JP2008024652A - Dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition stably containing catechins, applying effective action of the catechins on the tooth and gingiva and having good usability. <P>SOLUTION: The dentifrice composition contains hydrogel particles containing catechins and a polymer to form a water-insoluble complex with catechins, a binder and water. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dentifrice composition containing catechins.

  It is known that cavity and periodontal disease are caused by oral bacteria. Therefore, in order to prevent cavity and periodontal disease, it is common to add a bactericidal agent to the oral composition to sterilize oral bacteria or suppress their activity. In particular, with the recent increase in natural orientation, ingredients derived from natural products are used as bactericides, avoiding the use of chemically synthesized substances. For example, it is known that a green tea extract and a tea polyphenol compound (catechins or the like) that is a component thereof are effective in suppressing the growth of oral bacteria (for example, Patent Documents 1 to 3). According to these documents, green tea extract etc. is effective in preventing cavity and periodontal disease because it inhibits the growth of Stereptcoccus mutans, which is the causative agent of cavity, and Porphyromonas gingivalis, which is the causative agent of periodontal disease. It is described that a composition can be provided. However, since polyphenol compounds (catechins and the like) are oxidized and polymerized by contact with oxygen and change their color significantly, discoloration over time of the oral composition containing the same is inevitable. As a method for suppressing such discoloration, for example, a method of blending a plant extract containing polyphenol with a sugar alcohol having 4 to 5 carbon atoms (for example, xylitol, erythritol, etc.) and separating it into an oxygen-impermeable individual bag is proposed. (Patent Document 4).

On the other hand, as a method for blending various drugs, easily denatured active ingredients, and the like into an oral composition, a method of encapsulating the ingredients or encapsulating them in a shell or the like has been proposed (Patent Literature). 5, 6 etc.).
JP-A-1-90124 JP-A-2-25413 Japanese Patent Laid-Open No. 3-86814 JP 2000-297022 A JP 61-225115 A JP-A-1-275520

  An object of the present invention is to provide a dentifrice composition having a good feeling of use, with catechins effectively acting on teeth and gums during use while stably holding catechins in the composition. is there.

  The present inventors include a hydrogel particle containing catechins and a specific polymer that forms a water-insoluble complex with catechins in a toothpaste composition, thereby stably holding catechins, It has been found that gel-like particles are easily broken by brushing, catechins effectively act in the vicinity of the surfaces of teeth and gums, and a toothpaste composition having a good feeling of use can be obtained.

  That is, the present invention provides a dentifrice composition containing hydrogel particles containing a catechin and a water-soluble polymer that forms a water-insoluble complex with the catechin, a binder, and water.

  The dentifrice of the present invention stably retains catechins, catechins effectively act near the surface of teeth and gums, can improve the condition of teeth and gums, and has a good feeling of use It is.

[Hydrogel particles]
The hydrogel particles contained in the toothpaste composition of the present invention contain catechins and a water-soluble polymer (hereinafter referred to as polymer A) that forms a water-insoluble complex with catechins.

  In the present specification, the “hydrogel” refers to a water-containing swelling body of a water-insoluble polymer (gel-forming agent) formed using water as a solvent, and a natural polymer compound is preferred as the gel-forming agent. .

  The catechins used in the present invention are non-polymerizable catechins, for example, non-epimeric catechins such as catechin, gallocatechin, catechin gallate, gallocatechin gallate; epicatechin, epigallocatechin, epicatechin gallate, epi Examples include epicatechins such as gallocatechin gallate. Catechins can be obtained by concentrating and purifying a green tea extract extracted from tea leaves with hot water or a water-soluble organic solvent. In addition, by using green tea extract concentrates such as commercially available Mitsui Norin Co., Ltd. “Polyphenone”, ITO EN Co., Ltd. “Theafuran”, Taiyo Kagaku Co., Ltd. “Sunphenon”, etc., by adjusting the components, A catechin suitable for the purpose can be obtained.

  The polymer A used in the present invention is not particularly limited as long as it is a polymer that forms a water-insoluble complex with catechins.

