JP5588630B2 - Dentifrice in a container - Google Patents

Description

  The present invention relates to a dentifrice in a container containing monoterpenes.

Dentifrices are generally blended with fragrances from the viewpoint of feeling of use and taste, and various fragrances including menthol are blended.
However, since some fragrances adsorb and penetrate into the container, there is a problem that the effectiveness of the fragrance decreases in a short period of time (Patent Documents 1 and 2). On the other hand, in patent document 1 and patent document 2, the preservation | save property of a fragrance | flavor is improved by comprising the innermost layer of a container with ethylene-vinyl alcohol copolymer resin. However, when a special polymer is used, there are problems in manufacturing such as a decrease in the manufacturability of the container and economic problems in terms of cost increase.

  On the other hand, as a technique for suppressing the adsorption of water-insoluble active ingredients to the container in terms of the composition of dentifrice, it contains a polyol such as glycerin, and the water content with respect to the polyol is made water-insoluble by making the weight ratio 0.4 or less. An oral composition (Patent Document 3) in which an active ingredient is stably blended has been proposed. Moreover, the composition for oral cavity which stabilized the lipophilic component, such as a fragrance | flavor, by the encapsulation which embeds with the film | membrane which has gellan gum as a main component is proposed (patent document 4).

JP 2005-82212 A JP-A-6-279249 JP 2001-199854 A JP-A-10-67625

However, when the amount of water is reduced by containing a large amount of glycerin or the like as in the oral cavity composition described in Patent Document 3, the viscosity increases, and the dispersibility of the dentifrice in the oral cavity becomes worse, The feeling of use may be impaired. In addition, glycerin has a bitter taste and affects not only the feeling of use but also the taste. Even in the case where the fragrance is encapsulated in the capsule as in the oral composition described in Patent Document 4, the fragrance is easily eluted in the water in which the anionic surfactant of the oral composition is dissolved. It is necessary to make the film thicker or water-insoluble film. However, if the capsule film is made thick or water-insoluble film, it becomes difficult to disintegrate the capsule or the film remains and the feeling of use is lost even if the capsule disintegrates. There is a fear.
Therefore, an object of the present invention is to provide a dentifrice containing an anionic surfactant and a monoterpene having a high adsorptivity and penetrability among the fragrances. The object is to provide a dentifrice in a container in which adsorption or penetration is suppressed.

  Therefore, as a result of various studies on the long-term stability of dentifrices containing monoterpenes and anionic surfactants contained in containers, the present inventor has found limonene, 1,8-cineole or linalool as monoterpenes. When combined with a high melting point oil that is solid at room temperature and has organic and inorganic values in a specific range, adsorption and penetration of monoterpenes into the container is suppressed, and the dentifrice after storage It was found that a dentifrice in a container with a high aroma persistence can be obtained by increasing the residual amount in the container.

That is, the present invention includes the following components (A), (B), (C) and (D):
(A) monoterpenes selected from limonene, 1,8-cineole and linalool,
(B) an anionic surfactant,
(C) It has a melting point of 50 ° C. or more and is solid at room temperature (25 ° C.), an organic value of 560 to 1500, an inorganic value of 0 to 470, and the organic value and the inorganic value are represented by the following formula ( Oil satisfying 1), (organic value) × 0.5-550 ≦ (inorganic value) ≦ (organic value) × 0.5-280 (1)
(D) A dentifrice in a container containing water is provided.

  The dentifrice in a container of the present invention is a monoterpene fragrance made of limonene, 1,8-cineol or linalool even when a special resin such as an ethylene-vinyl alcohol copolymer is not used as the material of the container. Is prevented from adsorbing and penetrating into the container, the residual amount of these fragrances in the dentifrice after storage is increased, the persistence of the fragrance is high, and the feeling of use is also good.

It is a figure showing the fragrance | flavor residual rate of this invention after a preservation | save in each tube container, and a comparative example.

