JP5703617B2 - Bad breath deodorant preparation - Google Patents

Description

The present invention relates to a mouth odor deodorant preparation which provides an oral care composition which has a high deodorizing effect on bad breath immediately after use, can further maintain the deodorizing effect, and has a good usability .

  The bad breath is caused by methyl mercaptan, hydrogen sulfide, or the like generated by decomposition of oral dirt (food residues, exfoliated mucous membranes, etc.) by the bacteria that cause bad breath.

  Conventional techniques for suppressing bad breath include (1) methyl mercaptan capture and deodorization, (2) removal of bad breath causing bacteria, (3) inhibition of enzymes that cause bad smell of bad breath causing bacteria (bacterial metabolism inhibition), (4) There are methods such as removal of dirt by promoting salivary secretion, and many effective deodorants have been reported for (1), which is particularly important. Among them, as a combination of deodorants with strong deodorizing power and considering safety and environmental aspects, the deodorizing effect is obtained by using a combination of oxidoreductases that oxidize phenolic compounds such as Lamiaceae plants and polyphenol oxidase. It is known that the effect can be enhanced synergistically (Patent Documents 1 to 5: JP 2008-029221 A, JP 2004-321077 A, JP 2003-175095 A, and Japanese Patent Publication No. 10-212221. Gazette, Japanese Patent Publication No. 7-53174). However, these methods have insufficient sustainability of the deodorizing effect of bad breath.

  In addition, the applicant has proposed the persistence of the halitosis suppression effect due to the combined effect of halitosis supplementation of Lamiaceae plants or their extracts and the metabolism inhibition of halitosis causal fungus plants or extracts by the citrus family Salamander plants or extracts (patents) Documents 6 to 8: Japanese Patent Application Laid-Open No. 2005-289918, Japanese Patent Application Laid-Open No. 01-016713, Japanese Patent Application Laid-Open No. 63-309269). In this case, when the amount of the plant extract increases, In some cases, it is difficult to maintain a high feeling of use while maintaining a good feeling of bad breath, and there is still room for improvement. A chewing gum composition having a deodorizing action using rosemary or an extract thereof and an oxidoreductase in combination has also been proposed (Patent Document 9: JP 2009-136240 A).

  On the other hand, polyglutamic acid or a salt thereof is known to have a salivary secretion effect (Patent Document 10: International Publication No. 2005/049050 pamphlet), and due to the salivary secretion promoting effect of polyglutamic acid or a salt thereof in the oral cavity An edible film for oral hygiene that removes soil and bad breath-causing bacteria has been proposed (Patent Document 11: Japanese Patent Application Laid-Open No. 2007-326808). However, although the edible film for oral hygiene can suppress bad breath by promoting saliva secretion, its bad breath suppression effect is lower than that of a composition having a known deodorant component, and the stain was washed away with saliva. The bad breath suppression effect was insufficient, such as no effect on bad breath generated later.

  Therefore, a new technique that provides a preparation that exhibits a high halitosis suppression effect continuously and has a good feeling in use is desired.

In addition, as a technique in which an enzyme or a polycationic substance is blended, Patent Document 12 (Japanese Patent Application Laid-Open No. 61-76411) discloses that dextranase is inactivated by chewing gum containing an anionic surfactant. As a method for retaining enzyme activity over a long period of time, a polycationic stabilizer is disclosed in Patent Document 13 (Japanese Patent Application Laid-Open No. 2002-370957), which removes plaque by basic peptide, glucan-degrading enzyme and anethole. It is disclosed that the effect is improved.
Patent Documents 14 and 15 (JP-A-5-310544 and JP-A-10-298048) disclose polycationic substances in which ε-poly-L-lysine or a salt thereof is used as a causative or periodontal disease-causing bacterium. It has been disclosed that it has an antibacterial action, and that polylysine has a neutralizing action of periodontal disease bacterial endotoxin and an adhesion suppressing effect of periodontal disease-causing bacteria. Further, Patent Documents 16 and 17 (International Publication No. 2007/105661 pamphlet, Japanese Patent Laid-Open No. 2-86731) have been proposed as methods for producing enzyme-containing candy.
However, it is difficult to predict from these techniques that the retention of laccase is improved by the polycationic substance in the oral cavity and the excellent deodorizing effect can be sustained.

JP 2008-029221 A JP 2004-321077 A JP 2003-175095 A Japanese Patent Publication No. 10-212221 Japanese Patent Publication No. 7-53174 JP 2005-289918 A Japanese Patent Laid-Open No. 01-016713 JP-A 63-309269 JP 2009-136240 A International Publication No. 2005/049050 Pamphlet JP 2007-326808 A JP 61-76411 A JP 2002-370957 A JP-A-5-310544 Japanese Patent Laid-Open No. 10-298048 International Publication No. 2007/105661 Pamphlet JP-A-2-86731

Applicant has a deodorizing effect on oral malodor and a long-lasting oral care composition by blending a Labiatae plant or extract thereof, laccase, and polyglutamic acid having one amino group in the molecule or a salt thereof. The product was proposed in Japanese Patent Application Laid-Open No. 2010-168353, but when this technology was further examined, when polyglutamic acid or its salt absorbs moisture during storage and the laccase activity after storage decreases accordingly. As it turned out, there was a need for new alternative technologies. Japanese Patent Application Laid-Open No. 2011-219386 proposed an oral care composition having a deodorizing effect on oral malodor and a long-lasting odor, which is a mixture of Lamiaceae plant extract, laccase and lactoferrin. This technology has achieved the deodorizing effect due to the antibacterial effect of lactoferrin and the synergistic effect of Labiatae plant extract and laccase, but since lactoferrin is an expensive substance, a new alternative technology is required .
The present invention has been made in view of the above circumstances, and the object thereof is an oral care composition that has a high deodorizing effect on bad breath immediately after use, can further maintain the deodorizing effect, and has a good feeling in use. It is to provide a deodorant preparation that gives a bad breath .