  The water-insoluble complex is a substance that precipitates out of water as an insoluble substance when an aqueous solution of catechins and an aqueous solution of polymer A are mixed. Precipitation of the water-insoluble complex can be confirmed by the turbidity of the mixed solution or the presence of a peak derived from the water-insoluble complex when the mixed solution is measured with a laser diffraction / scattering particle size distribution analyzer. .

  Examples of the polymer A include polyvinyl pyrrolidone, polyvinyl alcohol, and hydroxyethyl cellulose, and polyvinyl pyrrolidone (hereinafter sometimes abbreviated as PVP) is preferable.

  The weight average molecular weight of the polymer A is preferably 6000 or more, more preferably 60000 or more, still more preferably 400,000 or more, and particularly preferably 1300000 or more, from the viewpoint of effectively suppressing catechin coloring. Moreover, 3000000 or less are preferable and 2000000 or less are more preferable from a viewpoint which suppresses that a water-insoluble composite_body | complex becomes a lump aggregate and obtains a fine water-insoluble composite_body | complex.

  In the present invention, the weight average molecular weight of the polymer A is a value measured by a viscosity method which is a general weight average molecular weight measurement method, a light scattering method or the like. When the polymer A is polyvinyl pyrrolidone, the weight average molecular weight is determined by the K-value calculated from the measured viscosity value based on the Fikentscher formula.

  The content of catechins in the hydrogel particles of the present invention is preferably 0.001 to 10% by mass from the viewpoint of catechins sufficiently acting on gums and the stability of hydrogel particles. 001-6 mass% is more preferable, and 0.01-2 mass% is still more preferable. In addition, the content of the polymer A is preferably 1 to 4 times by mass, more preferably 1 to 3 times by mass with respect to the catechins, from the viewpoint of effectively suppressing the coloring of the catechins. Two times by mass is more preferable.

  In addition, the content of the water-insoluble complex contained in the hydrogel particles is preferably 12% by mass or less from the viewpoint of suppressing the water-insoluble complex from becoming agglomerated aggregates and obtaining a fine water-insoluble complex. 8 mass% or less is more preferable, and 6 mass% or less is still more preferable.

  Examples of the gel-forming agent used in the hydrogel particles in the present invention include seaweed extracts such as agar, κ-carrageenan, ι-carrageenan, λ-carrageenan, furseleran, alginate, propylene glycol alginate; guar gum, locust Plant seed sticky substances such as bean gum, tamarind seed polysaccharide, tara gum and cassia gum; Plant fruit sticky substances such as pectin and arabinogalactan; Microbial production stickies such as xanthan gum, scleroglucan, pullulan, dextran, duran gum and curdlan Animal protein such as gelatin, albumin and casein; plant protein such as soybean protein and wheat protein; cellulose such as carboxymethylcellulose, methylcellulose and microcrystalline cellulose and derivatives thereof; starch, starch phosphate, Include starch and its derivatives such as flour glycolic acid esters, these may be used alone or in admixture of two or more. As the polymer that forms brittle gel particles that are physically easily broken, κ-carrageenan, agar, and duran gum are preferable.

  The content of the gel-forming agent in the hydrogel particles of the present invention is preferably from 0.25 to 5% by mass, preferably from 0.5 to 4 from the viewpoint of preventing breakage when the hydrogel particles are blended into the dentifrice composition. The mass% is more preferable, and 1-3 mass% is still more preferable.

  The hydrogel particles of the present invention contain components such as water-soluble organic compounds such as saccharides and polyhydric alcohols, colorants, preservatives, and water-soluble fragrances in addition to catechins, polymer A, gel-forming agent and water. It may be.

  Examples of the saccharide include glucose, galactose, fructose, mannose, mannitol, saccharose, maltose, lactose and the like.

  Examples of the polyhydric alcohol include glycerin, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and oligosaccharide.

  Although the manufacturing method of the hydrogel particle of this invention is not specifically limited, For example, gel forming agents, such as agar, and the polymer A are mixed with ion-exchange water, and it heats to the temperature beyond the melting temperature, and fully dissolves. After adding an aqueous solution of catechins here, hydrogel particles can be obtained by a general dropping method, spraying method, stirring method or the like.

