JP2018104302A - Granular dentifrice production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granular dentifrice production method having high yield, excellent wet disintegration strength and calcium supplementation or remineralization promoting effect on a tooth, and the granular dentifrice.SOLUTION: The granular dentifrice production method [1] comprises: a step 1 which is a granulation step in which (A) a water soluble calcium salt, (B) a water-insoluble powder material, and (C) one or more silicates selected from sodium silicate and potassium silicate are blended using a container rotating granulation machine wherein an aqueous solution containing at least one type of (C) silicate selected from sodium silicate and calcium silicate added to (B) the water insoluble powder material is made into droplets and supplied; and a step 2 of coating the surface of the granules obtained in step 1 with a coating solid (D) at normal temperature (20°C). In addition, the granular dentifrice [2] obtained by the method is provided.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a dentifrice granule and a dentifrice granule.

  In recent years, dentifrices containing granules that can effectively remove dental plaque causing causative teeth and periodontal disease and are palpable are known. These granules are substantially spherical agglomerated particles and contain functional materials such as drugs, enzymes, and abrasives so as not to damage the enamel and gums on the tooth surface. And there is something that aimed at the visual effect.

  Patent Document 1 contains (A) a water-soluble organic acid calcium salt or a water-soluble organic phosphate calcium salt and (B) a water-soluble phosphate, and releases calcium ions and phosphate ions in the oral cavity. An oral preparation, which is an oral preparation, in which components (A) and (B) are blended in solutions having different viscosities, is disclosed.

JP 2007-238633 A

Patent Document 1 describes that any one of the components (A) and (B) is blended in the coated granule, and the granules containing either the component (A) or (B) are subjected to centrifugal rolling. It is described that it is produced by a mold granulator and coated with paraffin by a fluidized bed granulator.
However, in this granule, even if calcium ion is blended in the granule, calcium ion is hardly eluted from the granule, so that calcium ion cannot be effectively used.
An object of the present invention is to provide a method for producing a dentifrice granule and a dentifrice granule having a high yield and excellent wet disintegration strength and calcium replenishment or remineralization promoting effect on teeth.

The present inventors have found a method for producing a dentifrice granule and a dentifrice granule having a high yield and excellent wet disintegration strength and excellent calcium replenishment or remineralization accelerating effect on the tooth.
That is, the present invention provides the following [1] to [2].
[1] A method for producing a dentifrice granule having the following steps 1 and 2.
Step 1: Mix water-soluble calcium salt (A), water-insoluble powder material (B) and one or more silicates (C) selected from sodium silicate and potassium silicate using a container rotating granulator. A step of granulating, wherein at least the water-insoluble powder material (B) is supplied with an aqueous solution containing at least one silicate (C) selected from sodium silicate and potassium silicate as droplets and granulated. Step 2: Step of supplying a solid coating agent (D) to the granule obtained in Step 1 at room temperature (20 ° C.) to coat the surface of the granule [2] Water-soluble calcium salt (A), water-insoluble A granule containing at least one silicate (C) selected from powder material (B), sodium silicate and potassium silicate, wherein the volume of pores having a diameter of 0.1 to 1 μm is 0.1 ml. / G or more, and at the normal temperature ( 0 ° C.) in a solid coating agent (D) dentifrice granules for coating layer is formed by.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the granule for dentifrice and the granule for dentifrice which have a high yield, the outstanding wet disintegration strength, and the calcium replenishment or remineralization acceleration effect to a tooth can be provided.

[Method for producing granules for dentifrice]
The present invention is a method for producing a dentifrice granule having the following steps 1 and 2.
Step 1: Mix water-soluble calcium salt (A), water-insoluble powder material (B) and one or more silicates (C) selected from sodium silicate and potassium silicate using a container rotating granulator. A step of granulating, wherein at least the water-insoluble powder material (B) is supplied with an aqueous solution containing at least one silicate (C) selected from sodium silicate and potassium silicate as droplets and granulated. Step 2: A step of supplying a solid coating agent (D) to the granules obtained in Step 1 at room temperature (20 ° C.) to coat the surface of the granules