  The dentifrice in a container of the present invention contains (A) monoterpenes selected from limonene, 1,8-cineole and linalool. These monoterpenes are known to be adsorbed and penetrated into the container when blended in a dentifrice together with an anionic surfactant, and a stable aroma cannot be obtained. Adsorption or permeation into the water is suppressed, and a stable aroma can be obtained. Among limonenes, d-limonene is contained in lemon oil, orange oil, lime oil, grapefruit oil and the like. l-limonene is contained in mint oil, spearmint oil, star anise oil and the like. dl-Limonene is contained in turpentine oil, camphor oil, fennel oil and the like. In the present invention, these essential oils can also be blended.

  1,8-cineole is contained in eucalyptus oil, kayapte oil, rosemary oil, laurel oil, and the like, and these essential oils can also be blended. Among linalool, d-linalool is contained in bored rose oil, linaloe oil, coriander oil, orange oil, and l-linalool is contained in melamine leaf oil, bergamot oil, lemon oil, etc. It can also be blended. These limonene, 1,8-cineole and linalool can be used alone or in combination of two or more.

(A) The content of the monoterpenes is 0.1 to 3 % by mass, more preferably 0.3 to 2% by mass, and particularly 0.3 to 1 % by mass in the dentifrice of the present invention from the viewpoint of obtaining a sufficient aroma. Is preferred.

The dentifrice of the present invention is blended with (B) an anionic surfactant for the purpose of diffusing other components in the mouth by cleaning action and foaming. Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; N-acyl sarcosine salts such as N-lauroyl sarcosine sodium; and N-acyl glutamate such as sodium N-lauroyl glutamate. Examples include acylamino acid salts; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfoacetates such as sodium lauryl sulfoacetate, α-olefin sulfonates, and polyoxyethylene monoalkyl phosphates. In these anionic surfactants, the hydrophobic alkyl group and acyl group preferably have 6 to 18 carbon atoms, particularly 10 to 14 carbon atoms. The salt is preferably a sodium salt. As the anionic surfactant, an alkyl sulfate is particularly preferable because it has good foamability and can be obtained at a low cost.
These anionic surfactants may be used alone or in admixture of two or more. From the viewpoint of cleaning action, foamability and perfume stability, 0.1 to 5.0 mass in the dentifrice of the present invention. %, More preferably 0.5 to 3.0% by mass, particularly preferably 1.0 to 3.0% by mass.

The (C) room temperature (25 ° C.) solid oil used in the dentifrice of the present invention has a melting point of 50 ° C. or higher, an organic value of 560 to 1500, an inorganic value of 0 to 470, and the organic It is an oil agent whose property value and inorganic value satisfy the following formula (1).
(Organic value) × 0.5-550 ≦ (inorganic value) ≦ (organic value) × 0.5-280 (1)

  The solid oil agent of component (C) improves the dispersibility of (A) monoterpenes in the dentifrice by using in combination with component (A) monoterpenes, and (A) monoterpenes into the container From the viewpoint of suppressing adsorption and permeation, component (A) and component (C) are blended in dentifrice at the same time, or component (A) and component (C) are mixed or dissolved in advance before blending in dentifrice. It is preferable to do.

  The (C) solid oil agent is preferably an oil agent having no production limitation and having a melting point of 50 ° C. or higher and a melting point of 60 ° C. or higher, particularly 70 ° C. or higher from the viewpoint of storage stability. The organic value of (C) the solid oil agent is 560 to 1500, preferably 600 to 1200, more preferably 600 to 1000, and the inorganic value is 0 to 470, 0 to 320, and further 0. It is preferable that it is -200. Further, the relationship between the organic value and the inorganic value of the solid oil agent (C) satisfies the above formula (1), but the lower limit of the organic value is (organic value) × 0.5−400 ≦ (inorganic value) Furthermore, (organic value) × 0.5-340 ≦ (inorganic value) is preferable, and the upper limit is preferably (inorganic value) ≦ (organic value) × 0.5-300.

  Examples of the solid oil (C) include hydrocarbon solid oils such as ceresin, whale wax, beeswax, carnauba wax, microcrystalline wax, ozokerite; solid oils such as tristearic acid glyceride; stearyl stearate, cholesteryl stearate, etc. Solid ester oil. Of these, (A) a hydrocarbon-based solid oil is preferable, and ceresin is particularly preferable from the viewpoints of stability of monoterpenes, adsorption to containers, and prevention of penetration.

