HK1168293A1 - Dentifrice composition - Google Patents

Abstract

Disclosed is a dentifrice composition which is characterized by containing (A) an ascorbic acid phosphate ester or a salt thereof, (B) isopropylmethylphenol, (C) one or more nonionic surfactants selected from among polyoxyethylene alkyl ethers having an alkyl group with 14-18 carbon atoms and an average mole number of added ethylene oxide units of 2-20 and polyoxyethylene-hardened caster oils having an average mole number of added ethylene oxide units of 5-30, (D) a chelating agent and (E) an alkaline agent. The dentifrice composition is also characterized by having a mass ratio (D)/(A) of 0.10-4.0 and an initial pH at 25°C of 8.0-9.3. The dentifrice composition exhibits excellent preventive effects on gingivitis and halitosis even after long storage, while having an excellently smooth composition surface. The dentifrice composition is almost free from unpleasant taste and has good feeling of use, while being effective for prevention or amelioration of periodontal diseases.

Description

Dentifrice composition

Technical Field

The present invention relates to a dentifrice composition having an excellent gingivitis prevention effect and an excellent halitosis prevention effect and having excellent smoothness of the composition surface and excellent taste during use.

Background

Periodontal disease is an infectious disease caused by bacteria such as porphyromonas gingivalis (p.gingivalis) mainly consisting of obligate anaerobic gram-negative bacteria. In addition, oral bacteria such as clostridium nucleatum (f.nucellum) are involved as causes of halitosis. Therefore, it is considered that, as an effective method for preventing and improving periodontal disease or halitosis, it is effective to control plaque, that is, to maintain the number of pathogenic bacteria in the oral cavity at a low level.

As a method for reducing the number of pathogenic bacteria in the oral cavity in this way, it has been effective to mix a sparingly water-soluble bactericide or a cationic bactericide in an oral care product. In particular, a sparingly water-soluble bactericidal agent such as isopropyl methylphenol is suitably mixed in a dentifrice composition because of its broad-spectrum antibacterial characteristics (see patent documents 1 to 4).

However, the occurrence of periodontal disease involves many factors, and thus, only mixing a sparingly water-soluble bactericidal agent having bactericidal activity in this way does not actually exhibit an excellent preventive effect.

On the other hand, in recent years, ascorbyl phosphate has attracted attention as an antioxidant vitamin capable of eliminating excess active oxygen generated in a living body and preventing a living tissue from being damaged by oxygen. Furthermore, ascorbyl phosphate has various physiological activities, and is known to be effective for prevention and treatment of gingivitis and periodontitis in the oral field, and it has been attempted to mix ascorbyl phosphate in oral compositions such as a dentifrice and a troche (see patent documents 5 and 6).

As a method for improving the effect of preventing periodontal disease, the applicant has proposed maintaining the composition of vitamin E or a derivative thereof by using a combination of ascorbic acid or a derivative thereof and an antiplasmin agent or by mixing a nonionic surfactant and an ascorbic acid derivative or a salt thereof with a composition containing vitamin E or a derivative thereof (patent documents 7 and 8). In addition, Japanese patent application No. 2007-329477 (Japanese patent application No. 2009-149565) proposes a composition in which ascorbic acid phosphate or a salt thereof and epsilon-aminocaproic acid and/or tranexamic acid are mixed in combination.

However, as a result of further intensive studies by the applicant, it has been found that the addition of vitamin E or a derivative thereof, or epsilon-aminocaproic acid and/or tranexamic acid to ascorbyl phosphate or a salt thereof has a certain effect of preventing periodontal disease, but has not yet been satisfactory for reducing the number of pathogenic bacteria that are major causes. Therefore, a new technique for obtaining a composition that can exhibit a better periodontal disease prevention effect and halitosis prevention effect is strongly desired.

Among these, it is known that the prevention and improvement effect on gingivitis can be improved by using a combination of an ascorbic acid phosphate salt, an antiplasmin agent and an antibacterial agent (see patent document 7).

In addition, many studies have been made on a technique for sufficiently exerting the effect of a poorly water-soluble antibacterial agent such as isopropyl methylphenol, and there is a finding that the bactericidal effect is improved by mixing a nonionic surfactant (see patent documents 1, 3, and 9).

Prior Art

Patent document

Patent document 1: japanese laid-open patent publication No. 2003-292426

Patent document 2: japanese patent application laid-open No. 2004-250381

Patent document 3: japanese patent laid-open No. 2005-179266

Patent document 4: japanese patent laid-open No. 2008-115115

Patent document 5: japanese patent laid-open No. Hei 2-292211

Patent document 6: japanese patent laid-open No. Hei 3-294227

Patent document 7: japanese patent laid-open No. Hei 11-012142

Patent document 8: japanese patent laid-open No. 2004-323488

Patent document 9: japanese patent laid-open No. 59-101417

Disclosure of Invention

Problems to be solved by the invention

However, the present inventors have found through studies that when an ascorbic acid phosphate salt, isopropyl methylphenol and a nonionic surfactant are mixed together, the stability of the ascorbic acid phosphate salt deteriorates over time after long-term storage, and the effect of preventing periodontal disease and halitosis cannot be sufficiently observed, and further, particles are generated on the surface of the composition, which causes problems such as a problem of smoothness.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a dentifrice composition which, when ascorbic acid phosphate ester or a salt thereof, isopropyl methylphenol, and a nonionic surfactant are mixed, can effectively exhibit the effect derived from ascorbic acid phosphate ester or a salt thereof, and isopropyl methylphenol after long-term storage because the stability of ascorbic acid phosphate ester or a salt thereof after long-term storage is well maintained, has an excellent effect of preventing or improving gingivitis and halitosis, and has excellent surface smoothness and feeling of use.