  The dripping method uses the property that a liquid mixture is discharged from a hole and the discharged liquid mixture becomes droplets due to its surface tension or interfacial tension, and the liquid droplets are cooled in a gas phase or liquid phase such as air. This is a method for producing hydrogel particles by solidification. In addition, it is preferable to give a vibration to the liquid mixture discharged from the hole from the viewpoint of producing hydrogel particles having a uniform particle size.

  The spraying method uses a spray nozzle, sprays the liquid mixture from the spray nozzle into the gas phase, forms droplets by the surface tension, and cools and solidifies the droplets in the gas phase to produce hydrogel particles. It is.

  In the stirring method, the mixed liquid is poured into a liquid that has a property that does not substantially mix with the mixed liquid and is adjusted to a temperature equal to or higher than the gelling temperature, and the mixed liquid is atomized by a shearing force by stirring. This is a method for producing hydrogel particles by utilizing the property of forming droplets and cooling and solidifying the droplets in a liquid that does not substantially mix with the liquid mixture.

  In any of the dropping method, the spraying method, and the stirring method, the temperature of the mixed solution at the time of discharging, spraying, or charging is preferably set to a temperature of not less than the gelling temperature and not more than 100 ° C. In addition, from the viewpoint that spherical particles having excellent aesthetics can be easily produced, the temperature of the oil-in-water dispersion is preferably set to a gelation temperature + 10 ° C. or higher, and a gelation temperature + 20 ° C. or higher. More preferably. The upper limit of this temperature is 100 ° C., which is the boiling point of water.

  The dissolution temperature of agar in water is generally 75 ° C. or higher, and the main one is 75 to 90 ° C. The gelation temperature when the agar is dissolved in water and then cooled is 30 to 45 ° C. It is.

  In the hydrogel particles of the present invention, the water-insoluble complex of catechins and polymer A is dispersed and encapsulated in a continuous phase containing a gel-forming agent and water.

  The average particle size of the hydrogel particles of the present invention is preferably from 5 to 10,000 μm, more preferably from 100 to 10,000 μm, particularly preferably from 200 to 5000 μm, from the viewpoints of appearance and productivity. The average particle size of the hydrogel particles is expressed as a weight average particle size using various sieves, 100 g of the particles are wet-classified in water, excess water is removed with a filter paper, and the weight is measured (Fluy method). .

  In addition, the shape of the hydrogel particles of the present invention is not particularly limited, but it is preferable to have a shape of a rotating body constituted by a curved surface. Here, the “rotary body constituted by a curved surface” means a closed figure constituted by a virtual axis and a continuous curve, rotated by the virtual axis, and has a shape such as a triangular pyramid or a cylinder. Is not included. The shape of the hydrogel particles is more preferably spherical or elliptical from the viewpoint of aesthetics.

[Toothpaste composition]
The toothpaste composition of the present invention contains the above hydrogel particles, a binder and water.

  Examples of the binder used in the present invention include sodium alginate, sodium carboxymethyl cellulose, carrageenan, xanthan gum, sodium polyacrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, pectin, tragacanth gum, gum arabic, guar gum, caraya gum, locust bean gum. , Gellan gum, tamarind gum, psyllium seed gum, polyvinyl alcohol, sodium chondroitin sulfate, methoxyethylene maleic anhydride copolymer and the like, particularly sodium alginate, sodium carboxymethylcellulose, carrageenan and xanthan gum are preferred.