  The content of the solid oil agent (C) in the dentifrice is the weight ratio (A / C) of the component (A) and the component (C) from the viewpoint of the stability of the component (A), adsorption to the container, and prevention of penetration. 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 8. Moreover, 0.01-10 mass% is preferable and, as for content in the dentifrice of a component (C), 0.02-5.0 mass% is more preferable.

  When the dentifrice contains the hydrogel particles containing the component (A) and the component (C), the content of the solid oil agent (C) in the hydrogel particles depends on the stability of the component (A) and the From the viewpoint of adsorption and penetration prevention, the mass ratio (A / C) of the component (A) to the component (C) is preferably 1-20, more preferably 2-20, and further preferably 2.6-20. Moreover, 1-10 mass% is preferable and, as for content when the hydrogel particle of a component (C) is 100 mass%, 1-8 mass% is more preferable.

Component (A) and component (C) are preferably contained in the dentifrice as hydrogel particles containing these two components. Here, the hydrogel particles are particles in which the component (A) and the component (C) are dispersed in the hydrogel. The hydrogel is a gel that is gelled by a gelling agent using water as a solvent. The hydrogel particles in the present invention are obtained by gelling by emulsifying or dispersing the component (A) and the component (C) in an aqueous solution in which the gelling agent of the non-crosslinked hydrogel is dissolved. Is preferred. The hydrogel particles of the present invention are composed of an outer layer outer shell and an inner layer core component. Unlike the capsules in which the inner layer and the outer layer are concentric, the hydrogel particles do not have a film and are blended in the hydrogel particles. The oil agent is dispersed or emulsified in a continuous phase containing a gel forming agent and water.

The gelling agent used for the hydrogel particles is a gelling agent that causes gelation due to the thermoreversibility of the sol-gel. For example, agar, gelatin, gellan gum and the like can be mentioned. These can be used alone or in admixture of two or more. Of these, agar is preferred. The jelly strength of the agar used is preferably 68.6 kPa (700 g / cm ² ) or less, and 19.6 kPa (200 g / cm ² ) to 63.7 kPa (650 g / cm ² ), from the viewpoint of feel during use. Is more preferable.

Here, the jelly strength is determined by the Nissho Water method. According to the Nissui water method, the jelly strength is determined by preparing a 1.5% by weight aqueous solution of a gelling agent and allowing the aqueous solution to stand for 15 hours at 20 ° C. to solidify the gel. The maximum weight [g] per 1 cm ² of surface area when a load is applied by (manufactured by Kiya Seisakusho Co., Ltd.) and the gel withstands the load for 20 seconds at 20 ° C.

The content of the gelling agent in the hydrogel particles is preferably from 0.1 to 8.0 mass%, more preferably from 0.5 to 5.0 mass%, from the viewpoint of the stability of the hydrogel particles.
1-60 mass% is preferable and, as for content of the components (A) and (C) in a hydrogel particle, 5-40 mass% is more preferable.

The hydrogel particles in the present invention contain water. The water content in the hydrogel particles is preferably 40 to 90 mass%, more preferably 50 to 80 mass%.
Further, the hydrogel particles can contain a surfactant, for example, an anionic surfactant, if necessary. Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl acetates, polyoxyethylene alkyl ether phosphates, fatty acid salts, N-acyl taurine salts and N-acyl amino acid salts. It is done.
Surfactant can be used individually or in mixture of 2 or more types. From the viewpoints of stability and suppression of agar gel strength reduction, anionic surfactants are preferred, N-acyl taurine salts are more preferred, and sodium N-stearoylmethyl taurate is even more preferred.

The content of the anionic surfactant in the hydrogel particles is preferably 0.1 to 5.0% by mass, and more preferably 0.15 to 3.0% by mass.
The method for producing hydrogel particles has a stirring treatment step of applying a stirring energy to a mixture of a gelling agent, component (A), component (B), water and surfactant to obtain a dispersion. The dispersion is subjected to a general method such as a dropping method, a spraying method, or a stirring method to form droplets, and then the droplets are cooled and solidified to produce hydrogel particles.