Means for solving the problems

The present inventors have found that the above object can be achieved by mixing (A) ascorbic acid phosphate or a salt thereof, (B) isopropyl methylphenol, (C) at least 1 nonionic surfactant selected from polyoxyethylene alkyl ether having an average molar number of addition of ethylene oxide having an alkyl group of 14 to 18 carbon atoms of 2 to 20 moles and polyoxyethylene hardened castor oil having an average molar number of addition of ethylene oxide of 5 to 30 moles, (D) chelating agent, (E) alkali agent, wherein the mass ratio of (D)/(A) is 0.10 to 4.0, and the initial pH at 25 ℃ is 8.0 to 9.3. According to the present invention, a dentifrice composition can be obtained which can sufficiently maintain the stability of ascorbic acid phosphate ester or a salt thereof after long-term storage and can maintain high bactericidal activity against pathogenic bacteria in the oral cavity, and thereby exhibits synergistic effects of ascorbic acid phosphate ester or a salt thereof and isopropyl methylphenol in preventing or improving gingivitis and halitosis, and which has excellent surface smoothness (degree of smoothness of the toothpaste surface) and a good feeling of use such as no odor derived from a chelating agent.

That is, according to the present invention, by simultaneously mixing ascorbic acid phosphate or a salt thereof, isopropyl methylphenol, and a nonionic surfactant, high bactericidal activity can be maintained against an oral pathogenic bacterium such as clostridium nucleatum (f.tuberculosis) which causes halitosis, and furthermore, since one of the main causes is metal in the chelating agent capturing composition, ascorbic acid phosphate or a salt thereof can be stably maintained even after long-term storage. As will be understood from the examples described later, the effects of the present invention are exhibited by combining the above components and mixing them at an appropriate mixing amount and ratio, and any one of the essential components and the mixing amount and ratio of each component according to the present invention is not appropriate, and a special effect cannot be achieved.

Further, the applicant proposed in japanese patent application No. 2009-136994 an oral composition having excellent appearance (separation) stability, which is obtained by mixing ascorbic acid phosphate or a salt thereof, vitamin E or a derivative thereof, an appropriate amount of polyoxyethylene hardened castor oil, a polyoxyethylene alkyl ether or alkyl glucoside, and a nonionic or cationic bactericide in an appropriate mixing amount and mixing ratio so that ascorbic acid phosphate or a salt thereof and vitamin E or a derivative thereof are stably mixed at the same time. This technique is technically different from the present invention in that the above-described excellent effects are achieved by stably mixing ascorbic acid phosphate ester or a salt thereof, vitamin E or a derivative thereof, and a bactericide at the same time. The present invention is based on the fact that the above-mentioned specific action and effect is achieved by using (a) ascorbic acid phosphate ester or a salt thereof, (B) isopropyl methylphenol, (C) a specific nonionic surfactant in combination with (D) a chelating agent and (E) an alkaline agent, and by maintaining the storage stability of ascorbic acid phosphate ester or a salt thereof even without mixing vitamin E or a derivative thereof, and by exerting an excellent effect of preventing or improving gingivitis and halitosis, and by providing a toothpaste agent having excellent surface smoothness.

Accordingly, the present invention provides the dentifrice compositions described below.

1: a dentifrice composition comprising (A) ascorbic acid phosphate or a salt thereof, (B) isopropyl methylphenol, (C) at least one nonionic surfactant selected from polyoxyethylene alkyl ethers having an alkyl group containing 14 to 18 carbon atoms and an ethylene oxide, and polyoxyethylene hardened castor oil having an ethylene oxide, wherein the average molar number of addition of the ethylene oxide is 2 to 20 moles, (D) a chelating agent, and (E) an alkaline agent; (D) the mass ratio of (A) is 0.10 to 4.0, and the initial pH at 25 ℃ is 8.0 to 9.3.

2: the dentifrice composition according to claim 1, wherein the chelating agent is at least one member selected from the group consisting of citric acid, pyrophosphoric acid, tripolyphosphoric acid, and alkali metal salts thereof.

3: the dentifrice composition according to claim 1 or 2, which comprises 0.2 to 1% by mass of the component (A), 0.03 to 0.2% by mass of the component (B), and 0.5 to 2% by mass of the component (C); (D) the mass ratio of (A) is 0.3 to 3.5.

ADVANTAGEOUS EFFECTS OF INVENTION

The dentifrice composition of the present invention can exhibit a prophylactic effect on gingivitis and halitosis after long-term storage, has excellent surface smoothness, gives a good feeling of use with little odor, and has an effect on prevention or improvement of periodontal disease.

Detailed Description

The present invention will be described in more detail below. The dentifrice composition of the present invention is characterized by comprising (A) ascorbic acid phosphate ester or a salt thereof, (B) isopropyl methylphenol, (C) at least 1 nonionic surfactant selected from polyoxyethylene alkyl ether having an average molar number of addition of ethylene oxide having an alkyl group of 14 to 18 carbon atoms of 2 to 20 moles and POE hardened castor oil having an average molar number of addition of ethylene oxide of 5 to 30 moles, (D) a chelating agent, and (E) an alkaline agent; (D) the mass ratio of (A) is 0.10 to 4.0, and the initial pH at 25 ℃ is 8.0 to 9.3.

