having 12 to 14 carbon atoms, and examples thereof include lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine and the like.
These fatty acid amide propyl betaines are, for example, Amphitol 20AB (Kao Corporation), Amphitol 55AB (Kao Corporation), Softazoline LPB (Kawaken Fine Chemicals Corporation), TEGO BETAIN CK (Goldschmidt), NIKKOL AM-3130N ( They are available under trade names such as Nikko Chemicals Co., Ltd., and can be suitably used.

  (B) The compounding quantity of a component is 0.4 to 1.6% of the whole composition, Preferably it is 0.6 to 1.2%. If it is less than 0.4%, sufficient foaming may not be obtained in brushing when brushing the teeth, and the stability of the enzyme may be reduced. If it exceeds 1.6%, the ability to remove plaque may be reduced or the liquid may be stable. May be inferior.

Component (C), hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose are all nonionic cellulose derivatives.
As the hydroxyethyl cellulose, those having a viscosity in a 1% aqueous solution of 50 to 10,000 mPa · s (B-type viscometer, rotor No. 4, 30 rpm, 20 ° C., 2 minutes later) can be used. From the viewpoint of imparting moldability, 500 mPa · s or more is preferable, and from the viewpoint of solubility, 8,000 mPa · s or less is preferable. Specific examples of hydroxyethyl cellulose include those sold by Daicel Chemical Industries, Ltd. under product names such as SE600, SE850, and SE900.

  Hydroxypropyl methylcellulose having a viscosity of 100 to 12,000 mPa · s (20 ° C., 2% aqueous solution, Japanese Pharmacopoeia rotational viscometer method) can be used. 10000 mPa · s or higher is preferable, and from the viewpoint of solubility, 10,000 mPa · s or lower is preferable. As such hydroxypropyl methylcellulose, those sold by Shin-Etsu Chemical Co., Ltd. under the product names such as METOLOSE 60SH 4000, METOLOSE 60SH 10000, and METOLOSE 65SH 4000 can be used.

  As the methyl cellulose, those having a viscosity of 100 to 10,000 mPa · s (20 ° C., 2% aqueous solution, Japanese Pharmacopoeia rotational viscometer method) can be used. In particular, the above viscosity is 1,000 mPa in terms of imparting moldability. -The thing of s or more is preferable and the thing of 5,000 mPa * s or less is preferable from solubility. As such methylcellulose, those sold by Shin-Etsu Chemical Co., Ltd. under the product names such as METOLOSE SM 1500 and METOLOSE SM 4000 can be used.

  Component (C), hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose may be used alone or in combination of two or more, and the blending amount is 0.5 to 3% of the total composition, preferably 1.0 to 2.5%. If the blending amount is less than 0.5%, the moldability of the dentifrice preparation may be deteriorated, sufficient foaming may not be obtained in brushing during tooth brushing, or the liquid separation stability may be poor. If it exceeds 3%, the plaque removal ability may be lowered and the liquid separation stability may be poor.

  As for the blending ratio of the cellulose derivative as the component (C) and the cationic polymer as the component (A), the mass ratio of the component (C) / the component (A) is 10 to 100, preferably 20 to 50. If the blending ratio is less than 10, the stability of the enzyme and the moldability of the dentifrice preparation may be inferior, and if it exceeds 100, the plaque removal power and the moldability of the dentifrice preparation may be inferior.

  Furthermore, in addition to the above components (A) to (C), the composition of the present invention preferably contains (D) condensed phosphate, particularly pyrophosphate and tripolyphosphate. The antiseptic power can be increased by blending the component (D).

As the condensed phosphate, the following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
In other words, sodium pyrophosphate or potassium pyrophosphate having a polymerization degree n = 2, sodium tripolyphosphate or potassium tripolyphosphate having n = 3, sodium tetrapolyphosphate or potassium tetrapolyphosphate having n = 4, Linear polyphosphates such as sodium metaphosphate and potassium metaphosphate, and the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
In other words, cyclic polyphosphorus such as sodium trimetaphosphate and potassium trimetaphosphate having a polymerization degree m = 3, sodium tetrametaphosphate and potassium tetrametaphosphate having m = 4, and sodium hexametaphosphate and potassium hexametaphosphate having m = 6 Acid salts are used. These polyphosphates can be used singly or in combination of two or more, but in these, linear polyphosphates are preferable, and those having a polymerization degree of 2 ≦ n ≦ 50 are used. In particular, those having a degree of polymerization of 2 ≦ n ≦ 4 are more preferable from the viewpoint of solubility.