As a result of diligent studies to achieve the above-mentioned object, the present inventors care by cleaning the oral cavity and solving troubles such as periodontal diseases, and QOL (Quality of Life) Oral care compositions useful for improving (A) one or more basic substances selected from polylysine, polyarginine and polyhistidine as a polycationic substance having two or more functional groups exhibiting cationic properties in the molecule and peptides, formulated in combination with (B) laccase, (a) shows the mixing ratio of the amount of the component (B) and the amount of the 360,000 units / g product component (a) / ( B) is at 0.005 to der Rukoto as a mass ratio, (a) a polycationic substance to improve the retention in the oral cavity of the (B) laccase, deodorizing bad breath derived laccase It found that results can be exhibited sustained effectively, leading to the completion of the present invention. According to the present invention, it is excellent in the quickness and sustainability of the deodorizing effect of bad breath, the high deodorizing effect of bad breath is continuously exerted, and there is no off-flavor and the feeling of use is good. Furthermore, the appearance of the preparation is also improved.
In this invention, a higher deodorizing effect is exhibited by further blending (C) Lamiaceae plant or an extract thereof. (A) in combination with polycationic materials of component (B) and laccase, and (C) by blending the Labiatae plant or its extract, deodorizing effect is synergistic derived from Labiatae plants or extracts thereof Therefore, a higher deodorizing effect can be exhibited quickly and continuously.
In the present invention, (D) one or more enzymes selected from dextranase, mutanase, actinidine, papain, and bromelain can be blended, and these enzymes are stabilized in the composition and sufficiently retained in the oral cavity. In addition, a decrease in activity during storage can be suppressed.

Therefore, the present invention provides the following bad breath deodorant preparation .
Claim 1:
(A) 0.001 to 5% by mass of one or more basic peptides selected from polylysine, polyarginine and polyhistidine , and (B) 0.001 to 3% by mass with 360,000 units / g of laccase (A) / (B) which shows the compounding ratio of the compounding quantity of (A) component and the compounding quantity as a 360,000 unit / g product of (B) component is 0.005-100 as mass ratio. bad breath deodorant formulation which is characterized in that there.
Claim 2 :
Furthermore, it contains (C) Labiatae plant or its extract, and shows the blending ratio between the blending amount of (C) component and the blending amount of (B) component as 360,000 units / g product (B) / (C) is breath freshening preparation according to claim 1, wherein Ru 0.001 der as a mass ratio.
Claim 3 :
The bad breath deodorant preparation according to claim 2 , wherein the Labiatae plant as component (C) is at least one selected from rosemary, sage, perilla, mint, thyme and melissa.
Claim 4 :
The oral deodorant preparation according to claim 2 or 3, which contains 0.001 to 5% by mass of component ( C).
Claim 5 :
5. The halitosis deodorant preparation according to any one of claims 1 to 4 , further comprising (D) one or more enzymes selected from dextranase, mutanase, actinidine, papain, and bromelain .
Claim 6:
The oral deodorant preparation according to any one of claims 1 to 5, wherein the water content in the preparation is 0 to 5% by mass.

  The oral care composition of the present invention is eaten when bad breath is worrisome or is applied to the oral cavity. It can be suppressed and has a good taste when used. Furthermore, it can have a good formulation appearance, is excellent in portability, can be easily applied when necessary, and is effective in preventing or suppressing bad breath. Furthermore, the composition of the present invention can stably contain an enzyme such as dextranase, and can maintain good activity during storage.

Hereinafter, the present invention will be described in more detail. The bad breath deodorant preparation that gives the oral care composition of the present invention contains (A) a polycationic substance having two or more functional groups having cationic properties in the molecule, and (B) laccase, and more preferably ( C) Contains Lamiaceae plants or extracts thereof.

  (A) As the polycationic substance, those having two or more functional groups exhibiting cationic properties in one molecule are used. By blending this polycationic substance, the retention of laccase in the oral cavity is increased and the deodorizing effect of bad breath is improved.

Here, specific examples of the functional group exhibiting cationic properties include an amino group, an ammonium group, an imidazolyl group, and a guanidyl group.
The number of functional groups exhibiting cationic properties may be two or more in the molecule, and those having 20 to 420 are particularly preferable.

  Examples of the polycationic substance include basic peptides, basic proteins, basic polysaccharides, and polyolefins having an amide group in the side chain, in which a 0.1% aqueous solution has a pH of 5.0 to 9.0. Of these, basic peptides are preferred. Specifically, polylysine, polyarginine, polyhistidine as basic peptides, lysozyme as basic protein, chitosan, cationized hyaluronic acid, cationized cellulose, etc. as basic polysaccharides, one or two of these The above can be used. Among these, polylysine, polyarginine, and polyhistidine are more preferable because they have a long-lasting deodorizing effect on bad breath and excellent stickiness during long-term storage. In the case of a highly hygroscopic substance, stickiness and low laccase activity may occur during long-term storage, and therefore a substance with as low a hygroscopic property as possible is preferable.

  The molecular weight of the polycationic substance is not particularly limited, but a number average molecular weight of 300 to 300,000, particularly 2,000 to 30,000 is preferable. If the number average molecular weight is less than 300, the retention of laccase is low, and the sustainability of the deodorizing effect may be reduced. If it exceeds 300,000, it may cause off-flavors, form a complex with laccase in the production process or saliva, precipitate, decrease the activity of laccase immediately after production and after storage, Odor effect and its sustainability may be reduced.