(A) The ascorbic acid phosphate ester is an ester of ascorbic acid in which 1 or 2 or more of any one of hydroxyl groups at 2, 3, 5, and 6 positions is a compound such as phosphoric acid or polyphosphoric acid. Examples thereof include: ascorbic acid-2-phosphate ester, ascorbic acid-3-phosphate ester, ascorbic acid-6-phosphate ester, ascorbic acid-2-polyphosphate ester, and the like, and salts thereof include: alkali metal salts such as sodium salt, potassium salt, calcium salt and magnesium salt, and alkaline earth metal salts. In particular, as an oral substance, a magnesium salt or a sodium salt of ascorbic acid phosphate is preferably used from the viewpoint of gingivitis preventive effect.

The amount of the ascorbic acid phosphate ester or salt thereof to be mixed is preferably 0.1 to 2% by mass of the whole composition, more preferably 0.2 to 1%. If the amount is less than 0.1%, the gingivitis and halitosis preventing effects may not be sufficiently exhibited, and if the amount exceeds 2%, the effects cannot be further improved from the original effects, and the feeling of use such as odor may be reduced.

(B) The isopropylmethylphenol is 1-hydroxy-4-isopropyl 3-methylphenol, and is commercially available, and for example, products sold by Kagaku K.K. under the trade name of ビオゾ - ル may be used.

The amount of isopropyl methylphenol to be mixed is preferably 0.01 to 0.5%, particularly preferably 0.03 to 0.2%, of the total composition. If the amount is less than 0.01%, the bactericidal effect may not be sufficiently exhibited, the effect of preventing halitosis may be poor, and if it exceeds 0.5%, the feeling of use such as odor may be reduced, resulting in a problem in storage stability.

The present invention comprises (C) at least 1 nonionic surfactant selected from Polyoxyethylene (POE) alkyl ether having an alkyl group with 14 to 18 carbon atoms and an average addition mole number of ethylene oxide (EO average addition mole number) of 2 to 20 moles, and POE hardened castor oil having an EO average addition mole number of 5 to 30 moles.

The number of carbon atoms of the alkyl group of the POE alkyl ether is 14 to 18, and more preferably 16 to 18. When the number of carbon atoms of the alkyl group is less than 14 or more than 18, the bactericidal effect cannot be sufficiently exhibited. Specific examples of such POE alkyl ethers include: POE cetyl ether, POE tetradecyl ether, POE stearyl ether, etc., and POE stearyl ether is especially preferable. The POE alkyl ether has an average EO molar number of addition of 2 to 20 mol, preferably 3 to 10 mol, and more preferably 5 to 10 mol. When the average molar number of EO added is less than 2 mol or more than 20 mol, the bactericidal effect may not be sufficiently exhibited. As such POE alkyl ethers, commercially available products such as EMALEX102, 103, 105, 107, 110, 112, 115, 117, 120, 602, 603, 605, 608, 611, 615, and 620 from japan エマルジヨン (strain) can be used.

The POE hardened castor oil has an average EO addition mole number of 5 to 30 moles, preferably 10 to 30 moles, and more preferably 20 to 30 moles. When the average molar number of EO added is less than 5 mol or more than 30 mol, the bactericidal effect may not be sufficiently exhibited, and the effect of preventing halitosis may be poor. As such POE hardened castor oil, commercially available products such as NIKKOLHCO-5, HCO-10, HCO-20 and HCO-30 of sunlight ケミカルズ (strain) can be used.

The component (C) may be a mixture of the POE alkyl ether or the POE hardened castor oil, or a mixture of 2 or more surfactants selected from the POE alkyl ether and the POE hardened castor oil, and particularly, it is more preferable to use a mixture of a POE stearyl ether having an average molar number of EO added of 5 to 10 moles and a POE hardened castor oil having an average molar number of EO added of 20 to 30 moles.

The total amount of these POE alkyl ethers and/or POE hardened castor oil is preferably 0.3 to 5%, particularly preferably 0.5 to 2%, of the total composition. If the amount is less than 0.3%, the problem of storage stability of isopropyl methylphenol may occur after long-term storage, the bactericidal effect may not be sufficiently exhibited, the effect of preventing halitosis may be poor, and if it exceeds 5%, the odor may be generated, and the problem of storage stability may occur.

The chelating agent (D) used in the present invention is presumed to be a substance which can prevent the ascorbic acid phosphate ester or a salt thereof from forming an insoluble precipitate by trapping metal particles in the composition, and stably exerts the effect of the composition. Specific examples of the chelating agent include: examples of the carboxyl group-containing substance include citric acid, tartaric acid, malic acid, succinic acid, gluconic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and alkali metal salts thereof such as sodium salts and potassium salts. Examples of the substance having a phosphate group include condensed phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid, phytic acid, and alkali metal salts thereof such as sodium salts and potassium salts. Among them, citric acid, pyrophosphoric acid, tripolyphosphoric acid, and sodium salts and potassium salts thereof are particularly preferably used.