When stirring the mixture, it is preferable to apply stirring energy of 200 to 5000 [kW × min / m ³ ] to the mixture. A preferable range of the stirring energy is 230 to 4500 [kW × min / m ³ ], and a more preferable range is 250 to 4200 [kW × min / m ³ ].

  Moreover, it does not restrict | limit especially as an apparatus which provides stirring energy to a mixture, A well-known stirring apparatus can be used. However, in order to give such stirring energy, a device capable of exhibiting a high shearing force is required. Therefore, the device is preferably a homomixer, a line mixer, a disper or the like, and more preferably a homomixer in terms of operation.

  In the stirring treatment step, the preferable temperature range is 60 to 90 ° C, and the preferable pH of the dispersion is pH 5.5 to 8.5 (80 ° C).

The “stirring energy” defined here is stirring power P / V [kW / m ³ ] × time [minute], and a detailed calculation formula is described in Japanese Patent Application Laid-Open No. 2007-161683. . The calculation formula (I) for stirring energy when using a homomixer is shown.

Stirring energy [kW × min / m ³ ] = [stirring power P (kW)] / [treatment liquid volume V (m ³ )] × stirring time (min) (I)
In the above formula (I), the stirring power P (kW) is calculated by the following experimental formula 1.
Stirring power P (kW) = Np × n ³ × d ⁵ × ρ / 1000 (empirical formula 1)
Here, in Np: power number → homomixer, the stirring tank capacity is less than 10 L: 1.5, 10 L or more: 1.3
n: Stirring speed [− / sec]
d: Diameter of stirring blade [m]
ρ: Density of contents [kg / m ³ ]

  The dropping method uses the property that a dispersion liquid is discharged from a hole and the discharged dispersion liquid becomes a droplet by its surface tension or interfacial tension, and the droplet is cooled in a gas phase such as air or in a liquid phase. It is a method of forming hydrogel particles by solidifying. In addition, from the viewpoint of forming hydrogel particles having a uniform particle size, it is preferable to vibrate the dispersion discharged from the holes.

  The spraying method uses a spray nozzle and discharges (sprays) the dispersion liquid into the gas phase from the spray nozzle, forms droplets by the surface tension, and cools and solidifies the droplets in the gas phase to form hydrogel particles. It is a method of forming.

  In the stirring method, the dispersion is poured into a liquid that has a property that does not substantially mix with the dispersion and is adjusted to a temperature equal to or higher than the gelling temperature, and the dispersion is atomized by shearing force by stirring, and the liquid is increased by interfacial tension. This is a method of forming 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 dispersion.

  In any of the dropping method, the spraying method, and the stirring method, it is preferable that the temperature of the dispersion liquid at the time of discharge, spraying, or charging is set to a temperature not lower than the gelling temperature and not higher than 100 ° C. Further, from the viewpoint that spherical particles having excellent aesthetics can be easily produced, the temperature of the dispersion is preferably set to a gelling temperature + 10 ° C. or higher, and to a gelling temperature + 20 ° C. or higher. More preferred. The upper limit of this temperature is 100 ° C., which is the boiling point of water. Specifically, the temperature of the dispersion is preferably in the range of 60 to 90 ° C, more preferably in the range of 70 to 80 ° C.

  The hydrogel particles formed as described above may be further made into fine hydrogel particles by pulverization or the like, if necessary.

  In the obtained hydrogel particles, components (A) and (C) are dispersed and encapsulated in a continuous phase containing water. The structure of such hydrogel particles can be confirmed, for example, by analyzing an SEM photograph of the hydrogel particles.

  Although the shape of the obtained hydrogel particles is not particularly limited, it is preferable to have a shape of a rotating body formed of 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.