Here, the number average molecular weight is the average molecular weight given by Mn = ΣMiNi / ΣNi when there are Ni molecules having a molecular weight Mi. Examples of the measuring method include an osmotic pressure method, a boiling point increasing method, a coagulation decreasing method, and a GPC (Gel Permeation Chromatography) method.
The GPC method measures the molecular weight distribution. The molecular weight is converted into a standard substance such as polystyrene, the low angle light scattering method (LALLS), the multi angle light scattering method (MALLS), and the multi angle light scattering method (MALLS). There are GPC-LALLS method and GPC-MALLS method which are measured by Scattering. GPC is also called SEC (Size Exclusion Chromatography). The method for measuring the number average molecular weight used in the present invention is not particularly limited, but the GPC-LALLS method can be measured, for example, under the following conditions. (A) The number average molecular weight of the polycationic substance is a measured value under the following conditions. It is.
GPC-LALLS method column: Tosoh Biosep G5000 PWXL, 7.8 mm × 30 cm
Moving layer: 0.1 mol / L sodium phosphate buffer (pH 7.0)
Flow rate: 0.5 mL / min
Column temperature: 40 ° C

  A commercially available product can be used as the polycationic substance. As polylysine, Sunkeeper No. 381 (trade name, number average molecular weight: 2,600, manufactured by Saneihara FFI Co., Ltd.), poly-L-lysine hydrochloride (trade name, number average molecular weight: 30,000, Sigma Aldrich Japan Co., Ltd.) )), 0.1% poly-L-lysine aqueous solution (trade name, number average molecular weight: 300,000, Sigma-Aldrich Japan Co., Ltd.), and polyarginine are poly-L-arginine hydrochloride (trade name, Number average molecular weight 15,000, manufactured by Sigma Aldrich Japan Co., Ltd.), poly-L-histidine as poly-L-histidine (trade name, number average molecular weight 10,000), and lysozyme as Sunkeeper No. 657 (trade name, number average molecular weight 14,300, manufactured by Saneihara FFI Co., Ltd.), COS-YS (trade name, number average molecular weight 680, manufactured by Yaizu Suisan Chemical Co., Ltd.) as chitosan oligosaccharide ) And the like.

  The blending amount of the polycationic substance is preferably 0.001 to 5% (mass%, the same applies hereinafter), particularly 0.001 to 2% of the entire composition. If it is less than 0.001%, the deodorizing effect of bad breath may not be satisfactorily exhibited. If it exceeds 5%, it may cause off-flavours, form a complex with laccase in the production process or saliva, precipitate, decrease the activity of laccase immediately after production and after storage, Odor effect and its persistence may be reduced.

The laccase of component (B) is E. coli. C. It is an oxidase classified as 1.10.3.2, and as a typical enzyme reaction example, it is known that urushiol is oxidized by laccase in lacquer sap to form lacquer. Laccase is widely present in many plants and microorganisms besides lacquer, and is an enzyme that catalyzes the oxidation reaction of aromatic compounds. In the present invention, laccase can be used regardless of its origin, and bad breath It is blended as a deodorant component.
In addition, laccase coated with sodium carboxymethylcellulose, sodium alginate, carboxyvinyl polymer or the like can be used for stabilization.
As the laccase, commercially available products such as laccase Daiwa manufactured by Amano Enzyme Co., Ltd. are used. This is formed by shaping 80,000 units / g of pure 80% with 20% dextrin.

The blending amount of laccase is preferably 3 to 10,000 units / g, more preferably 30 to 10,000 units / g, and particularly preferably 30 to 3,500 units / g. If it is less than 3 units / g, the enzyme activity may be low and the deodorizing effect may be insufficient or the sustainability may be inferior, and the activity may easily decrease during production and storage. If it exceeds 10,000 units / g, it may cause an unpleasant taste, and the candy may have poor appearance uniformity.
When based on a product of 360,000 units / g, the blending amount of laccase is 0.001 to 3% of the total composition, preferably 0.01 to 3%, more preferably 0.01 to 1 in terms of pure content. %. If it is less than 0.001%, the enzyme activity is low, the deodorizing effect is insufficient, the sustainability may be inferior, and the activity may be easily lowered during production and storage. If it exceeds 3%, it may cause an unpleasant taste, and the appearance uniformity of the candy may be deteriorated.
In addition, when acting on 4-aminoantipyrine and phenol at pH 4.5 and 30 ° C., the absorbance at 505 nm of the quinoneimine dye produced by the oxidative condensation reaction catalyzed by laccase is increased by 0.1 in the first minute of the reaction. The amount of enzyme required is 1 unit.

  The blending ratio of (A) polycationic substance and (B) laccase is not particularly limited, but is preferably 0.005 to 100, and particularly preferably 0.01 to 50, by mass ratio of (A) / (B). If it is less than 0.005, the deodorizing effect of bad breath may not be satisfactorily exhibited. If it exceeds 100, a complex is formed and precipitates in the saliva or in the concentration process during candy production, and the activity of laccase immediately after production and after storage is reduced. May decrease. Further, the appearance of candy may be inferior.

  (C) Labiatae plant or its extract is blended as a deodorant component of bad breath, such as rosemary, sage, perilla, mint, thyme, melissa, sage, marjoram, oregano, basil, naginata, koju, lavender, bergamot, etc. In particular, Lamiaceae plants selected from rosemary, sage, perilla, mint, thyme, and melissa or extracts thereof can be used. Among them, rosemary and / or sage plants or extracts thereof are more preferable because they have a particularly high deodorizing effect on bad breath. These may be used alone or in combination of two or more.