The amount of the chelating agent to be mixed is preferably 0.05 to 2%, particularly 0.1 to 1.0%, and particularly preferably 0.1 to 0.8% of the total amount of the composition. If the amount is less than 0.05%, the effect of improving the surface smoothness of the toothpaste may not be sufficiently exhibited, and the storage stability of the ascorbic acid phosphate ester or salt thereof may not be maintained, resulting in a poor effect of preventing halitosis. If it exceeds 2%, an odor may be generated.

In order to ensure the effectiveness, stability and usability of the composition, the mixing ratio of the component (D) to the component (A) is preferably 0.10 to 4.0, more preferably 0.2 to 4.0, and particularly preferably 0.3 to 3.5 in terms of the mass ratio of (D)/(A). If the (D)/(a) in the dentifrice composition is less than 0.10, the storage stability of the ascorbic acid phosphate ester or salt thereof cannot be maintained after long-term storage, and the gingivitis-preventing effect and the halitosis-preventing effect are poor. On the other hand, if it exceeds 4.0, an odor derived from the chelating agent is generated, and the effects of the present invention cannot be sufficiently exhibited.

(E) The alkali agent can be any commonly used alkali agent, and sodium hydroxide or potassium hydroxide can be suitably used, and sodium bicarbonate, triethanolamine and the like can also be preferably used.

The amount of the alkali agent to be mixed is preferably 0.01 to 1.0% based on the whole composition. If the amount is less than 0.01%, the effect of raising the initial pH to 8.0 may not be obtained, and if it exceeds 1.0%, problems may occur in the smoothness of the toothpaste surface and the taste during use.

In order to maintain the stability and effectiveness of the ascorbic acid phosphate ester or a salt thereof, the dentifrice composition has an initial pH of 8.0 to 9.3, preferably 8.0 to 9.0, at 25 ℃. If the initial pH is less than 8.0, the storage stability of the ascorbic acid phosphate ester or a salt thereof cannot be maintained, the gingivitis prevention effect and the halitosis prevention effect cannot be sufficiently exhibited, and the feeling of use is poor. When the initial pH and the pH at 25 ℃ after storage exceed 9.3, the storage stability of the ascorbic acid phosphate ester or a salt thereof cannot be maintained, the gingivitis prevention effect and the halitosis prevention effect cannot be sufficiently exhibited, and the user feels an unpleasant odor during or after brushing teeth.

The dentifrice composition of the present invention may be formulated into toothpaste, liquid toothpaste, moist toothpaste, etc., and in particular, may be formulated into toothpaste, and may contain other known additives as optional components in the essential components as long as the effects of the present invention are not impaired. Specifically, suitable ingredients such as abrasives, binders, thickening agents, humectants, surfactants, sweeteners, preservatives, flavors, coloring agents, storage stabilizers, and active ingredients (medicinal ingredients) which are generally mixed in dentifrice compositions can be mixed.

As the polishing agent, a commonly used polishing agent may be mixed within a range not impairing the effect of the present invention. For example, in addition to the anhydrous silicic acid generally used, there can be specifically mentioned: calcium hydrogen phosphate, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate, magnesium triphosphate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, titanium oxide, synthetic resin abrasive, etc. for toothpaste, and particularly anhydrous silicic acid is preferable. The amount of the abrasive to be mixed is usually 2 to 40%, particularly preferably 10 to 25% of the total composition.

Examples of the binder include: cellulose derivatives such as carboxymethyl cellulose; gums such as xanthan gum, tragacanth gum, karaya gum, and acacia gum; carboxyvinyl polymers such as polyvinyl alcohol, crosslinked sodium polyacrylate, and non-crosslinked sodium polyacrylate; organic binders such as carrageenan, sodium alginate, and polyvinylpyrrolidone; inorganic binder such as silica gel, alumina silica gel, propolis, and montmorillonite. The amount of the binder is usually 0.2 to 10% of the total composition.

As the thickening agent, there may be mentioned: polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, sorbitol, xylitol, maltitol (maltol), lactitol (lactitol), polyethylene glycol having an average molecular weight of 200 to 6,000, ethylene glycol, and reduced starch sugar compounds. The amount to be mixed is usually 5 to 50%, particularly 20 to 45% of the total composition.

The surfactant (C) may be mixed with other nonionic, anionic, cationic or amphoteric surfactants. Examples of the anionic surfactant include: sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; sodium N-acylmethylglycinate such as sodium N-lauroyl methylglycinate and sodium N-tetradecanoyl methylglycinate; n-acyl glutamates such as sodium dodecylbenzenesulfonate, sodium hydrogenated coconut fatty acid monoglyceride monosulfate, sodium lauryl sulfoacetate, and sodium N-palmitoyl glutamate; sodium N-methyl-N-acyl taurate, N-methyl-N-acyl alanine, sodium alpha-olefin sulfonate, and the like. Examples of the nonionic surfactant include: sugar alcohol fatty acid esters such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and sucrose fatty acid esters; polyhydric alcohol fatty acid esters such as glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyethylene glycol fatty acid ester; ether surfactants such as polyoxyethylene polyoxypropylene copolymers and polyoxyethylene alkylphenyl ethers; fatty acid alkanolamides such as lauric acid diethanolamide. Examples of the cationic surfactant include: alkylammonium, alkylbenzylammonium salts, and the like. As amphoteric surfactants, there may be mentioned: betaine acetate, imidazolinium betaine, lecithin, etc. The amount of these surfactants to be mixed is usually 0.2 to 15%, preferably 0.5 to 10%, of the total composition, and the total amount of the surfactant(s) to be mixed is preferably 0.3 to 15%.