  Among the above-mentioned binders, sodium alginate is commercially available from Kimika Co., Ltd., Dainippon Pharmaceutical Co., Ltd., etc., and easily available intramolecular manuronic acid / guluronic acid (M / G ratio) is 0.5-2. .5 is preferred. Sodium carboxymethylcellulose is commercially available from Daicel Chemical, Daiichi Kogyo Seiyaku, etc., and preferably has an etherification degree of 0.6 to 2.5, but the etherification degree is 0.8 to 1.5. Are more preferred. Carrageenan may be any of the three isomers of kappa type, lambda type and iota type, and commercially available from Kelco, MRC polysaccharide, Taiyo Kagaku, etc. A mold and a lambda type are more preferable. Xanthan gum is commercially available from Taiyo Kagaku, Kelco, Dainippon Pharmaceutical Co., Ltd., etc., and can be easily obtained, but when used in combination with carboxymethyl cellulose, cellulase from which cellulase mixed in a small amount in xanthan gum has been removed. It is preferred to use low activity xanthan gum.

  The binder may be used alone or in combination of two or more, and the content of the binder in the composition is storage stability, viscosity of the composition, from the viewpoint of obtaining a higher refreshing feeling, 0.1-3 mass% is preferable, 0.1-2 mass% is more preferable, 0.2-1.2 mass% is still more preferable.

  In the toothpaste composition of the present invention, the content of the hydrogel particles is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and 1 to 5% from the viewpoint of the stability of the toothpaste composition. More preferred is mass%.

  The water content in the toothpaste composition of the present invention is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass from the viewpoint of obtaining storage stability and a higher refreshing feeling. .

  The toothpaste composition of the present invention may further contain a powder or particulate erythritol having a particle diameter of less than 355 μm from the viewpoint of a refreshing feeling, a cooling feeling and a taste. As the structure of erythritol, there are three isomers of L-erythritol, D-erythritol, and meso-erythritol, and any of these structures can be used in the present invention. As erythritol, those which are usually available can be used, and examples thereof include crystalline erythritol obtained by recrystallization after fermentation of glucose. As crystalline erythritol, commercially available products such as those manufactured by Nikken Chemical Co., Ltd., Mitsubishi Chemical Foods Co., Ltd., and Celestor are available. Moreover, the thing with a large particle size can use what adjusted the particle diameter by grind | pulverizing. A roller mill, a hammer mill, a high-speed pulverizer, a pulverizer, etc. are generally used to pulverize erythritol, but a high-speed pulverizer and hammer mill that are easy to adjust the particle size and excellent in production efficiency. Is preferred.

  The particle diameter of erythritol is preferably 45 μm or more and less than 355 μm, more preferably 53 μm or more and less than 300 μm, and even more preferably 75 μm or more and less than 250 μm, from the viewpoint that the cooling sensation continues in the oral cavity for a long time. Erythritol particles having a particle size of 45 μm or more are preferred because they do not dissolve instantaneously in the mouth and a long cool feeling. Moreover, the thing less than 355 micrometers can melt | dissolve easily in an oral cavity, and can exhibit a cool feeling.

The erythritol particle size is measured as follows.
Sieve: JIS standard sieve φ75mm
Opening: From the upper stage, a receiver is provided under a sieve having openings of 500 μm, 355 μm, 250 μm, 180 μm, 125 μm, 90 μm and 45 μm, respectively.
Shaker: Micro type electromagnetic vibrator M-2 type (Tsutsui Rikenki Co., Ltd.)
Method: Place 15 g of sample on 500 μm sieve and classify with electromagnetic vibrator for 5 minutes. The total amount of erythritol present on a sieve having openings of 250 μm, 180 μm, 125 μm, 90 μm and 45 μm is defined as erythritol having a particle size of 45 μm or more and less than 355 μm.

  In the toothpaste composition of the present invention, the blending amount of erythritol is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, and still more preferably 25 to 50% by mass, from the viewpoints of coolness and coolness. ˜50 mass% is particularly preferred.

  The erythritol is preferably dispersed in the dentifrice composition in powder form. For this purpose, erythritol is preferably added as a powder to the final production process. By using such a method, erythritol can be present in a powdered state in the toothpaste composition without being substantially dissolved in water.

  The toothpaste composition of the present invention can further contain an abrasive. As abrasives, silica such as precipitated silica, silica gel, aluminosilicate, silconosilicate, gluconosilicate, calcium carbonate, calcium hydrogen phosphate, calcium pyrophosphate, aluminum hydroxide, alumina, magnesium carbonate, magnesium phosphate Etc. The content of the abrasive is preferably 0 to 15% by mass, particularly preferably 0 to 12% by mass in the toothpaste composition of the present invention.