In the production method of the present invention, since the silicate (C) is supplied in the form of an aqueous solution into the container rotary granulator, a porous structured granule is obtained. Even when a coating layer is formed with a solid coating agent (D), the granules are easily disintegrated by brushing during use, and the water-soluble calcium salt (A) in the granules is dissolved by water, and calcium ions are easily released. Is done. The released calcium ions combine with fluoride ions and phosphate ions contained in the dentifrice to form a calcium fluoride or calcium phosphate film on the tooth surface, thereby suppressing the occurrence of dental caries. it can. Alternatively, calcium ions can be supplied to the teeth to promote tooth remineralization.
Further, the dentifrice granules obtained by the production method of the present invention have excellent wet disintegration strength. This is because the dentifrice granule of the present invention has a porous structure, so that the aqueous solution of silicate (C) existing inside the granule is easily dried, and dehydrated silicate (C) is present inside the granule. It is thought that the granules became stronger by taking the network structure.
In the production method of the present invention, granules having a particle size suitable as a dentifrice granule can be obtained in high yield. This is probably because in the present invention, by supplying the silicate (C) as droplets of an aqueous solution into the container rotating granulator, a large liquid mass formed by coarse particles is hardly generated.
Hereafter, each component used for the process 1 and 2 of this invention and a manufacturing method are demonstrated one by one.

<Water-soluble calcium salt (A)>
The water-soluble calcium salt (A) used in the present invention is preferably at least one selected from water-soluble organic acid calcium salts and water-soluble organic phosphate calcium salts from the viewpoint of easily forming calcium fluoride.
Examples of the water-soluble organic acid calcium salt used in the present invention include calcium lactate, calcium gluconate, calcium benzoate, calcium isobutyrate, calcium propionate, calcium salicylate, and mixtures thereof.
Examples of water-soluble organic phosphate calcium salts include calcium glycerophosphate, glucose-1-calcium phosphate, glucose-6-calcium phosphate, phosphorylated oligosaccharide calcium, and mixtures thereof.
Among these, at least one selected from calcium lactate, calcium gluconate, calcium glycerophosphate, and glucose-1-calcium phosphate is preferable, and calcium lactate or calcium glycerophosphate is more preferable.
The water solubility of the water-soluble calcium salt (A) means that the amount of the water-soluble calcium salt (A) dissolved in 100 g of water (25 ° C.) is 1 g or more, preferably 1.5 g or more, more preferably 2 g or more. It means that there is.

  The average particle diameter of the water-soluble calcium salt (A) used in the present invention is preferably 0.1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, and even more preferably 30 μm or more, from the viewpoint of granulation properties. From the viewpoint of calcium ion release, the upper limit is preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 70 μm or less. The said average particle diameter can be measured as an average particle diameter of the raw material before granule manufacture by the method of an Example description. The water-soluble calcium salt (A) may be added as an aqueous solution, and in that case, it is preferably supplied as droplets of a mixed aqueous solution of the water-soluble calcium salt (A) and silicate (C).

<Water-insoluble powder material (B)>
The water-insoluble powder material (B) used in the present invention is preferably those usually used for tooth abrasives, and specifically, inorganic materials are preferred. Here, “water-insoluble” means that the amount dissolved in 100 g of water (20 ° C.) is less than 1 g.

Specific examples of the water-insoluble powder material (B) include light calcium carbonate, heavy calcium carbonate, zeolite, silica, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium phosphate, calcium pyrophosphate, One or more selected from magnesium carbonate, titanium oxide, and the like can be given. These can be used alone or in combination of two or more.
Among these, from the viewpoint of increasing wet disintegration strength and suppressing the elution of calcium ions from the granules before disintegration, one or more selected from light calcium carbonate, heavy calcium carbonate, zeolite, and silica are preferable. 1 type or 2 types chosen from light calcium carbonate and heavy calcium carbonate are more preferable, and heavy calcium carbonate is still more preferable.

The average particle size of the water-insoluble powder material (B) is preferably 0.1 μm or more, more preferably 0.5 μm, from the viewpoint of increasing wet disintegration strength and suppressing the elution of calcium ions from the granules before disintegration. Above, more preferably 1 μm or more, still more preferably 3 μm or more, and from the viewpoint of reducing the feeling of foreign matter when used as a dentifrice, the upper limit is preferably 20 μm or less, more preferably 15 μm or less, still more preferably Is 10 μm or less, more preferably 7 μm or less.
An average particle diameter can be measured as an average particle diameter of the raw material before granule manufacture by the method of an Example description.