  As the Labiatae plant or an extract thereof, known ones can be used. For example, those made from leaves and stems such as rosemary, sage, perilla, mint, thyme, melissa, etc., pulverized and powdered can be used, and the above Lamiaceae plants can be used as polar solvents and / or nonpolar solvents ( For example, polar solvents such as water, ethyl ether, ethylene chloride, dioxane, acetone, ethanol, methanol, ethyl acetate, propylene glycol, or n-hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1, 2-polar ethane, nonpolar solvents such as toluene and benzene, or mixed solvents thereof), and extraction obtained by performing solvent extraction on the raw material selected from the extract obtained by extraction and its extraction residue As well as carnosol, carnosic acid isolated from the above plant, , 11,12-trihydroxy-6,10- (epoxymethano) abieta-8,11,13-trien-20-one (Rosmanol), and salts thereof, etc. (JP 59-203445 A) No. 5, JP-A-57-204278, and JP-A-59-103665). Alternatively, the extract may be dried to a powder, and powdered by adding an excipient such as dextrin.

The solvent used in the solvent extraction treatment may be an organic solvent or an inorganic solvent as described in the above publication, and may be a mixed solvent of an organic solvent and an inorganic solvent, or one kind alone or two or more kinds. May be used in combination. Specific examples of the organic solvent include ethyl ether, ethylene chloride, dioxane, acetone, ethanol, methanol, ethyl acetate, propylene glycol, n-hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2 -Dichloroethane, toluene, benzene and the like. As the inorganic solvent, water, and an aqueous solution of acid, alkali or a salt thereof can be used. Specifically, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, carbonic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, water Examples thereof include calcium oxide and sodium sulfate. These acids, alkalis and salts are preferably used at a concentration of 2 mol or less. Preferred solvents are water, lower monohydric alcohols having 1 to 3 carbon atoms, and polyhydric alcohols. Moreover, it is preferable that the usage-amount of the solvent quoted above shall be equal capacity or more with respect to a raw material.
As the Lamiaceae plant or an extract thereof, commercially available products such as those manufactured by Toyoda Fragrance Co., Ltd. can be used.

  When compounding Lamiaceae plants or extracts thereof, the compounding amount is 0.001 to 5%, preferably 0.01 to 3%, more preferably 0.01 to 2% of the total composition in terms of pure content. is there. If it is less than 0.001%, the deodorizing effect may not be synergistically improved, and if it exceeds 5%, it may cause a taste.

  The blending ratio of (B) laccase and (C) Labiatae plant or an extract thereof is not particularly limited, but the mass ratio of (B) / (C) is preferably 0.001 to 100, particularly preferably 0.01 to 10. If it is less than 0.001, the synergistic effect by using the Lamiaceae plant or its extract in combination with laccase is not sufficiently exhibited, and the deodorizing effect of bad breath may not be synergistically improved. If it exceeds 100, the oxidation rate of the Labiatae plant or the extract thereof becomes too fast, and the deodorizing effect of bad breath may decrease.

The composition of the present invention can further contain an enzyme other than laccase as component (D). In the composition of the present invention, the enzyme is stabilized by the polycationic substance of the component (A), the retention of the component (D) in the oral cavity is improved, and an excellent deodorizing effect and its sustainability are exhibited. can do. Furthermore, the activity fall at the time of long-term storage can be suppressed.
Specific examples of the component (D) enzyme include polysaccharide-degrading enzymes and proteolytic enzymes. Particularly, one or more selected from dextranase, mutanase, papain, actinidine, bromelain and the like are preferably used. it can.

  (D) When mix | blending the enzyme of a component, the compounding quantity can be made into the effective quantity according to the kind and titer of an enzyme. For example, when dextranase is based on 12,000 unit products, 0.01 to 5% of the total composition, and mutanase is based on 6,000 unit products and is 0.01 to 5% of the total composition. can do. The above unit of dextranase and mutanase means that each enzyme that produces free reducing sugar corresponding to 1 μmol of glucose per minute when reaction is carried out at 40 ° C. and pH 5 using dextran and mutan as substrates. Amount.

The composition of the present invention is an oral care composition useful for improving the QOL by taking care of the oral cavity by cleansing the oral cavity or solving troubles such as periodontal diseases. Various preparations can be prepared. In this case, the composition of the present invention is used after being chewed in the oral cavity or dissolved in saliva or used after being chewed. A dosage form that retains for about 10 minutes is preferred. Furthermore, it is more desirable to prepare a dosage form and shape that can prevent the enzyme such as laccase from coming into contact with oxygen and prevent contact with oxygen as much as possible.
Specifically, it can be prepared as a confectionery, a food such as a health food, a preparation for the oral cavity, etc., such as a confectionery such as tablet confectionery, gummy, jelly, caramel, health food, candy, chewing gum, troche, chewable tablet, buccal tablet, etc. Examples include oral tablets that are used without being swallowed and dissolved in the oral cavity. Among these, preparation as candy, tablet confectionery, oral tablet, or chewing gum, particularly candy or chewing gum is preferable because high laccase activity can be maintained even after storage. The shape is not particularly limited, and for example, it can be prepared in the form of granules, granules, tablets, plates, films, capsules, and the like.
In addition, it is desirable that the amount of water in the preparation is small, and it is preferably 5% or less, particularly preferably 3% or less, or 0% of the whole composition. If it exceeds 5%, the activity of laccase tends to decrease during storage, and the activity of laccase after storage may decrease.

The candy includes soft candy such as caramel and nougat, hard candy such as drop and toffee and the like, and is not particularly limited. However, a hard candy is preferable in that it can suppress a decrease in laccase activity after storage.
Candy can be produced by a conventional method, for example, by the following method.