Examples of the sweetener include: saccharin sodium, stevioside, stevia rebaudiana extract, neohesperidin dihydrochalcone, glycyrrhizin, perillaseed, p-methoxycinnamaldehyde, aspartame, xylitol and the like.

Examples of preservatives include: parabens such as butyl paraben, propyl paraben and ethyl paraben; parabens, sodium benzoate, cetylpyridinium chloride, potassium sorbate, and the like.

The perfume can be selected from Peppermint oil (Peppermint oil), spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cinnamon oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, Peppermint oil (ハツカ oil), cardamom oil, coriander oil, mandarin oil, lime berry oil, lavender oil, rosemary oil, bay oil, chamomile oil, caraway oil, marjoram oil, bay oil, lemongrass oil, oregano oil, pine needle oil, orange flower oil, rose oil, jasmine oil, iris flower extract, Peppermint oil, rose essential oil, orange flower oil, etc., and those obtained by processing (fore run, after run, fractionation, liquid-liquid extraction, refining, powder flavoring, etc.) these natural perfumes, and menthol, carvone, anethole, oleyl alcohol, methyl salicylate, cinnamaldehyde, eugenol, 3-I-menthoxypropane-1, 2-diol, thymol, linalool acetate, limonene, menthone, menthyl acetate, N-substituted-p-menthane-3-carboxamide, pinene, octanal, citral, pulegone, carvacrol acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethylmethylphenyl glycidate, vanillin, undecalactone, hexanal, propanol, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, methylcyclopentenone, furfural, trimethylpyrazine, ethyl lactate, methyl lactate, ethyl thioglycolate and like individual perfumes; known flavor materials used in dentifrice compositions such as a strawberry flavor, an apple flavor, a banana flavor, a pineapple flavor, a grape flavor, a mango flavor, a butter flavor, a milk flavor, a fruit mix flavor, a tropical fruit flavor, and other blending flavors can also be used. The amount to be mixed is not particularly limited, and the perfume raw material is preferably used in an amount of 0.000001 to 1% in the formulation component. In addition, as the perfuming perfume using the perfume raw material, 0.1-2.0% of the preparation composition is preferably used.

Examples of the dyeing material include: blue No. 1, blue No. 4, green No. 3, etc. The amount of these active ingredients to be mixed is usually within a range not to impair the effects of the present invention.

Examples of the storage stabilizer include: vitamin C, sodium metabisulfite, sodium bisulfite, butyl hydroxy toluene, propyl gallate, butyl hydroxy aryl ester, etc.

The effective components other than the components (A) and (B) may be mixed in an effective amount as follows as long as the effect of the present invention is not impaired: fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, and sodium monofluorophosphate; water-soluble phosphoric acid compounds such as potassium salts and sodium salts of orthophosphoric acid; chelating phosphate compounds such as allantoin, allantoin aluminum chlorohydrate, thujaplicin, ascorbic acid, sodium chloride, coenzyme Q10, dihydrocholesterol, alpha-bisabolol, chlorhexidine salts, triclosan, thujaplicin, sanguinarine extract, azulene, glycitein, glycyrrhetinic acid, sodium copper chlorophyllin, chlorophyll, and glycerophosphate; copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, aluminum lactate, berberine, hydroxamic acid and derivatives thereof, zeolite, methoxyethylene, maleic anhydride copolymer, polyvinylpyrrolidone, epidihydrocholesterol, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, sodium chloride, dihydrocholesterol, triclosan, zinc citrate, dextranase, mutanase, proteolytic enzyme, and the like; soft extract of radix Angelicae sinensis, cortex Phellodendri extract, flos Matricariae Chamomillae, flos Caryophylli, herba Rosmarini officinalis, Scutellariae radix, Carthami flos, etc.

The material for the container for holding the dentifrice composition of the present invention is not particularly limited, and a container generally used for oral compositions can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, nylon, and the like can be used.

Examples

The present invention will be specifically described below by way of experimental examples, comparative examples and formulation examples, but the present invention is not limited to the following examples. In the following examples, the% number refers to mass% unless otherwise specified.

The dentifrice compositions having the compositions shown in tables 1 to 4 were prepared by the following production methods.

Method of manufacturing dentifrice composition:

(1) the water-soluble components (except the binder and propylene glycol) were mixed and dissolved in pure water at room temperature to prepare phase A.

(2) Dispersing the binder in propylene glycol at normal temperature to prepare phase B.

(3) Phase B was added to the stirred phase A to prepare phase C.

(4) Ingredients other than water-soluble ingredients such as a flavor and a polishing agent were mixed with the C phase using a 6L kneader (manufactured by Shishan Corp.) at room temperature, and defoaming was performed under reduced pressure (4kPa) to obtain 5kg of the dentifrice composition.

Further, sodium hydroxide as an alkali agent is prepared into a 20% aqueous solution, and the alkali agent is added so that the initial pH of the dentifrice composition at 25 ℃ is 8.0 to 9.3. The amount of sodium hydroxide in the table is expressed in terms of purity.