  The mass ratio [(A) / (B)] of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is preferably from the viewpoint of enhancing calcium replenishment or remineralization promoting effect to the teeth. From the viewpoint of increasing wet disintegration strength, it is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3. It is as follows.

<Silicate (C)>
The silicate (C) used in the present invention is at least one of sodium silicate and potassium silicate. These sodium silicate and potassium silicate are silicates which are water-soluble inorganic binders. The silicate (C) is used for imparting excellent wet disintegration strength to the granules. This silicate (C) is a water-soluble binder, but as will be described later, the wet disintegration strength of the granules is further improved by appropriately drying the granules as necessary. The silicate (C) which is a water-soluble inorganic binder is a silicate having a dissolution amount (20 ° C.) in 100 g of water of preferably 30 g or more, and the dissolution amount is more preferably 50 g or more.
The silicate (C) preferably contains sodium silicate from the viewpoint of improving wet disintegration strength.

  The granule may contain a silicate other than the silicate (C). From the above viewpoint, the content of the silicate (C) in all the silicates is preferably 95% by mass or more, more preferably. It is 99 mass% or more, More preferably, it is 99.5 mass% or more, More preferably, it is 100 mass%. From the same viewpoint, the content of sodium silicate in all silicates is preferably 95% by mass or more, more preferably 99% by mass or more, still more preferably 99.5% by mass or more, and still more preferably 100% by mass. It is.

Examples of sodium silicate include sodium metasilicate (Na ₂ SiO ₃ ), sodium orthosilicate (Na ₄ SiO ₄ ), sodium disilicate (Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ Si ₄ O ₉ ), and These hydrates are mentioned.
Sodium silicate is generally represented by a molecular formula of Na ₂ O.nSiO ₂ .mH ₂ O. The coefficient n (molecular ratio of SiO _{2 to} Na ₂ O) is called molar ratio and can be expressed by the following formula (1).
Molar ratio = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × Na ₂ O molecular weight / SiO ₂ molecular weight = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × 1.032 (1)
As sodium silicate, water glass having various molar ratios can be used in addition to sodium silicate Nos. 1, 2, and 3 described in JIS K1408.
Although the physical properties of sodium silicate vary depending on the molar ratio, the molar ratio is preferably 2.0 or more, more preferably 2. from the viewpoint of compatibility with quasi-drug raw material specifications and the pH of the granules to be obtained. 4 or more, more preferably 2.8 or more, even more preferably 3.0 or more, and preferably 4.0 or less, more preferably 3.7 or less, still more preferably 3.5 or less, and still more preferably Is 3.3 or less.

  The mass ratio [(C) / {(A) + (B)}] of the silicate (C) (solid content) to the total of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is a wet disintegration. From the viewpoint of increasing the strength and suppressing the elution of calcium ions from the granule before disintegration, it is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and the production cost. From the viewpoint of reducing the thickness and the viewpoint of making it porous, it is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.3 or less.

<A solid coating agent (D) at room temperature (20° C.)>
The melting point of the coating agent (D) which is solid at room temperature (20 ° C.) used in the present invention is the viewpoint of suppressing aggregation of the granules during production and storage of the obtained granules, and the calcium ions from the granules before disintegration. From the viewpoint of suppressing elution, the melting point is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, and from the viewpoint of ease of production, preferably 90 ° C. or lower, more preferably It is 80 degrees C or less.
Specific examples of the coating agent (D) that is solid at room temperature (20 ° C.) include fatty acids, fatty acid derivatives, fats and oils, resins, and the like. More preferably, fatty acids having 16 to 22 carbon atoms, fatty acid derivatives having 16 to 22 carbon atoms (wax, higher alcohol, surfactant), fats and oils, and the like can be used.
Examples of the fatty acid having 16 to 22 carbon atoms include palmitic acid, stearic acid, eicosanoic acid, and behenic acid.
Examples of the higher alcohol having 16 to 22 carbon atoms include higher alcohols such as cetyl alcohol, stearyl alcohol, and behenyl alcohol (melting point: 67 to 73 ° C.).
Examples of the wax include paraffin wax, distearyl ketone, beeswax, whale wax, candelilla wax, rice wax, carnauba wax and the like.
Examples of the fat include hardened rapeseed oil and hardened castor oil.
Examples of the resin include ethyl cellulose, polyethylene, and polypropylene. Among these, waxes are preferable from the viewpoints of coating properties and costs when granulated, beeswax, candelilla wax (melting point: 68 to 72 ° C.), rice wax and carnauba wax are more preferable, and candelilla wax is still more preferable. .