  The toothpaste composition of the present invention contains other ingredients that can be used in oral compositions, such as antioxidants, wetting agents, medicinal ingredients, foaming agents, preservatives, flavoring agents, sweetening agents, pH adjusting agents and the like. , And may be appropriately blended within a range that does not impair the object of the present invention.

  Antioxidants include components that have antioxidant or reducing power and can be used in oral compositions such as L-ascorbic acid and salts thereof, erythorbic acid and salts thereof, α-tocopherol acetate, dl-α -Tocopherol, rosemary extract, stevia extract, sunflower seed extract, propyl gallate, dibutylhydroxytoluene, butylhydroxyanisole, L-cysteine hydrochloride, phytic acid, hydroquinone and its glycoside, nordihydroguaiaretin Examples include acids, higher fatty acid esters of ascorbic acid (such as lauric acid esters, stearic acid esters, isostearic acid esters, and palmitic acid esters), guaiac fats, and the like. Examples of the salt of L-ascorbic acid, erythorbic acid, or α-tocopherol acetic acid include sodium salt, calcium salt, ferrous salt, palmitic acid ester salt, and the like. These antioxidants may be used alone or in combination of two or more. The content of the antioxidant is 0.0005 to 50% by mass, further 0.001 to 20% by mass, particularly 0.01 to 5% by mass in the toothpaste composition of the present invention, from the viewpoint of the effect of suppressing the change in appearance color. % Is preferred.

  Examples of the wetting agent include glycerin, sorbitol, polyethylene glycol, propylene glycol, ethylene glycol, 1,3-butylene glycol, polypropylene glycol, xylitol, erythritol, maltitol, lactitol, and the like. It can mix | blend in combination. The content of these wetting agents is preferably 40 to 95% by mass, and more preferably 60 to 80% by mass in the toothpaste composition of the present invention from the viewpoint of ensuring transparency.

  The toothpaste composition of the present invention can be made into a toothpaste composition, a liquid toothpaste composition, a gel-like toothpaste composition or the like according to a conventional method according to its use.

  Unless otherwise specified,% in the examples is% by mass.

Production Example 1
An aqueous solution (85 ° C.) prepared by dissolving 15 g of agar (Ina Food Industry Co., Ltd., UP-37) and 16 g of PVP (ISP, K-90, weight average molecular weight 1300000) in 319 g of ion-exchanged water, An aqueous solution (20 ° C.) prepared by dissolving 10 g of tea extract (Sanphenon 100S Taiyo Kagaku Co., Ltd., catechin content 60 to 70%) in 140 g of exchanged water was mixed (8000 r / min, 1 minute) with a homomixer. Then, hydrogel particles having the composition shown in Table 1 were obtained by spraying in the gas phase. The average particle size of the hydrogel particles was 200 μm.

Example 1
Using the hydrogel particles or tea extract (Sanphenon 100S Taiyo Kagaku Co., Ltd., catechin content 60-70%) obtained in Production Example 1, the toothpaste composition A (comparative product) and toothpaste composition having the composition shown in Table 2 Product B (product of the present invention) was prepared. About the obtained toothpaste composition A and B, discoloration and a taste were evaluated by the following method. The results are shown in Table 2. In addition, the effect on gums was examined by the following method. The results are shown in FIGS.

<Evaluation method of discoloration>
The obtained toothpaste composition was filled into a container, stored at 50 ° C. for 1 month, the brightness difference after storage was measured by the following method, and the degree of discoloration was evaluated based on the brightness difference. Pack the toothpaste composition after storage into a transparent case with a volume of 3cm x 3cm x 1cm (AS ONE, PS CASE No. 1). Along with the case, 9 points of KODAK GRAY SCALE A, 2, 4, 6, 8, 10, 12, 14, and B (color density 1-9) and CASMATCH (Dai Nippon Printing) Was in the same field of view and shot on a blank sheet. The shooting conditions were constant illumination of the ringlight, constant shutter speed, squeezing, and focal length. ADOBE PHOTOSHOP uses color correction with CASMATCH as a reference, and WINROOF (Mitani Corporation) quantifies the brightness of the measurement area (HSB color model Brightness) at 50 ° C for 1 month The difference between the lightness and the lightness immediately after production (initial) was obtained by the following formula (I) and used as the discoloration.