60g of the dentifrice composition prepared as described above was packed in a laminated tube (LDPE55/PET12/LDPE 20/white LDPE60/EMAA20/AL10/EMAA30/LDPE20/LLDPE30, 257 μm thick (manufactured by Dainippon printing Co., Ltd.) having an innermost layer of 26mm diameter and 8mm diameter and made of linear low density polyethylene, and dispensed into a20 mL-capacity plastic container, and the pH after 3 minutes at the initial 25 ℃ was measured (measuring instrument: メトラ -. トレド (Co., Ltd.) MP220, electrode: メトラ -. トレド (Co., Ltd.) InLab 410).

The shorthand notation and the designation of the layer structure of the used laminated tube are as follows, the number following the shorthand notation indicating the thickness (μm) of the respective layer.

LDPE (Low-Density polyethylene): low density polyethylene

White LDPE: white low density polyethylene

LLDPE: linear low-density polyethylene

AL: aluminium

PET: polyethylene terephthalate

EMAA: ethylene-methacrylic acid copolymer resin

Experimental example 1 evaluation of sterilizing power after 6 months of storage at 40 deg.C

After the dentifrice compositions (toothpastes) shown in tables 1 to 4 were prepared, they were stored in a thermostatic bath at 40 ℃ for 6 months. After storage, after leaving to reach room temperature, each dentifrice composition was measured in an amount of 10g, and added to human saliva (30mL), followed by stirring and centrifugation (10,000 rpm, 20min), and the supernatant was taken as a sample stock solution. Dispersing a previously cultured oral bacteria dispersion (Fusobacterium tuberculosis) in saliva of human oral cavity to obtain a sample stock solution 2mL with respect to turbidity (OD) at 660nm₆₆₀) After 2mL of the solution adjusted to 1 was allowed to act for 30 seconds, 50. mu.L of the solution was collected and used as a bactericidal activity evaluation sample to evaluate the bactericidal activity by the following method.

And (3) evaluation of bactericidal activity:

each bactericidal activity evaluation sample solution (50. mu.L) was added to a THB liquid medium (4mL), incubated at 37 ℃ for 8 hours, and then subjected to turbidity (OD)₆₆₀) The amount of the grown bacteria was measured as an index, and a sample having a small value was evaluated as a sample having high bactericidal activity.

Further, 3.73g of potassium chloride, 0.14g of potassium dihydrogen phosphate, 0.15g of calcium chloride dihydrate, and 0.02g of magnesium chloride hexahydrate were dissolved in pure water, and the pH was adjusted to 7 with potassium hydroxide to prepare 1,000mL of the solution, which was used as saliva in the oral cavity of a human.

And (3) scoring:

turbidity (OD)₆₆₀)

Very good: less than 1.0

O: 1.0 or more and less than 2.0

X: 2.0 or more

Experimental example 2 storage stability of magnesium ascorbate-2-phosphate (hereinafter abbreviated as APM), sodium ascorbate-2-phosphate (hereinafter abbreviated as APS) or sodium ascorbate after 6 months of storage at 40 deg.C

After preparing the dentifrice compositions shown in tables 1 to 4, the dentifrice compositions were stored in thermostatic chambers at-5 ℃ and 40 ℃ for 6 months. The samples were stored at-5 ℃ as a non-decomposed control. After the storage was returned to normal temperature, the obtained solution was evaluated for storage stability of APM, APS or sodium ascorbate, and the average was determined by the following method. All reagents were made from Kanto Chemicals.

Quantification of APM or APS:

0.1g of each dentifrice composition was weighed, and 10mmol/L phosphoric acid buffer solution (1.5mmol/L potassium dihydrogenphosphate, 23.5mmol/L dipotassium hydrogenphosphate, pH8.0) was added thereto, and after vigorously stirring with a shaker for 20 minutes, the volume was adjusted to 10 mL. 1mL of this liquid was collected, filtered through a pretreatment filter, and then quantified by an absolute calibration line method using high-speed liquid chromatography (pump: Japanese Spectroscopy PU1580, autosampler: Shimadzu SIL-10A, UV detector: Shimadzu SPD-6A, recording apparatus: Shimadzu C-R4A). The mobile phase was a mixed solution (volume ratio) of 25mmol/L potassium dihydrogen phosphate +5mmol/L tetrabutylammonium/acetonitrile 91/9, the column was a stainless steel tube having a diameter of about 4.6mm and a length of about 150mm, and was packed with 5 μm of octadecylsilylated silica gel (e.g., TSK-gel ODS-80Ts (manufactured by DOW ソ Co., Ltd.)) for liquid chromatography, the column temperature was about 40 ℃, the detection wavelength was 240nm, the flow rate was 0.8 mL/min, and the retention time of APM and APS was about 7 minutes. APM and APS in the sample stored at 40 ℃ were calculated, and the residual ratio was determined by taking the APM content in the sample stored at-5 ℃ as 100%.

Quantification of sodium ascorbate:

10g of the dentifrice composition shown in Table 4 was weighed, 10mmol/L of phosphate buffer (pH7.2) was added thereto, and after stirring vigorously for 20 minutes, the volume was increased to 50 mL. The content of sodium ascorbate in the dentifrice composition was measured by a sodium ascorbate quantitative method in accordance with the standards for cosmetic raw materials using 10mL of this solution, and the residual ratio was determined with the content of APM in a sample stored at-5 ℃ as 100%.