  Mass ratio of coating agent (D) solid at room temperature (20 ° C.) to the total of water-soluble calcium salt (A), water-insoluble powder material (B) and silicate (C) (solid content) [(D) / {(A) + (B) + (C)}] is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably, from the viewpoint of suppressing elution of calcium ions from the granules before disintegration. 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, and still more preferably 0.6 or more, and the granules are easily broken down during brushing to increase the amount of fluorine adsorption. From the viewpoint, it is preferably 1.5 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

<Step 1>
In step 1, a water-soluble calcium salt (A), a water-insoluble powder material (B), and one or more silicates (C) selected from sodium silicate and potassium silicate are used in a container rotating granulator. Mixing and granulating, supplying at least water-insoluble powder material (B) as an aqueous solution containing at least one silicate (C) selected from sodium silicate and potassium silicate as droplets It is a process to do.
Here, the aqueous solution containing silicate (C) may contain at least silicate (C), preferably an aqueous solution of silicate (C), or water-soluble calcium salt (A) and silicate (C ).

In Step 1, the water-insoluble powder material (B) may be granulated by adding droplets of a mixed aqueous solution of the water-soluble calcium salt (A) and silicate (C). From the viewpoint of facilitating granulation and suppressing the elution of calcium ions, the water-soluble calcium salt (A) and the water-insoluble powder material (B) are mixed, and at least the water-insoluble powder material (B) It is preferable to granulate by adding the droplet of the aqueous solution of silicate (C) to the said mixture containing.
That is, it is preferable to granulate by adding droplets of an aqueous solution of silicate (C) to at least the water-insoluble powder material (B).

(Container rotating granulator)
In the present invention, a container rotating granulator is used in step 1 from the viewpoint of improving yield, obtaining porous granules, and increasing wet disintegration strength. In Step 2, it is preferable to use a container rotating granulator from the viewpoint of improving the yield.
Hereinafter, it describes in common with process 1 and 2.
As the container rotating granulator, a drum granulator and a bread granulator are preferable. The drum granulator is not particularly limited as long as the drum-shaped cylinder rotates and performs processing. A horizontal or slightly inclined drum granulator can also be used. These apparatuses may be either batch type or continuous type.
If the wall friction coefficient between the water-insoluble powder material (B) and the inner wall of the container rotating granulator is small and it is difficult to apply sufficient ascending kinetic force to the powder, the container inner wall should be mixed. It is preferable to provide a plurality of baffles for assisting. By providing the baffle plate, it is possible to impart an upward movement to the powder, and the powder mixing property and the solid-liquid mixing property are improved.

The operating conditions of the container rotating granulator are not particularly limited as long as the powder in the granulator can be flowed as uniformly as possible and stirred. From the viewpoint of productivity, the fluid number defined by the following formula (2) is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.05 or more, And, from the viewpoint of increasing wet disintegration strength, from the viewpoint of improving yield, and from the viewpoint of obtaining porous granules, the upper limit is preferably 1.0 or less, more preferably 0.6 or less. More preferably, it is 0.4 or less.
The preferred fluid number is the same also in the preliminary mixing in which the water-soluble calcium salt (A) and the water-insoluble powder material (B) are mixed using a container rotating granulator. The operation time during the premixing is preferably 3 minutes or more, more preferably 5 minutes or more, still more preferably 7 minutes or more, and preferably 90 minutes or less, more preferably 60 minutes or less, still more preferably. 30 minutes or less.
Fluid number: Fr = V / {(R × g) ^1/2 } (2)
V: Circumferential speed [m / s]
R: Radius from the center of rotation to the circumference of the rotating object [m]
g: Gravity acceleration [m / s ² ]
In a drum granulator or a bread granulator in which granulation proceeds by rotation of the main body, V and R are values of the main body, and in a pan granulator equipped with crushing blades. , V and R are the values of the crushing blade.