Candy production:
Add about half of the total amount of water to each component excluding the components (A), (B), if necessary, the functional component (C), the enzyme (D), non-heat-resistant components such as fragrance, etc. Then, the mixture is heated and dissolved in a mixing kettle, and further heated and concentrated to 180 ° C. to prepare a candy base. Then, it cools slowly stirring, adds a non-heat-resistant component between 90-130 degreeC, mixes uniformly, and also cools and shape | molds and produces. In this case, it is desirable that the cooling after the addition of the non-heat resistant component is performed by moving to a cooling plate or the like. In addition, since enzymes such as laccase are very sensitive to heat, it is more preferable to add between 70 to 120 ° C. during the cooling process on the cooling plate and to stir and mix on the cooling plate than to cool in the mixing kettle. It is preferable for maintaining the activity of the enzyme and the high deodorizing effect. In this case, the amount of powder containing an enzyme such as laccase to the cooling plate is preferably 5% or less, more preferably 3% or less of the entire composition. If it exceeds 5%, the powder may not be mixed uniformly and the appearance uniformity may deteriorate.

  Tablet confectionery is a saccharide-based material that is compression-molded with a tableting machine or the like, and may be sugar-coated. The manufacturing method of tablet confectionery is not specifically limited, It can prepare by a well-known method, Specifically, it can manufacture by mixing each component and compressing with 5-20 kN with a tableting machine etc.

  The main ingredients of candy and tablet confectionery are excipients, sweeteners and the like. Furthermore, if necessary, flavors, acidulants, thickeners, gelling agents, coloring agents, preservatives, fruit juices, fruit processing as described below Products, salting agents, bittering agents and the like can be added. An emulsifier, a lubricant, a disintegrant, a binder, a static eliminating agent and the like can be further added to the tablet confectionery.

Excipients include sugars such as sucrose, glucose, dextrose, invert sugar, fructose, sugar alcohols such as xylitol, erythritol, sorbitol, mannitol, maltitol, lactitol, reduced palatinose, reduced starch syrup, palatinose, trehalose, oligosaccharide, A dextrin etc. are mentioned, Among them, sugar alcohol, palatinose, and trehalose having non-cariogenic properties are preferable. In particular, tablet confectionery is preferably selected from sorbitol, maltitol, erythritol, xylitol, and reduced palatinose in terms of moldability and flavor, and candy is preferably reduced palatinose and reduced starch syrup in terms of low hygroscopicity.
These excipients can be blended singly or in combination of two or more, and the blending amount is desirably 50 to 99%, particularly 70 to 99% of the entire composition.

  As sweeteners for tablet candy and candy, stevia, sucralose, saccharin, aspartame, acesulfame potassium and the like can be contained in addition to the above-mentioned excipients. The blending amount of these sweeteners is usually 0.001 to 3%.

  The chewing gum may be any of taste gum, bubble gum and sugar-coated gum. For example, the chewing gum is mainly composed of a gum base, sweeteners, and flavors, active ingredients, coloring agents and the like as described below are blended to form a sugar coating layer. Is a sweetener such as maltitol, and can further contain a binder such as edible gum, other active ingredients, sweeteners, pigments, acidulants, flavors and the like.

  As a gum base, commonly used polyvinyl acetate resins having a polymerization degree of 100 to 1,000, natural resins (such as chicle, gelton, and solver), polyisobutylene, polybutene, ester gum, and other basic agents, calcium carbonate, and calcium phosphate In addition, fillers such as talc, plasticizers or softeners such as lanolin, stearic acid, sodium stearate, potassium stearate, glyceryl triacetate, glycerin, natural wax, petroleum wax, paraffin wax, etc. can also be incorporated into the gum base. . The blending amount of the gum base is preferably 10 to 50%, particularly preferably 15 to 35% of the entire composition.

  As sweeteners to be mixed in chewing gum, commonly used sweeteners can be used, for example, sugars such as sucrose, glucose, dextrose, invert sugar, fructose, xylitol, erythritol, sorbitol, mannitol, maltitol, lactitol, palatinose, reduced It is preferable to contain at least one selected from palatinose, trehalose, oligosaccharide, reduced starch syrup, stevia, sucralose, saccharin, aspartame, particularly those selected from xylitol, maltitol, sucralose in terms of flavor to improve the texture. It is preferable to contain reduced palatinose in that respect. The blending amount of the sweetener is desirably 10 to 75%, particularly 15 to 70% of the whole composition.

  In the oral care composition of the present invention, in addition to the above components, other known additives depending on the dosage form, if necessary, such as fragrances, emulsifiers, acidulants, colorants, pH adjusters, preservatives, glosses An agent, a static eliminating agent, a fluidizing agent, a disintegrant, a binder, a lubricant, and the like may be appropriately added within a range not impairing the effects of the present invention. Furthermore, you may add active ingredients other than the said enzyme, a Labiatae plant, and its extract, a thickener, a gelling agent, fruit juice, processed fruit products, a salty seasoning, a bittering agent, etc. if needed.

  As a fragrance | flavor mix | blended with the oral care composition of this invention, 1 type (s) or 2 or more types of fats and oils fragrance | flavors and powdered fragrance | flavors, such as a natural fragrance | flavor and a synthetic fragrance | flavor, can be used. For example, natural flavors such as mastic oil, parsley oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, menthol oil, spearmint oil, peppermint oil, lemon oil, coriander oil, orange oil, mandarin oil, lime oil, lavender Oil, laurel oil, chamomile oil, cardamom oil, caraway oil, bay oil, lemongrass oil, pine needle oil, neroli oil, rose oil, jasmine oil, Iris concrete, absolute peppermint, absolute rose, orange flower, citrus oil, Examples include mixed fruit oil, strawberry oil, cinnamon oil, clove oil, and grape oil.