(rating)

Residual rate of APM, APS or sodium ascorbate after 6 months storage at 40 deg.C

O: the residual rate is more than 90 percent

X: the residue rate is less than 90 percent

[ Experimental example 3] gingivitis prevention Effect after 6 months of storage at 40 ℃

After the dentifrice compositions shown in tables 1 to 4 were prepared, a use test was performed for 10 days using the dentifrice compositions after 6 months of storage at 40 ℃ to observe the effect of preventing gingivitis.

That is, 50 normal healthy persons were divided into 5 groups of 10 persons, and each group was evaluated as follows, using about 1g of the dentifrice composition of one of the following <1> - <5> sample groups each time, using one week, then stopping cleaning the oral cavity for 3 days, and observing the state of the gingival margin portion of the upper and lower jaws of the incisor portion. In addition, the interval between the use of each dentifrice composition was 1 week to eliminate gingivitis, during which the dentifrice composition of comparative example 20 containing no gingivitis prevention effect ingredient was used. Then, the same experiment was also performed for the remaining samples. Additionally, the order of use of the dentifrice compositions of each group is randomly adjusted.

<1>

Example (b): 1,2,3,4,5,6,7,8,9, 10

Comparative example: 1,2,3,4

<2>

Example (b): 11, 12, 13, 14, 15, 16, 17, 18, 19, 20

Comparative example: 5,6,7,8

<3>

Example (b): 21, 22, 23, 24, 25, 26, 27, 28, 29, 30

Comparative example: 9,10, 11, 12

<4>

Example (b): 31, 32, 33, 34, 35, 36, 37, 38, 39, 40

Comparative example: 13, 14, 15, 16

<5>

Example (b): 41, 42, 43, 44, 45, 46, 47, 48, 49, 50

Comparative example: 17, 18, 19

Evaluation criteria for gingivitis prevention effect:

gingivitis was identified: inflammation symptoms such as reddening and swelling of the gingival margin are found

No gingivitis was identified: no inflammation at the gingival margin

And (3) scoring:

the number of subjects with gingivitis

Very good: 0 to 1 person

O: 2 to 3 persons

And (delta): 4 to 5 persons

X: 6 to 10 persons

[ Experimental example 4] halitosis-preventing Effect after 6 months of storage at 40 ℃

After the dentifrice compositions shown in tables 1 to 4 were prepared, the oral malodor evaluation test was performed using the dentifrice compositions after 6 months of storage at 40 ℃.

For evaluation of halitosis, 1 odor identification and judgment specialist (odor judgment specialist) used a UBC-type sensory evaluation method. After rinsing the mouth with water for 1 hour without brushing teeth, 25 subjects who had an evaluation criterion score of 2 or less were named as subjects, and subjects were divided into 5 groups of 5 persons each having the same average of the intensity of halitosis. After brushing about 1g of the dentifrice composition of 1 sample group out of the <1> - <5> sample groups of [ Experimental example 3] each time, oral cavity cleaning and eating were stopped for 2 hours, and then oral malodor was evaluated for each subject. Thereafter, the same experiment was performed for the remaining samples. Additionally, the order of use of the dentifrice compositions of each group is randomly adjusted.

The breath was taken by a method of breathing three times through the mouth, closing the mouth for 1 minute, blowing only the breath accumulated in the oral cavity to an odor determination agent through a predetermined plastic tube, and the strength of the odor was evaluated as follows.

Evaluation criteria for halitosis:

and 4, dividing: no odor was felt

And 3, dividing: hardly smells the odor

And 2, dividing: feeling a little stink

1 minute: smelly and very smelly

And (3) scoring:

average score of halitosis

Very good: 3.5 min or more

O: more than 3.0 minutes to less than 3.5 minutes

And (delta): more than 2.0 minutes to less than 3.0 minutes

X: less than 2.0 minutes

EXAMPLE 5 evaluation of surface smoothness of dentifrice composition after 6 months of storage at 40 ℃

Regarding the dentifrice compositions shown in tables 1 to 4, 15cm was extruded on paper, and the presence or absence of wrinkles and particles on the paste surface of the dentifrice compositions was visually evaluated.

And (3) scoring:

very good: no wrinkles or particles were observed on the surface of the dentifrice composition

O: almost no wrinkles or particles were observed on the surface of the dentifrice composition

X: wrinkles and particles were observed on the surface of the dentifrice composition

[ Experimental example 6] evaluation of toothpaste agent for absence of foreign odor

With respect to the dentifrice compositions shown in tables 1 to 4, 25 subjects were divided into 5 groups of 5 subjects, and 1 sample group of the <1> to <5> sample groups in [ experimental example 3] was used for each group to brush teeth using approximately 1g of the dentifrice composition. After completion of brushing, each subject was subjected to sensory evaluation of the degree of odor during and after brushing with the following criteria. Then, the same experiment was also performed for the remaining samples. Additionally, the order of use of the dentifrice compositions of each group is randomly adjusted.

Average standard without off-notes:

and 4, dividing: no peculiar smell is felt

And 3, dividing: hardly causing any unpleasant odor

And 2, dividing: slight off-flavor

1 minute: feel heavy peculiar smell

And (3) scoring:

average score without off-flavor

Very good: 3.5 min or more

O: more than 3.0 minutes to less than 3.5 minutes

And (delta): more than 2.0 minutes to less than 3.0 minutes

X: less than 2.0 minutes

The results are shown below.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4-1]

*: storage stability of sodium ascorbate (comparative product)

[ tables 4-2]

**: dentifrice composition free of ingredients relating to gingivitis prevention

The components used in the above examples are as follows.