  The average particle diameter of the hydrogel particles and the emulsified diameter of the oil component can be measured by a laser diffraction / scattering method. In the laser diffraction / scattering method, the median diameter measured using a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) was defined as the average particle diameter. The average particle size of the hydrogel particles is preferably 5 to 300 μm, more preferably 30 to 280 μm, and particularly preferably 50 to 280 μm.

  The dentifrice of the present invention contains (D) water. The content of water is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and particularly preferably 40 to 60% by mass in the total amount of the dentifrice from the viewpoint of dispersibility in the oral cavity and usability. The water content mentioned here includes the amount of water in the hydrogel particles and the water in each component such as sorbitol liquid. The water content in the dentifrice can be measured, for example, with a Karl Fischer moisture meter. As the Karl Fischer moisture meter, for example, a trace moisture measuring device (Hiranuma Sangyo) can be used. In this apparatus, 5 g of the dentifrice is taken and suspended in 25 g of anhydrous methanol, and 0.02 g of this suspension is taken and the amount of water can be measured.

  To the dentifrice of the present invention, in addition to the above components, abrasives, binders, wetting agents, fragrances, surfactants other than component (B), sweeteners, bactericides, as long as the effects of the present invention are not impaired. Preservatives, water-soluble fluorides, various medicinal ingredients, and the like can be blended as necessary.

  As an abrasive compounded in a dentifrice base material, calcium hydrogen phosphate, calcium carbonate, calcium pyrophosphate, insoluble potassium metaphosphate, anhydrous silicic acid, hydrous silicic acid, aluminum silicate, zirconium silicate, bentonite, Zeolite, aluminum oxide, aluminum hydroxide, resin and the like can be mentioned.

  The binders used in dentifrice base materials include sodium alginate, sodium carboxymethylcellulose, carrageenan, xanthan gum, sodium polyacrylate, hydroxyethylcellulose, hydroxypropylcellulose, pectin, tragacanth gum, gum arabic, guar gum, caraya gum, locust It is preferable to blend one or more selected from bean gum, gellan gum, tamarind gum, psyllium seed gum, polyvinyl alcohol, sodium chondroitin sulfate, and a methoxyethylene maleic anhydride copolymer.

  Examples of the wetting agent blended in the dentifrice base material include polyethylene glycol, propylene glycol, sorbitol, glycerin, 1,3-butylene glycol, maltitol, lactitol, xylitol, etc. Among them, sorbitol and glycerin are preferable. .

  As a fragrance | flavor mix | blended with the base material or hydrogel particle of a dentifrice, in the range which does not inhibit the effect of this invention, 1-menthol, carvone, anethole, eugenol, ocimene, n-amyl alcohol, citronellol, alpha-terpineol Synthetic fragrances such as methyl salicylate, methyl acetate, citronole acetate, ethyl linalool, crocodile, thymol, cinnamon oil, pimento oil, perilla oil, anise oil, winter green oil, peppermint oil, winder green oil, sassafras oil Natural flavors such as clove oil, sage oil, mayonnaise oil, cinnamon oil and thyme oil.

  Examples of the disinfectant include chlorhexidine salts, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, and the like.

  Examples of the preservative include benzoic acid, sodium benzoate, parahydroxybenzoic acid, parahydroxybenzoic acid ester, and the like.

  Examples of the water-soluble fluoride include sodium fluoride, tin fluoride, ammonium fluoride, potassium fluoride, lithium fluoride, sodium monofluorophosphate, potassium monofluorophosphate, and ammonium fluoride.

  In addition, various medicinal ingredients include anti-inflammatory agents such as allantochlorhydroxyaluminum, azulene, glycyrrhetinic acid, epidihydrocholesterin, α-bisabolol, glycyrrhizic acid and salts thereof; phenolic compounds such as hinokitiol; tranexamic acid, epsilon aminocapron Anti-plasmin agents such as acids; α-tocopherol, α-tocopherol acetate (dl-form, d-form) and salts thereof; copper compounds such as copper chlorophyllin sodium and copper gluconate; salts such as sodium chloride and potassium nitrate; dextranase, Enzymes such as mutanase, amylase, lysozyme chloride; extracts of sugarcane, duck, clove, urgon, safflower, etc .; aluminum lactate, strontium chloride, berberine, hydroxamic acid and its derivatives, sodium tripolyphosphate Um, zeolites, dihydrocholesterol, and zinc citrate.