(nozzle)
In Step 1 of the present invention, from the viewpoint of suppressing the formation of coarse particles and increasing the yield, an aqueous solution containing a silicate (C) is supplied as droplets, preferably using a nozzle, more preferably a multi-fluid. It supplies using a nozzle, More preferably, it supplies using a two fluid nozzle. In Step 2, from the viewpoint of increasing the yield, the solid coating material (D) at normal temperature (20 ° C.) is preferably supplied at a temperature equal to or higher than the melting point, preferably using a nozzle, and more preferably a multi-fluid. It supplies using a nozzle, More preferably, it supplies using a two fluid nozzle.
By using a multi-fluid nozzle, the droplets can be made fine and dispersed.
A multi-fluid nozzle is a nozzle that mixes and atomizes a liquid and atomizing gas (air, nitrogen, etc.) through an independent flow path to the vicinity of the nozzle tip, and is a two-fluid nozzle, three-fluid nozzle, four-fluid A nozzle etc. can be mentioned. Further, the mixing portion of the aqueous solution containing silicate (C) and the gas for spraying, or the mixing portion of the melt or solution of the coating material (D) solid at normal temperature (20 ° C.) and the gas for spraying is within the nozzle tip. Either an internal mixing type for mixing or an external mixing type for mixing outside the nozzle tip may be used.
As such a multi-fluid nozzle, an internally mixed two-fluid nozzle made by Spraying Systems Japan Co., Ltd., Kyoritsu Alloy Manufacturing Co., Ltd., Ikeuchi Co., Ltd., etc., manufactured by Spraying Systems Japan Co., Ltd., Kyoritsu Co., Ltd. Examples thereof include an external mixed type two-fluid nozzle manufactured by Alloy Seisakusho, manufactured by Atmax Co., Ltd., and an external mixed type four-fluid nozzle manufactured by Fujisaki Electric Co., Ltd.

The average droplet diameter of the aqueous solution containing silicate (C) and the melt or solution of the coating agent (D) solid at room temperature (20 ° C.) is the nozzle tip shape, spray pattern, and silicate (C). It can be adjusted to a desired range by adjusting the balance of the flow rate of the molten solution or solution of the coating solution (D) solid at normal temperature (20 ° C.) and the flow rate of the spray gas. That is, in order to reduce the average droplet diameter, an atomizing gas is applied to an aqueous solution containing a silicate (C) at a constant flow rate and a melt or solution of a coating material (D) that is solid at room temperature (20 ° C.). The flow rate of the molten solution or solution of the aqueous solution containing silicate (C) and the solid coating agent (D) at room temperature (20 ° C.) with respect to the spray gas at a constant flow rate Should be reduced.
For example, when a two-fluid nozzle is used, the flow rate of the atomizing gas is preferably 10 NL / min or more, more preferably 30 NL / min or more, and still more preferably, from the viewpoint of adjusting the average droplet diameter to the following average particle diameter. 50 NL / min or more, and preferably 300 NL / min or less, more preferably 200 NL / min or less, and still more preferably 150 NL / min or less from the viewpoint of equipment load.

In Step 1, the average droplet diameter of the aqueous solution containing silicate (C) is reduced from the coarse particle ratio, and from the viewpoint of obtaining a granule having a suitable particle size as a dentifrice granule with high yield, silicate (C) is used. The average droplet diameter of the aqueous solution to be contained is preferably 210 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, still more preferably 80 μm or less, and from the viewpoint of productivity, preferably 1 μm or more, more preferably Is 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and still more preferably 50 μm or more.
In Step 2, the average droplet size of the melt or solution of the coating material (D) that is solid at room temperature (20 ° C.) reduces the coarse particle ratio and produces granules with a suitable particle size as a dentifrice granule with high yield. From the viewpoint of obtaining, it is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, still more preferably 80 μm or less, and from the viewpoint of productivity, preferably 1 μm or more, more preferably 5 μm or more, and further Preferably it is 10 micrometers or more, More preferably, it is 20 micrometers or more, More preferably, it is 30 micrometers or more.

As the average droplet diameter is decreased, the flow rate of the aqueous solution containing the silicate (C) and the melt or solution of the solid coating material (D) at room temperature (20 ° C.) decreases, and the productivity decreases. By using a plurality of fluid nozzles and reducing the flow rate per nozzle, the addition rate can be increased while maintaining the fineness of the droplets. The number of multi-fluid nozzles may be one or more, but preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
In addition, the melt or solution average droplet diameter of an aqueous solution containing a silicate (C) and a coating material (D) that is solid at room temperature (20 ° C.) is calculated on a volume basis. It is a value measured using a particle size distribution measuring apparatus (Malvern Co., Ltd., spray tech). Specifically, it can be measured by the method described in the examples.