  Single flavors include carvone, anethole, methyl salicylate, cinnamic aldehyde, linalool, linalyl acetate, limonene, menthone, menthyl acetate, pinene, octyl aldehyde, citral, pregon, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate Rate, allylcyclohexanepropionate, methylanthranilate, ethylmethylanthranilate, vanillin, undecalactone, hexanal, ethinone alcohol, propyl alcohol, butanol, isoamyl alcohol, hexenol, dimethylsulfide, cycloten, furfural, trimethyl Examples include pyrazine, ethyl lactate, and ethyl thioacetate. Single flavor and / or natural flavors including strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, tropical fruit flavor, butter flavor, milk flavor, yogurt flavor, fruit mix flavor, herbal mint Flavors and the like. Moreover, the form of a fragrance | flavor may be an essential oil, an extract, a solid substance, or the powder which spray-dried these. The blending amount of the fragrance is preferably 0.001 to 15%, particularly 0.001 to 10% of the whole composition, and if it is less than 0.001%, sufficient palatability may not be obtained, and 15% If it exceeds 1, the flavor and texture of the composition may be impaired.

As an emulsifier, as a nonionic surfactant, a sucrose fatty acid ester which is a fatty acid ester of sugar or sugar alcohol, maltose fatty acid ester, maltitol fatty acid ester, maltotriitol fatty acid ester, maltotetrathol fatty acid ester, maltopentai Examples include tall fatty acid ester, maltohexaitol fatty acid ester, maltoheptytitol fatty acid ester, sorbitan fatty acid ester, lactose fatty acid ester, and lactitol fatty acid ester. In addition, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, and the like can be used. It is preferable to use a fatty acid having 12 to 18 carbon atoms. Further, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, betaine laurylmethylaminoacetate, and the like, anionic surfactants such as sodium N-lauroylglutamate, sodium N-palmitoylglutamate N-acyl glutamic acid sodium, N-lauroyl sarcosine sodium, N-acyl sarcosine sodium, such as sodium N-myristoyl sarcosine, N-lauroyl methyl taurine sodium, N-methyl-N-acyl taurine, such as sodium N-myristoyl methyl taurine Sodium or the like can be blended. Of these, nonionic surfactants are preferred, and sugar or sugar alcohol fatty acid esters and glycerin fatty acid esters are more preferred.
These surfactants can be blended arbitrarily, but when blended, the blending amount is preferably 0.01 to 3%.

  Moreover, organic acids, such as a citric acid, malic acid, succinic acid, tartaric acid, can be mix | blended as a sour agent, and a compounding quantity is 0.001 to 5% normally.

Further, as coloring agents, natural dyes such as safflower red pigment, gardenia yellow pigment, gardenia blue pigment, perilla pigment, red potato pigment, red cabbage pigment, carrot pigment, hibiscus pigment, cacao pigment, spirulina pigment, coumarindo pigment, and red 3 , Red 104, red 105, red 106, yellow 4, yellow 5, green 3, blue 1, etc., riboflavin, copper chlorofin sodium, etc., citric acid, apple as pH adjuster Examples thereof include organic acids such as acid, tartaric acid, and succinic acid and sodium salts or potassium salts thereof, phosphates such as sodium phosphate and sodium hydrogen phosphate, and carbonates such as sodium carbonate and sodium hydrogen carbonate.
Examples of the preservative include benzoic acid or a salt thereof, parabens (paraoxybenzoic acid ester) such as methylparaben, ethylparaben, propylparaben, and butylparaben, sorbic acid or a salt thereof, and the like. As brighteners, waxes such as shellac, carnauba wax and candelilla wax and calcium stearate can be blended, and as neutralizing agents and fluidizing agents, fine particle silicon dioxide and the like can be blended.
These blendings are optional, but when blended, the colorant is preferably 0.00001 to 3%, and the other components are each preferably 0.01 to 5%.

Further, in tablet confectionery, pregelatinized starch, sodium alginate, crospovidone, carboxymethylcellulose and the like can be blended as disintegrating agents, and hydroxypropylcellulose, hydroxymethylcellulose, karaya gum and the like can be blended as binders. When blending these, the blending amount is preferably 0.1 to 10%.
Moreover, glycerin fatty acid ester etc. can be mix | blended as a lubricant.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited by the following Example. In addition, unless otherwise indicated, all the% shown below mean the mass%, and the compounding ratio of a component is a mass ratio.
The number average molecular weight of the polycationic substance is a value measured under the same conditions as described above by the GPC-LALLS method.

Examples and comparative examples
The oral care compositions having the compositions shown in Tables 1 to 8 were prepared into candy, tablet confectionery or chewing gum dosage forms by the following methods and evaluated by the following methods. The results are shown in Tables 1-8.

<Preparation of candy (Example 1～27,29～ 44, Comparative Examples 1 to 3)>
(A) Component, (B) component, (C) component, (D) component, add about half of the total amount of water to each component except for the fragrance, heat and dissolve in a mixing kettle, and reach 180 ° C. Until concentrated. Then, it allowed to cool, stirring slowly, added (A) component and fragrance | flavor between 90-130 degreeC, and also (C) component as needed, and stirred well. When uniformly mixed, move the candy base to the cooling plate, add (B) component and (D) component as needed between 70-120 ° C, mix for 1 minute, mold, about 1g / Grain candy was prepared. Each step was prepared by a conventional method. In addition, the candy of Comparative Examples 1-3 was produced according to the said method.