  The dentifrice of the present invention can be used as a liquid dentifrice or a toothpaste, and is used by filling a container such as a tube container, a pump container, or a bottle container. Since the perfume is prevented from adsorbing and penetrating into the container, the innermost layer of the container may be composed of, for example, a polyolefin resin. As the polyolefin resin forming the innermost layer of the container, for example, low density polyethylene (including linear low density polyethylene), high density polyethylene, medium density polyethylene, polypropylene and the like can be used. In the tube container in which the body part for containing the contents is formed of a laminate having a plurality of resin layers, the innermost layer and the shoulder part of the body part can be formed using, for example, a polyolefin resin. In this case, the innermost layer of the laminated body of the trunk portion functions as a seal layer (sealant layer) when the trunk portion of the tube container is formed using the laminated body. For this reason, low-density polyethylene (including linear low-density polyethylene) is preferably used as the polyolefin resin forming the innermost layer of the laminate. A polyethylene layer may be used for the trunk | drum and shoulder part of a tube. When a tube container is used that includes a shoulder portion in which a shoulder portion and a discharge port continuous therewith are integrally formed, and a body portion, the shoulder portion is preferably made of high-density polyethylene.

  In the following test examples and examples,% means mass%.

Test example 1
Test solutions 1 to 3 were prepared according to the formulation in Table 1. 15 g each of test solutions 1 to 3 in which limonene is dissolved in each of ceresin, carnauba wax and ethylene glycol distearate and mixed with the other ingredients, immediately put in a tray container and cooled with water to form a solid material Were cut into 1 cm squares to prepare test pieces 1 to 3. Test pieces 1 to 3 (7.5 g) were immersed in 30 g of water in which 1.5% of sodium lauryl sulfate was dissolved, and turbidity after storage at 50 ° C. for 1 day was observed.

  As shown in Table 1, the test piece 3 made of the test solution 3 was turbid after storage at 50 ° C. for 1 day. The turbidity is considered to be due to the fact that the components of the oil contained in the test piece 3 are eluted in the sodium lauryl sulfate aqueous solution.

Test example 2
In Table 2, limonene and fragrance in component I are dissolved in an oil such as ceresin, mixed with component I and heated at 80 ° C., mixed at room temperature, heated and mixed at 90 ° C. for 30 minutes, and heated to 80 ° C. The cooled second component is mixed, stirred with a homomixer, and the treated liquid mixture is sprayed into the cooling air from the holes while maintaining 80 ° C., and solidified to obtain hydrogel particles 1 to 5. It was.
In the same manner as in Test Example 1, the hydrogel particles 1 to 5 were immersed in 30 g of water in which 1.5% of sodium lauryl sulfate was dissolved, and stored at 50 ° C. for 2 weeks.
The state after storage was evaluated.

  As shown in Table 2, the particles 1 to 3 were not confirmed to be turbid by storage at 50 ° C., but the particles 4 and 5 were confirmed to be turbid and the oil agent was eluted from the hydrogel particles. It was. Table 3 shows the melting point, organic property, and inorganic property of the oil agent and carnauba wax blended in the particles 1-5.

(Dentifrice)
A dentifrice (Example 1, Comparative Example 1) was prepared according to the formulation shown in Table 4. Particles 6 and 7 were produced by replacing limonene of particle 1 with 1,8-cineole and l-menthol, respectively.

  The dentifrices of Example 1 and Comparative Examples 1, 3, and 4 are filled into the following tube containers 1 to 3, respectively, and the dentifrices of Example 2 and Comparative Example 2 are filled into the following tube containers 3 and sealed. Stored at 50 ° C. for 1 month. In the tube container, a shoulder portion is a portion in which a shoulder portion and a discharge port continuous therewith are integrally formed, and includes a trunk portion that is continuous with the shoulder portion. As for the trunk | drum of a tube container, the innermost layer is comprised with the low density polyethylene.