In the production method of the present invention, the silicate (C) (solid content) in the silicate (C) aqueous solution supplied as droplets is from the viewpoint of granulating the water-insoluble powder material (B) as a water-soluble inorganic binder. , Preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and still more preferably 35% by mass or more. From the viewpoint of improving the wet disintegration strength of the granule, it is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 58% by mass or less.
In addition, the silicate (C) (solid content) in the aqueous solution of a silicate (C) can be calculated | required by the method of an Example description.
Furthermore, the aqueous solution of silicate (C) can contain a polymer, inorganic particles, or the like, or can contain a lower alcohol having 1 to 3 carbon atoms, as long as the present invention is not inhibited.
For example, when measuring the solid content of the water-soluble calcium salt (A) and the silicate (C) in the mixed aqueous solution of the water-soluble calcium salt (A) and the silicate (C), before mixing the aqueous solution The solid content of the water-soluble calcium salt (A) in the aqueous solution of the water-soluble calcium salt (A) and the solid content of the silicate (C) in the aqueous solution of the silicate (C) It can be determined by the same method as the method for measuring salt (C) (solid content). Even when the aqueous solution containing the silicate (C) contains components other than those described above, the amount of each component can be determined by the same method before mixing the aqueous solution containing each component.

The temperature of the aqueous solution containing the silicate (C) when supplying the aqueous solution containing the silicate (C) as droplets is preferably 5 ° C. or more, more preferably from the viewpoint of the stability of the supply state of the droplets. It is 10 ° C. or higher, more preferably 15 ° C. or higher, and preferably 50 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 25 ° C. or lower.
The time for supplying the aqueous solution containing the silicate (C) as droplets is preferably 2 minutes or more, more preferably 3 minutes or more, from the viewpoint of the stability of the supply state of the droplets, although it depends on the blending amount. More preferably, it is 5 minutes or more, Preferably it is 90 minutes or less, More preferably, it is 60 minutes or less, More preferably, it is 30 minutes or less, More preferably, it is 15 minutes or less.
The addition rate of the aqueous solution of the silicate (C) to 100 parts by mass of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is preferable from the viewpoint of suppressing the formation of coarse particles and increasing the yield. Is 35 parts by mass / min or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less, still more preferably 5.0 parts by mass / min or less, still more preferably 3.0 parts by mass. The lower limit is preferably 0.2 parts by mass / min or more, more preferably 0.5 parts by mass / min or more, still more preferably 1 part by mass / min or more, and even more preferably 1. 5 parts by mass / min or more. The above range is suitable when using sodium silicate No. 1, 2 or 3 described in JIS K1408.

<Drying process>
In the present invention, from the viewpoint of improving wet disintegration strength and uniformly coating the granule surface in step 2, it is preferable to have a drying step after step 1 to dry the obtained granules.
By performing the drying operation, the wet disintegration strength of the granules can be improved, and the stability in the dentifrice can be improved. Although the detailed reason is not clear, it is thought that the dehydration condensation of silicate (C) progressed with drying, the network structure of silicate (C) was developed, and the strength was improved.
Examples of the drying method include shelf drying, fluidized bed drying, reduced pressure drying, and microwave drying. Among these, from the viewpoint of equipment, shelf drying and fluidized bed drying are preferable.
From the viewpoint of suppressing the disintegration of the granules during drying, a drying method that does not give as much shearing force as possible is preferable. For example, in the batch type, there are a method of drying with an electric shelf dryer or a hot air dryer, a method of drying in a batch type fluidized bed, etc., and a continuous type is dried with a fluidized bed, rotary dryer, steam tube dryer or the like. The method of letting it be mentioned.

The drying temperature can be appropriately determined in consideration of the drying speed, but is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher. Moreover, from a viewpoint of the thermal load of an apparatus, Preferably it is 200 degrees C or less, More preferably, it is 150 degrees C or less, More preferably, it is 110 degrees C or less.
The drying time varies depending on the effective amount and amount of the aqueous solution containing the silicate (C) used in the production, but is appropriately adjusted so that the wet disintegration strength is within the preferable range of the present invention. The drying time is preferably 10 minutes or more, more preferably 20 minutes or more, still more preferably 30 minutes or more, and preferably 24 hours or less, more preferably 10 hours or less, and even more preferably 3 hours or less.
In the case of electric shelf drying, the drying time is preferably 20 minutes or more, more preferably 30 minutes or more, and preferably 24 hours or less, more preferably 12 hours or less.
In the case of fluidized bed drying, the drying time is preferably 10 minutes or more, more preferably 20 minutes or more, and preferably 5 hours or less, more preferably 3 hours or less.