<Preparation of candy (Example 28)>
(A) Component, (B) component, (C) component, and each component except perfume are added with about half of the total amount of water, dissolved by heating in a mixing kettle, and further heated and concentrated to 180 ° C. . Then, it allowed to cool, stirring slowly, added (A) component, (B) component, (C) component, and the fragrance | flavor between 70-120 degreeC, and stirred for 1 minute. After stirring, the candy base was moved to a cooling plate and then molded to prepare about 1 g / grain of candy. Each step was prepared by a conventional method.

<Preparation of chewing gum (Examples 45 to 49 )>
All other components were added to a gum base (manufactured by Natural Base Co., Ltd.) and kneaded uniformly at around 50 ° C. using a 1 L capacity kneader (TKI-1 manufactured by Toshin Co., Ltd.). Next, about 1 g of gum processed into a plate shape was produced.

<Preparation of tablet confectionery (Example 50 )>
After all the ingredients were added and mixed uniformly, a tableting machine having a mass of 1 g and a diameter of 13 mmφ was produced at a pressure of about 1,000 kg using a tableting machine (manufactured by Fuji Pharmaceutical Co., Ltd.).

<Experiment 1> Enzyme activity of laccase immediately after production and after storage About 10 g of a sample immediately after production was enclosed in an aluminum pouch having a capacity of 50 mL and stored at 40 ° C. and 75% humidity for 3 months.
The laccase activity was measured for the laccase drug substance, immediately after production and after storage by the following method.
The original substance and the sample which were returned to room temperature were dissolved in 30 mL of water to prepare a sample solution. Add 100 μL of sample solution and 900 μL of water to 1 mL of 0.1 M acetate buffer (pH 5.0) in a test tube, mix well, incubate at 30 ° C. for 5 minutes, then add 100 μL of 0.1 g / L shilling aldazine solution. Immediately after mixing, the mixture was transferred to a cell and measured with an absorbance meter (UV-160A, manufactured by Shimadzu Corporation). From the change in absorbance at 530 nm in 30 seconds from immediately after the start of the reaction to 30 seconds later, the enzyme was expressed by the following formula. Activity was calculated. Based on this, the enzyme activity of laccase immediately after production and after storage was calculated by the following formula.

Total enzyme activity (U / mL)
= ΔOD × 2.1 × 60 × 0.001 / 0.065 × 0.05 × 30 × D
= ΔOD × 87.2 × D
ΔOD: Absorbance change for 30 seconds at 530 nm
D: Dilution multiple of sample solution Residual rate of laccase activity immediately after production (%)
= {(Total activity value immediately after production) / (total activity value of drug substance)} × 100
Residual rate of laccase activity after storage (%)
= {(Total activity value after 3 months at 40 ° C. 75%) / (total activity value immediately after production)} × 100

The activity remaining rate of laccase calculated by the above formula was evaluated according to the following criteria, and a value of ◯ or higher was judged as a good level.
◎: Activity remaining rate of laccase is 70% or more ○: Activity remaining rate of laccase is 50% or more and less than 70% Δ: Activity remaining rate of laccase is 30% or more and less than 50% ×: Activity remaining rate of laccase is less than 30%

<Experiment 2> Deodorizing Effect of Bad Breath and its Persistence For 20 healthy men and women, the sample was rinsed with a 0.1% methionine aqueous solution for 30 seconds before being ingested, then exhaled and allowed to rest for 10 minutes. Thereafter, 1 g of the sample was taken in the mouth for 5 minutes without chewing until it disappeared from the mouth (gum chewing for 5 minutes). Before taking the sample after mouth washing, immediately after taking the sample and disappearing from the mouth (the chewing gum was chewed for 5 minutes), and after 60 minutes, the exhalation in the oral cavity after 1 minute with the mouth closed, respectively. 200 mL was collected. The intensity of bad breath was determined by comparing the odor intensity by one expert evaluator and the awareness of bad breath, and evaluated according to the following criteria.

The odor intensity of exhaled breath before sample intake and the expired breath immediately after sample ingestion and 60 minutes after ingestion were compared, and the deodorizing effect immediately after ingestion and its persistence were evaluated according to the following criteria.
5 points: Deodorized remarkably, and there was also a noticeable deodorization feeling 4 points: Deodorized, and there was also a noticeable deodorization feeling 3 points: Slightly deodorized, somewhat receptive There was a sense of deodorization. 2 points: Slightly deodorized and no subjective sense of deodorization. 1 point: No change. Calculate the average score based on the results of the evaluation based on the above criteria. Was evaluated as a good level.
◎: 4.5 points or more and 5 points or less ○ to ◎: 4.0 points or more and less than 4.5 points ○: 3.0 points or more and less than 4.0 points Δ: 2.0 points or more and less than 3.0 points ×: 1.0 to less than 2.0

<Experiment 3> Unsavory taste The taste when ingesting 1 g of sample without chewing it in the mouth for about 5 minutes (gum chewing for 5 minutes) was ingested by 20 panelists according to the following criteria.
5 points: I did not feel any nasty taste 4 points: I felt a slightly tasty taste but no problem 3 points: I felt somewhat nasty 2 points: I felt quite nasty 1 point: I felt very nasty and I could not eat The average score was calculated from the results of evaluation based on the above criteria and evaluated as follows, and a value of ○ or higher was judged to be a good level.
◎: 4.5 points or more and 5 points or less ○: 4.0 points or more and less than 4.5 points △: 3.0 points or more and less than 4.0 points ×: 1.0 points or more and less than 3.0 points

<Experiment 4> Uniformity of candy (appearance)
The appearance of the candy sample immediately after production was visually evaluated, and the uniformity was evaluated according to the following criteria. ○ The above was regarded as a good level.
◎: Uniformly distributed ○: Slight unevenness was observed, but there was no problem △: Slightly unevenness was observed ×: Remarkable unevenness was observed