  As the component (D), pyrophosphate and tripolyphosphate are particularly preferable from the viewpoint of irritation to the oral mucosa. Pyrophosphate and tripolyphosphate are condensed phosphates generated by dehydration condensation of phosphoric acid. Pyrophosphate is a dimer and tripolyphosphate is a trimer. Examples of the salt include sodium, potassium, and magnesium salts, and sodium salts are preferred from the viewpoint of water solubility.

  Commercially available products can be used as the condensed phosphate, such as sodium pyrophosphate (anhydrous sodium pyrophosphate (Taihei Chemical Industrial Co., Ltd.)), sodium tripolyphosphate (sodium polyphosphate (Taihei Chemical Industrial Co., Ltd.)), etc. Is mentioned.

  (D) When mix | blending the condensed phosphate of a component, the compounding quantity is 0.1 to 2% of the whole composition, and 0.5 to 1.5% is especially suitable. If the blending amount is less than 0.1%, satisfactory antiseptic power may not be obtained, and if it exceeds 2%, although the antiseptic power is excellent, oral mucosal irritation becomes strong and the usability may be poor.

  In addition to the above-described components, the dentifrice composition of the present invention is usually added as an optional component to other known components such as abrasives, thickeners, binders, surfactants, sweeteners, and the like. Appropriate components such as a colorant, a colorant, a preservative, a pH adjuster, a fragrance, and a medicinal component can be blended within a range that does not impair the effects of the present invention.

As abrasives, abrasive silica, dibasic calcium phosphate dihydrate, dibasic calcium phosphate anhydrate, calcium pyrophosphate, aluminum hydroxide, alumina, titanium dioxide, polymethyl methacrylate, insoluble calcium metaphosphate, light calcium carbonate, heavy Examples include calcium carbonate, magnesium carbonate, tribasic magnesium phosphate, zeolite, zirconium silicate, hydroxyapatite, fluoroapatite, calcium deficient apatite, tricalcium phosphate, tetracalcium phosphate, and eighth calcium phosphate. Moreover, when mix | blending the condensed phosphate of (D) component, the abrasive | polishing agent which does not have a possibility of a calcium ion eluting is favorable, and a silica type abrasive | polishing agent is suitable.
The blending amount of the abrasive is preferably 10 to 60%, particularly 15 to 40% of the whole composition.

  As the surfactant, in addition to the fatty acid amidopropyl betaine of the component (B), other surfactants can be added. For example, as the amphoteric surfactant, for example, N-acylglutamate, 2-alkyl-N- Carboxymethyl-N-hydroxyethyl imidazolinium betaine etc. are mentioned. Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, alkyl glycosides, sucrose fatty acid esters, alkylol amides, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, fatty acid polyglyceryl, polyoxyethylene hardened castor Oil etc. are mentioned. The blending amount of these surfactants is preferably about 0 to 5% of the entire composition. In addition, when an anionic surfactant such as an alkyl sulfate such as sodium lauryl sulfate, polyoxyethylene alkyl sulfate, N-lauroyl taurine salt, lauroyl sarcosine salt or α-olefin sulfonate is added, the oral cavity of the enzyme The internal retention tends to decrease, and it is preferable not to add these anionic surfactants.

  As the thickener, sorbitol, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, polypropylene glycol, xylitol, maltitol, erythritol and other sugar alcohols and polyhydric alcohols may be blended. The blending amount of the thickener is usually 10 to 50%, particularly 20 to 40%.

  As the binder, other than the cellulose derivative of the component (C), for example, sodium polyacrylate, carrageenan, sodium carboxymethylcellulose, sodium alginate, xanthan gum and the like can be blended. The amount of these binders is preferably 0 to 1% of the entire composition.