1) Magnesium ascorbate-2-phosphate ester: showa electrician Co., Ltd. (ascorbic acid PM)

2) Sodium ascorbate-2-phosphate: DMS ニユ - トリシヨンジヤパン (ステイ C50)

3) Isopropyl methylphenol: osaka formation (shares company) (ビオゾ - ル)

4) Polyoxyethylene (5) stearyl ether: manufactured by Japan エマルジヨン (EMALEX605)

5) Polyoxyethylene (10) hexadecyl ether: manufactured by Japan エマルジヨン (EMALEX110)

6) Polyoxyethylene (20) hardened castor oil: manufactured by Japan ケミカルズ (NIKKOLHCO-20)

7) Polyoxyethylene (30) hardened castor oil: manufactured by Japanese ケミカルズ (NIKKOLHCO-30)

8) Citric acid: fusang chemical industry Co Ltd

9) Tartaric acid: fusang chemical industry Co Ltd

10) Succinic acid: fusang chemical industry Co Ltd

11) Malic acid: fusang chemical industry Co Ltd

12) Sodium gluconate: fusang chemical industry Co Ltd

13) Sodium pyrophosphate: manufactured by Taiping chemical industries Ltd

14) Sodium tripolyphosphate: manufactured by Taiping chemical industries Ltd

15) Sodium hydroxide: made by Sakai pharmaceutical corporation

From the results in tables 1 to 3, it is understood that the dentifrice compositions (examples 1 to 51) containing the components (a) to (E) of the present invention, wherein (D)/(a) is 0.10 to 4.0, and the initial pH is 8.0 to 9.3, have excellent bactericidal effect and gingivitis preventive effect, and are synergistically effective for preventing halitosis when used in combination with an ascorbate salt and isopropyl methylphenol. The dentifrice composition of the present invention has no odor during and after use, and is excellent in surface smoothness and excellent in feeling of use and appearance.

On the other hand, as is clear from the results in table 4, the dentifrice compositions lacking any of the requirements of the present invention (comparative examples 1 to 19) did not fully satisfy the bactericidal effect, gingivitis prevention effect, halitosis prevention effect, odor-free property during and after use of the dentifrice, and smoothness of the surface of the dentifrice composition. In this case, even if sodium ascorbate was mixed instead of ascorbyl phosphate, sodium ascorbate could not be stably mixed, and the preventive effect for gingivitis and halitosis was poor (comparative examples 1 and 2); even when cetylpyridinium chloride was mixed instead of isopropyl methylphenol, the bactericidal activity and the halitosis-preventing effect were poor (comparative examples 4 and 5); the bactericidal activity and the halitosis-preventing effect were also poor when the surfactant was not appropriate (comparative examples 9 to 12). In addition, when the D/A ratio is not appropriate, the storage stability of the ascorbic acid phosphate salt is not improved, satisfactory prevention effects of gingivitis and halitosis cannot be obtained, and when the initial pH is not appropriate, satisfactory prevention effects of gingivitis and halitosis cannot be obtained, and in any case, the object of the present invention cannot be achieved.

Then, dentifrice compositions of formulation examples 1 to 10 below were prepared in the same manner as in examples, and filled in a container to perform the same evaluation. In addition, the initial pH of any of the following examples is in the range of 8.0 to 9.3. The dentifrice compositions of the following formulation examples were excellent in bactericidal activity after long-term storage, storage stability of ascorbic acid phosphate salts, gingivitis prevention effect and halitosis prevention effect, and were also excellent in oral cavity irritation and toothpaste surface smoothness during use and after use.

[ prescription example 1] toothpaste

[ prescription example 2] toothpaste

[ prescription example 3] toothpaste

[ prescription example 4] toothpaste

[ prescription example 5] toothpaste

[ prescription example 6] toothpaste

[ prescription example 7] toothpaste

[ prescription example 8] toothpaste

[ prescription example 9] toothpaste

[ prescription example 10] toothpaste

Claims (3)

1. A dentifrice composition comprising (A) 0.1 to 2% by mass of ascorbic acid phosphate ester or a salt thereof, (B) 0.01 to 0.5% by mass of isopropylmethylphenol, (C) 0.3 to 5% by mass of at least one nonionic surfactant selected from polyoxyethylene alkyl ethers having 14 to 18 alkyl carbon atoms and 2 to 20 moles of ethylene oxide added on the average and polyoxyethylene-hardened castor oils having 5 to 30 moles of ethylene oxide added on the average, (D) a chelating agent, and (E) an alkali agent;

(D) the mass ratio of (A) is 0.10-4.0;

the initial pH at 25 ℃ is 8.0 to 9.3.

2. The dentifrice composition according to claim 1, wherein the chelating agent is at least 1 selected from the group consisting of citric acid, pyrophosphoric acid, tripolyphosphoric acid, and alkali metal salts thereof.

3. The dentifrice composition according to claim 1 or 2, which comprises 0.2 to 1% by mass of the component (A), 0.03 to 0.2% by mass of the component (B), and 0.5 to 2% by mass of the component (C); (D) the mass ratio of (A) is 0.3 to 3.5.