<Experiment 5> Storage stability of enzyme of component (D) About 10 g of a sample immediately after production was sealed in an aluminum pouch having a capacity of 50 mL and stored at 40 ° C. and 75% humidity for 3 months.
For each enzyme, the enzyme activity immediately after production and after storage was calculated by a conventional method, and the storage stability was evaluated according to the following criteria.
◎: Enzyme activity remaining rate is 70% or more ○: Enzyme activity remaining rate is 50% or more and less than 70% △: Enzyme activity remaining rate is 30% or more and less than 50% ×: Enzyme activity remaining rate is less than 30%

Details of the measurement of the enzyme activity of each enzyme are as follows.
-Dextranase Each said test liquid was added to 1% dextran solution, it was made to react at 35 degreeC for 10 minute (s), and the amount of produced | generated reducing sugars was measured using the somogie Nelson method. The amount of enzyme that liberates reducing sugar corresponding to 1 μg of glucose per minute was defined as 1 unit (U).
-Mutanase Each said test liquid was added to the 1% mutan solution prepared from Streptococcus mutans, and it was made to react at 35 degreeC for 10 minutes, and the amount of produced | generated reducing sugars was measured using the Somogie Nelson method. The amount of enzyme that liberates reducing sugar corresponding to 1 μg of glucose per minute was defined as 1 unit (U).
・ Protease (papain, actinidine, bromelain)
Using peptidyl p-nitroaniline as a substrate, the increase rate of p-nitroaniline released by hydrolysis was determined by measuring the absorbance at 405 nm.

The raw materials used are as follows.
・ Polylysine A (50% product):
Sunkeeper No. 381 (trade name, number average molecular weight: 2,600)
Polylysine 50% + Dextran 50% [San-Eihara FFI Co., Ltd.]
Polylysine B:
Poly-L-lysine hydrochloride (trade name, number average molecular weight: 30,000) [manufactured by Sigma Aldrich Japan Co., Ltd.]
Polylysine C:
0.1% poly-L-lysine aqueous solution (trade name, number average molecular weight: 300,000) [manufactured by Sigma Aldrich Japan Co., Ltd.]
・ Polyarginine:
Poly-L-arginine hydrochloride (trade name, number average molecular weight 15,000) [manufactured by Sigma-Aldrich Japan Co., Ltd.]
・ Polyhistidine:
Poly-L-histidine (trade name, number average molecular weight 10,000)
・ Lysozyme:
Sunkeeper No. 657 (trade name, number average molecular weight 14,300) [manufactured by Saneihara FFI Co., Ltd.]
・ Chitosan oligosaccharide:
COS-YS (trade name, number average molecular weight 680) [manufactured by Yaizu Suisan Chemical Co., Ltd.]
・ Laccase (80% product):
Laccase Daiwa (108,000 units) 360,000 units / g solids 80%
Shaped with dextrin (Amano Enzyme Co., Ltd.)
・ Rosemary extract (80% product):
Water / ethanol extract, shaped with dextrin (Toyotama Fragrance Co., Ltd.)
・ Sage extract (50% product):
Water extract, shaped with dextrin (Toyotama Fragrance Co., Ltd.)
・ Perilla extract (50% product):
Water extract, shaped with dextrin (Toyotama Fragrance Co., Ltd.)
・ Mint extract (50% product):
Mint Polyphenol 50 (trade name) Water extract, shaped with dextrin [Ogawa Fragrance (
Made by Co., Ltd.]
・ Thyme extract (50% product):
Water extract, shaped with dextrin (Toyotama Fragrance Co., Ltd.)
・ Melissa extract (50% product):
Water extract, shaped with dextrin (Toyotama Fragrance Co., Ltd.)
Dextranase:
12,000 units / g [Mitsubishi Chemical Foodtech Co., Ltd.]
・ Mutanase:
6,000 units (Amano Enzyme Co., Ltd.)
・ Actinidin:
Enzyme activity 9000 units [Asahi Food and Healthcare Co., Ltd.]
・ Papain:
Papain W-40 (trade name) [Amano Enzyme Co., Ltd.]
・ Bromeline:
Bromelain F (trade name) [manufactured by Amano Enzyme Co., Ltd.]
・ Lysine (comparative product):
L-Lysine [Sigma Aldrich Japan Co., Ltd.]

Claims (6)

(A) 0.001 to 5% by mass of one or more basic peptides selected from polylysine, polyarginine and polyhistidine , and (B) 0.001 to 3% by mass with 360,000 units / g of laccase (A) / (B) which shows the compounding ratio of the compounding quantity of (A) component and the compounding quantity as a 360,000 unit / g product of (B) component is 0.005-100 as mass ratio. bad breath deodorant formulation which is characterized in that there. Furthermore, it contains (C) Labiatae plant or its extract, and shows the blending ratio between the blending amount of (C) component and the blending amount of (B) component as 360,000 units / g product (B) / (C) is breath freshening preparation according to claim 1, wherein Ru 0.001 der as a mass ratio. The bad breath deodorant preparation according to claim 2 , wherein the Labiatae plant as component (C) is at least one selected from rosemary, sage, perilla, mint, thyme and melissa. The oral deodorant preparation according to claim 2 or 3, which contains 0.001 to 5% by mass of component ( C). 5. The halitosis deodorant preparation according to any one of claims 1 to 4 , further comprising (D) one or more enzymes selected from dextranase, mutanase, actinidine, papain, and bromelain . The oral deodorant preparation according to any one of claims 1 to 5, wherein the water content in the preparation is 0 to 5% by mass.