  Medicinal components other than glucanase enzymes, such as fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, chlorhexidine, triclosan, isopropylmethylphenol, chlorhexidine salts Antibacterial substances such as sorbate, hinokitiol, azulene sulfonate, proteases such as protease, lysozyme, anti-inflammatory substances such as tranexamic acid, epsilon aminocaproic acid, allantoin, glycyrrhizic acid, glycyrrhetinic acid, sodium chloride, potassium nitrate, Inorganic salts such as aluminum lactate, zinc chloride, zinc citrate and strontium chloride, chelating compounds such as zeolite, copper chlorophyllin sodium, chlorophyll and glycerophosphate Colvin acid, various vitamins such as tocopherol acetate, pyridoxine, Japanese angelica root soft extract, Phellodendron bark extract, Kamirre, clove, rosemary, scutellaria root, and a natural extract of safflower like. The compounding quantity of these active ingredients can be made into an effective quantity in the range which does not prevent the effect of this invention.

  As the sweetener, saccharin sodium, stevioside, neohesperidyl dihydrochalcone, perilartin, p-methoxycinnamic aldehyde, aspartame and the like can be blended.

  As coloring agents, Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 204, Green No. 3, mica titanium, titanium oxide and the like.

  Examples of the preservative include benzoates such as paraoxybenzoate and sodium benzoate, and quaternary ammonium type preservatives such as cetylpyridinium chloride, benzalkonium chloride, and benzethonium chloride. In the present invention, particularly when the component (D) is blended, the antiseptic power is satisfactorily increased, so that a preservative may not be blended.

  Examples of the pH adjuster include citric acid, malic acid, lactic acid, tartaric acid, acetic acid, phosphoric acid, glycerophosphoric acid, various salts thereof, sodium hydroxide, and the like, which are appropriately selected according to a desired pH. Can be used. It is preferable that the dentifrice composition of this invention is adjusted to pH 6-10, especially 7-9.

Perfumes are peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, lime Oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete, absolute peppermint Natural fragrances such as absolute rose and orange flower, and fragrances processed by these natural fragrances (total reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and , Menthol, carvone, anethole, cineol, salicylic acid , Cinnamic aldehyde, eugenol, 3-1-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octyl Acetaldehyde, citral, pregon, calbeetoacetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, propyl Alcohol, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate Toothpaste composition such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. The well-known fragrance | flavor raw material used for a thing can be used, It is not limited to the fragrance | flavor of an Example.
Moreover, although a compounding quantity is not specifically limited, It is preferable to use said fragrance | flavor raw material 0.000001 to 1% in a formulation composition. Moreover, as a fragrance | flavor for fragrance | flavor using the said fragrance | flavor raw material, it is preferable to use 0.1 to 2.0% in a formulation composition.

The material in particular of a container is not restrict | limited, Usually, the container used for a dentifrice composition can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used. For example, a laminated tube tube having a diameter of 26 mm and an inner diameter of 8 to 12 mm (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30 from the outermost layer) can be preferably used. The above abbreviations are as follows, and the number at the end indicates the thickness (μm).
LDPE: Low density polyethylene White LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Copolymer resin of ethylene / methacrylic acid

  EXAMPLES Hereinafter, although an experimental example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the blending amount is mass%.

[Experimental Example 1]
Toothpaste compositions (toothpastes) having the compositions shown in Tables 1 to 3 were prepared by the following method and filled into a laminate tube having a diameter of 26 mm and a mouth inner diameter of 8 mm. About the obtained dentifrice composition, plaque removal power, stability of dextranase, moldability on a toothbrush, foaming at the time of toothbrushing, and liquid separation stability of the preparation were evaluated by the following methods. The results are shown in Tables 1-3.

Preparation of test dentifrice composition:
To prepare the dentifrice composition, saccharin sodium, sodium fluoride, (D) component pyrophosphate, tripolyphosphate and other water-soluble substances are dissolved in purified water, sorbite is added, and then separately added to polyethylene glycol # 400. A liquid in which the cationic polymer of component (A) and the hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and methyl cellulose of component (C) were dispersed was added and stirred. Then, a fragrance | flavor, abrasive silica, and the fatty acid amide propyl betaine of (B) component were added in order, and also it stirred under reduced pressure (5.3 kPa), and the dentifrice composition was obtained. A unimixer (FM-SR-25, POWEX CORPORATION) was used for the production.