Discoloration degree = [lightness after storage at 50 ° C. for one month] − [initial lightness] (I)
<Taste evaluation method>
For the flavors of the toothpaste compositions A and B, the taste was evaluated by nine panelists according to the following three-stage criteria, and the average value was shown.
・ Evaluation criteria 1: Not astringent 2: Not very astringent 3: Astringent <Effect on gums>
Nine men and women in their 20s to 50s used toothpaste compositions A and B for 1 week, respectively, and examined changes in BOP (Bleeding On Probing) before and after use. BOP (Bleeding On Probing) refers to a state where a WHO probe is inserted into the gingival floor of the periodontal pocket (gap between the teeth and gums) and then bleeding, and if the gums are healthy, they will not bleed. Inflammation easily causes bleeding. That is, the larger the number of BOP sites, the worse the gum state.

* 1: Polyethylene glycol with an average molecular weight of 600
* 2: Sorbosyl AC43 (Ineos silica)
* 3: Sorbosyl TC15 (Ineos silica)
* 4: CMC <1150> Daicel Chemical Co., Ltd.
* 5: Sanphenon 100S; Taiyo Kagaku Co., Ltd., catechin content 60-70%
As is apparent from Table 2, the dentifrice composition B containing the hydrogel particles of the present invention encapsulating catechins is significantly discolored as compared to the dentifrice composition A containing catechins without encapsulating them. It was suppressed and the taste was excellent.

  Further, as apparent from FIGS. 1 and 2, when the toothpaste composition A was used, the BOP value did not change substantially in one week, and the gum condition did not improve, but the toothpaste composition B was used. If it does, the value of BOP decreases in one week, and it can be seen that the state of gums has improved. By using catechin hydrogel particles, the effect of improving gingivitis is improved and is considered useful.

Example 2
Using the hydrogel particles or tea extract (Sanphenon 100S Taiyo Kagaku Co., Ltd., catechin content 60 to 70%) obtained in Production Example 1, the toothpaste composition C (comparative product) and toothpaste composition having the composition shown in Table 3 Product D (product of the present invention) was prepared. The obtained toothpaste compositions C and D were evaluated for discoloration and taste in the same manner as in Example 1. The results are shown in Table 3.

* 1 to * 5 are the same as Table 2.
* 6: Erythritol having a particle size distribution of 13% by mass of less than 45 μm, 82% by mass of 45 μm to less than 250 μm, and 5% by mass of 250 μm to less than 355 μm As shown in Table 3, the catechins are encapsulated in the present invention. The toothpaste composition D containing hydrogel particles was remarkably suppressed in color change and excellent in taste as compared with the toothpaste composition C containing catechins as it was without being encapsulated.

It is a figure which shows the effect on the gum of the toothpaste composition A. It is a figure which shows the effect on the gum of the toothpaste composition B.

Claims (3)

  A dentifrice composition containing catechins and hydrogel particles containing a water-soluble polymer (hereinafter referred to as polymer A) that forms a water-insoluble complex with catechins, a binder, and water.   The dentifrice composition according to claim 1, wherein the polymer A is polyvinylpyrrolidone. Binder is sodium alginate, sodium carboxymethylcellulose, carrageenan, xanthan gum, sodium polyacrylate, hydroxyethylcellulose, hydroxypropylcellulose, pectin, tragacanth gum, gum arabic, guar gum, caraya gum, locust bean gum, gellan gum, tamarind gum, psyllium seed The dentifrice composition according to claim 1 or 2, which is at least one selected from the group consisting of gum, polyvinyl alcohol, sodium chondroitin sulfate and a methoxyethylene maleic anhydride copolymer.

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