Tube container 1: The shoulder is formed of low density polyethylene (LDPE). The body of the tube container includes an inorganic vapor-deposited resin layer and a metal vapor-deposited resin layer (aluminum vapor-deposited layer) disposed as an outer layer on the intermediate layer.
Tube container 2: The shoulder is formed of high-density polyethylene (HDPE). The body of the tube container includes an inorganic vapor-deposited resin layer and a metal vapor-deposited resin layer (aluminum vapor-deposited layer) disposed as an outer layer on the intermediate layer.
Tube container 3: The shoulder is formed of low density polyethylene (LDPE). The body of the tube container includes an inorganic vapor-deposited resin layer as an intermediate layer.

(Measurement of residual amount of limonene and other terpenes)
The dentifrice is diluted 4 times with ion-exchanged water and stirred until uniform to obtain a dentifrice 4 times diluted water.
Next, the dentifrice 4 times dilution water is diluted 5 times with ethanol, and dentifrice 20 times dilution ethanol water is obtained. The supernatant is obtained by centrifuging the dentifrice 20-fold diluted ethanol water. The supernatant is measured by gas chromatography and the amount of limonene is measured. The amount of limonene in the dentifrice after storage was the amount of limonene remaining, and the ratio of the amount of limonene remaining after storage when the amount of limonene at the time of filling was 100% was determined. Other terpenes were measured in the same manner as limonene.

  Table 5 shows a comparison of the remaining amounts of limonene and other terpenes in each tube container in Examples 1 and 2 and Comparative Examples 1 to 4.

  1 (a) shows the ratio of the remaining amount of limonene in Table 5 (1) to the ratio of the remaining amount of limonene in Example 1 and Comparative Example 1 on the basis of Comparative Example 1 of the tube container 3. FIG. The remaining amount of 1,8-cineole in Table 5 (2) is the ratio of the remaining amount of 1,8-cineole of Example 2 with reference to Comparative Example 2 of the tube container 3, and FIG. The ratio of the residual amount of l-menthol in Comparative Example 3 and Comparative Example 4 based on Comparative Example 4 of the tube container 3 is shown as the residual amount of l-menthol in Table 5 (3). As shown in FIGS. 1 (a) and 1 (b), Examples 1 and 2 mixed with limonene, 1,8-cineole and the oil of the component (C) of the present invention are comparative examples for any tube container. A residual amount of limonene and 1,8-cineole higher than 1 and 2 was observed. As shown in FIG. 1 (c), l-menthol has a large residual amount of l-limonene in any of the tube containers of Comparative Example 3 and Comparative Example 4 mixed with the oil of the component (C) of the present invention. There was no difference.

Claims (4)

The following components (A), (B), (C) and (D):
(A) monoterpenes selected from limonene, 1,8-cineole and linalool,
(B) an anionic surfactant,
(C) It has a melting point of 50 ° C. or more and is solid at room temperature (25 ° C.), an organic value of 560 to 1500, an inorganic value of 0 to 470, and the organic value and the inorganic value are represented by the following formula ( An oil agent selected from ceresin , spermaceti, beeswax, beeswax, carnauba wax, microcrystalline wax, ozokerite, glyceryl tristearate, stearyl stearate, and cholesteryl stearate satisfying 1), (organic value) × 0.5-550 ≦ (Inorganic value) ≦ (Organic value) × 0.5-280 (1)
(D) Contained in a container containing water , wherein component (A) and component (C) are contained in hydrogel particles having an average particle size of 5 to 300 μm, and the innermost layer of the trunk is made of low-density polyethylene A dentifrice in a container. Component (A) and the mass ratio of component (C) (A / C) is packaged dentifrice according to claim 1, wherein 1 to 20. Hydrogel particles, non-crosslinked claim 1 or 2, wherein hydrogel gelling agent component in an aqueous component solution prepared by dissolving (A) and the component (C) is a hydrogel particles obtained by emulsifying or dispersing Dentifrice in a container. The dentifrice in a container according to claim 3 , wherein the gelling agent is agar.

Images