  Each component used for the preparation of these dentifrice compositions was dextranase (Daiichi Sankyo Propharma Co., Ltd.), hydroxyethyl cellulose dimethyl diallylammonium chloride (Cellcoat L-200, 2% aqueous solution viscosity: 150 mPa · s, Akzo Nobel Co., Ltd.), O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose (Leogard GP, 2% aqueous solution viscosity: 350 mPa · s, manufactured by Lion Corporation), hydroxyethyl cellulose (SE900) 1% aqueous solution viscosity: 5,000 mPa · s, manufactured by Daicel Chemical Industries, Ltd.), hydroxypropylmethylcellulose (METOLOSE 60SH 4000, 2% aqueous solution viscosity: 4,000 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd.), methylcellulose (METOLO SE SM 4000, 2% aqueous solution viscosity: 4,000 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd.), palm oil fatty acid amidopropyl betaine solution (30% aqueous solution product, TEGO BETAIN CK, manufactured by Goldschmidt), amidopropyl laurate Betaine (30% aqueous solution product, Amhitor 20AB (manufactured by Kao Corporation), sodium pyrophosphate (manufactured by Taihei Chemical Sangyo Co., Ltd.), sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo Co., Ltd.) and other components. As for certain silicic anhydride, thickening silicic anhydride, sorbit (70% aqueous solution product), xanthan gum, polyethylene glycol # 400, sodium saccharin, sodium fluoride, and water, those conforming to the quasi-drug raw material standard 2006 were used. For components of aqueous solution, including those in the table Shows the amount of pure content conversion. Perfume, perfume A~ perfume I shown in Table 6, were prepared using the flavor compositions shown in Table 7-12 were formulated.

  The container used in the following evaluation was a laminated tube (Dai Nippon Printing Co., Ltd.) having a diameter of 26 mm and a mouth inner diameter of 8 mm, and the layer structure was LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / from the outermost layer. AL10 / EMAA30 / LDPE20 / LLDPE30, and thickness is 257 μm. The abbreviations are as described above, and the numerical values indicate the thickness (μm) of each layer.

(1) Evaluation of plaque removal power The dentifrice composition is artificial saliva (final concentrations are 50 mM KCl, 1 mM KH ₂ PO ₄ , 1 mM CaCl ₂ , 0.1 mM MgCl _2), and the pH is adjusted to 7.0 with KOH. The centrifugal supernatant (2,000 G × 10 minutes, 20 ° C.) diluted 10-fold with 1 mL of distilled water was used as a sample solution. Streptococcus sobrinus (S. Sobrinus NIDR6715) was cultivated in a 1% sucrose-containing TSB medium (Becton, Dickinson company) (anaerobic, 37 ° C.), and plaques were attached to the test tube (KIMBLE 13 × 100 mm) wall I let you. After washing twice with 0.1 M phosphate buffer (pH 6.0), the plaque was treated (immersed) in 4 mL of the above sample sample solution at 37 ° C. for 3 minutes, and then 0.1 M phosphate buffer (pH 6). 0.0) 3 times, 4 mL of 0.1 M phosphate buffer (pH 6.0) was added, and the mixture was allowed to stand (immerse) at 37 ° C. for 60 minutes. After removing plaques that had been washed twice with 0.1 M phosphate buffer (pH 6.0) and removed by peeling, 4 mL of 0.1 M phosphate buffer (pH 6.0) was added, and the remaining plaques were subjected to an ultrasonic homogenizer ( The amount of plaque was measured as turbidity. Turbidity was measured at OD 550 nm, and the reduction rate of plaque amount (turbidity) relative to a blank (treated with artificial saliva without adding a dentifrice composition) was defined as a plaque removal rate. The experiment was repeated three times, the average value of the three times was calculated, and those with the results of ◎ and ○ on the following criteria were judged to be dentifrice compositions with high plaque removal effect.
Evaluation criteria ◎: Plaque removal rate 80% or more ○: Plaque removal rate 70% or more and less than 80% △: Plaque removal rate 50% or more and less than 70% ×: Plaque removal rate less than 50%

(2) Evaluation of stability of dextranase 50 g of a dentifrice composition blended with dextranase was filled in a 26 mm diameter laminated tube made of linear low density polyethylene and stored at 45 ° C. for 2 weeks. 0.6 g of the dentifrice composition was suspended in 15 mL of 0.1 M phosphate buffer, and the centrifuged supernatant was used as a test solution. 1 mL of this test solution was added to 2 mL of a 1% dextran solution, reacted in a thermostat at 35 ° C. for exactly 10 minutes, and the amount of reducing sugar produced was measured using the Somogy Nelson method. One unit of dextranase was defined as the amount of dextranase that produces free reducing sugar corresponding to 1 μmol of glucose per minute, and the average of three repetitions was evaluated according to the following criteria.
A: Dextranase remaining rate of 90% or more O: Dextranase remaining rate of 80% or more and less than 90% Δ: Dextranase remaining rate of 60 or more and less than 80% ×: Dextranase remaining rate of less than 60%

(3) Evaluation of formability on toothbrush The sample (test dentifrice composition) was filled in the laminate tube, and the shape change on the toothbrush when 1.5 g was placed on the toothbrush was evaluated according to the following criteria.
4 points: No deformation of the mold is observed.
3 points: Slight deformation is observed, but there is no problem in use.
2 points: gradually loses shape.
1 point: Immediately deforms.
The five evaluation results were averaged, and the formability on the toothbrush was determined in the following four stages. The samples with and ○ were judged to be dentifrice compositions that ensure formability on a toothbrush.
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

(4) Evaluation of foaming at the time of tooth brushing It evaluated by the sensory test using ten expert panelists. About 1.5 cm of the test dentifrice composition was placed on a toothbrush and used in a normal brushing method. For the dentifrice composition in the oral cavity, foaming during brushing was evaluated according to the following criteria.
4 points: The amount of foaming is sufficient and the feeling of use is excellent.
3 points: The amount of foaming is moderate and the feeling of use is satisfactory.
2 points: The amount of foaming is small and the feeling of use is slightly inferior.
1 point: There is almost no foaming and the feeling of use is bad.
The evaluation results of 10 people were averaged and shown by the following criteria, and ◎ and ○ were judged to be a dentifrice composition that ensured foaming at the time of brushing and provided a satisfactory feeling of use.
◎: Bubbling in the oral cavity is 3.5 points to 4.0 points or less ○: Bubbling in the oral cavity is 3.0 points to less than 3.5 points △: Bubbling in the oral cavity is 2.0 points Or more to less than 3.0 points x: foaming in the oral cavity is less than 2.0 points

(5) Evaluation of liquid separation stability of the formulation 50 g of the dentifrice composition was filled in the above laminate tube, each composition was stored at 50 ° C. for 1 month, and then the 10 cm dentifrice composition was extruded onto the straw half paper, The length of the oozed liquid was measured, and the degree of liquid separation was evaluated in the following four stages. The liquid separation stability of the preparation tended to promote liquid separation depending on the temperature, and 50 ° C. was selected as a storage temperature that can be evaluated in a storage period of one month.
4 points: No liquid separation is observed.
3 points: When extruded, liquid separation is slightly observed at the mouth, but there is no problem in use.
2 points: When extruded, 1 to 3 cm of liquid separation is observed at the mouth.
1 point: When extruded, liquid separation is recognized at the mouth over 3 cm.
The average value of the three evaluation points was determined, and the degree of liquid separation was determined in the following four stages. The samples with 及 び and ○ were judged to be dentifrice compositions with excellent liquid separation stability when stored at 50 ° C.
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

＊：表中の配合量は、純分換算の配合量を示す（以下、同様）。

*: The blending amount in the table indicates the blending amount in terms of pure content (hereinafter the same).

  From the results of Tables 1 to 3, the dentifrice composition of the present invention improves the plaque removal power by increasing the retention in the mouth of the glucanase enzyme having a plaque degrading action, and the enzyme stability in the dentifrice composition. It was found that the dentifrice composition was excellent in moldability, foaming and liquid separation stability over time.

[Experiment 2]
Toothpaste compositions (toothpaste) having the compositions shown in Tables 4 and 5 were prepared in the same manner as described above, and filled into a laminate tube having a diameter of 26 mm and a mouth inner diameter of 8 mm. About the obtained dentifrice composition, plaque removal power, stability of dextranase, moldability on toothbrush, foaming at the time of toothbrushing, liquid separation stability of the preparation were evaluated by the same method as above, The antiseptic power of the preparation and the absence of irritation of the preparation were evaluated by the following methods. The results are shown in Tables 4 and 5.

(6) Evaluation of Preservative Strength of Formulation Bacteria were cultured in soy bean / casein / digest agar medium for 24 hours, and yeast and mold were cultured in potato dextrose medium for 48 hours and 7 days, respectively. After culturing, bacteria and yeast are suspended in sterile physiological saline at about 10 ⁸ to 10 ⁹ cells / mL, and mold is about 10 ^{7 in} physiological saline containing 0.005% dioctyldodecyl sodium sulfosuccinate. / ML to make a test bacterial solution.
The test bacteria solution 0.2mL was added to 20g of dentifrice composition which is an evaluation sample, and after mixing sufficiently, bacteria were preserve | saved at 20 degreeC, yeast, and mold | fungi were preserve | saved at 25 degreeC. 28 days later, 1 g of each sample was aseptically collected and diluted and mixed with 9 mL of Soybean / Casein / Digest / Lecithin / Polysorbate 80 liquid medium. 1 mL of the solution was placed in a petri dish, and the bacteria were poured with soybean / casein / digest / lecithin / polysorbate 80 agar medium, and yeast and mold were mixed with glucose / peptone / lecithin / polysorbate 80 agar medium. Bacteria were cultured at 30 ° C. for 4 days, yeasts and molds were cultured at 25 ° C. for 7 days, and the number of surviving bacteria in the sample was measured. The criteria for evaluation of antiseptic power were set as follows. The antiseptic power of the preparation was evaluated according to the following criteria, and those with ◎ and ○ were judged to be excellent in plaque removal power.
Bacteria die within 7 days: ◎
Bacteria die within 14 days, exceeding 7 days: ○
More than 14 days but within 28 days the bacteria die: △
Bacteria do not die for more than 28 days: ×

(7) Evaluation of non-stimulation Evaluation was made by a sensory test using 10 expert panelists. About 1 g of the dentifrice composition was placed on a commercially available toothbrush and brushed in the oral cavity for 3 minutes. The tongue and oral mucosal irritation felt during use was evaluated according to the following criteria.
Evaluation criteria 4 points: No stimulation 3 points: Little stimulation 2 points: Slight stimulation 1 point: Stimulation 10 evaluation results are averaged, and ◎ and ○ are evaluated according to the following criteria Was determined to be an unstimulated dentifrice composition.
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

  From the results of Tables 4 and 5, the dentifrice composition of the present invention improves the plaque removal power by increasing the retention in the oral cavity of the glucanase enzyme having a plaque degrading action, and the enzyme stability in the dentifrice composition. The dentifrice composition was excellent in moldability, foaming, and liquid separation stability over time, and excellent antiseptic power was obtained.

Claims (3)

  To a dentifrice composition containing a glucanase enzyme, (A) a cationic polymer in an amount of 0.02 to 0.2% by mass, and (B) fatty acid amidopropyl betaine having a fatty acid having 12 to 14 carbon atoms in an amount of 0.4 to 1.6. 0.5% by mass to 3% by mass of at least one selected from mass%, (C) hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and methyl cellulose, and the mass ratio of (C) component / (A) component is 10-100. The dentifrice composition characterized by the above-mentioned.   The dentifrice composition according to claim 1, wherein the cationic polymer (A) is hydroxyethylcellulose dimethyldiallylammonium chloride and / or O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride.   Furthermore, the dentifrice composition of Claim 1 or 2 which mix | blended 0.1-2 mass% of (D) condensed phosphate.