<Process 2>
In step 2, the granules obtained in step 1 are coated with a solid coating agent (D) at room temperature (20 ° C.), preferably as a melt or solution, more preferably as a melt, preferably the container rotating mold. This is a step of supplying the granulator to coat the surface of the granule.

In step 2, as in step 1, it is preferable to use a container rotating granulator from the viewpoint of suppressing the formation of coarse particles and increasing the yield. Examples of other granulators include fluidized bed granulators. Examples of the container rotating granulator include those described above, and preferable apparatuses and preferable operating conditions are the same as described above.
Furthermore, from the viewpoint of increasing the yield, the coating material (D) that is solid at room temperature (20 ° C.) is made to have a melting point or higher, and is supplied as a melt, preferably using a nozzle, more preferably using a multi-fluid nozzle. More preferably, it is supplied using a two-fluid nozzle. Examples of the multi-fluid nozzle include those described above, and preferred devices are the same as those described above. In addition, even if it is the melting | fusing point fall of solid coating material (D) at normal temperature (20 degreeC) by mixing a solvent etc., it can supply as a solution of this coating material (D).
The temperature of the coating agent (D) when supplying the solid coating agent (D) at normal temperature (20 ° C.) is preferably a temperature equal to or higher than the melting point, more preferably 70 ° C. from the viewpoint of supply. From the viewpoint of productivity, it is preferably 110 ° C. or lower, more preferably 105 ° C. or lower, and further preferably 100 ° C. or lower.
Moreover, the addition speed | rate of solid coating material (D) at normal temperature (20 degreeC) with respect to a total of 100 mass parts of water-soluble calcium salt (A) and water-insoluble powder material (B) suppresses formation of a coarse particle, From the viewpoint of increasing the yield, it is preferably 35 parts by mass / min or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less, still more preferably 5 parts by mass / min or less, and even more preferably. Is 3 parts by mass / min or less, and the lower limit thereof is preferably 0.2 parts by mass / min or more, more preferably 0.5 parts by mass / min or more, and further preferably 1 part by mass from the viewpoint of productivity. Part / min or more, more preferably 1.5 parts by mass / min or more.

[Granule for dentifrice]
The dentifrice granules of the present invention are granules containing one or more silicates (C) selected from water-soluble calcium salt (A), water-insoluble powder material (B), sodium silicate and potassium silicate, In the granules, the volume of pores having a diameter of 0.1 to 1 μm is 0.1 ml / g or more, and a coating layer made of a solid coating agent (D) is formed on the surface of the granules at room temperature (20 ° C.). It is a dentifrice granule.
The granules for dentifrice of the present invention are preferably those obtained by the above production method. Other production methods include, for example, granulating water-soluble calcium salt (A), water-insoluble powder material (B), and silicate (C), and an oil agent by rolling granulation or spray drying, Granules having pores may be produced by a method such as extracting the oil agent into a solvent and removing it.

<Contents of components (A) to (D), etc.>
In the dentifrice granule, the content of the water-soluble calcium salt (A) is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of enhancing the calcium supplementation or remineralization promoting effect to the teeth. Preferably it is 5 mass% or more, More preferably, it is 7 mass% or more. From the viewpoint of increasing wet disintegration strength, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 13% by mass or less. More preferably, it is 12 mass% or less, More preferably, it is 10 mass% or less.

  In the dentifrice granule of the present invention, the content of the water-insoluble powder material (B) is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of increasing wet disintegration strength and increasing the polishing power. The upper limit is preferably 92% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, more preferably 35% by mass or more, and from the viewpoint of suppressing damage to teeth. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less.

  In the granule for dentifrice of the present invention, the content of silicate (C) (solid content) is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4%, from the viewpoint of increasing wet disintegration strength. From the viewpoint of reducing production cost, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 15% by mass or more. Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 7 mass% or less, More preferably, it is 6 mass% or less.

  In the granule for dentifrice of the present invention, the content of the coating agent (D) solid at normal temperature (20 ° C.) is preferably 5 mass from the viewpoint of suppressing elution of calcium ions when blended in the dentifrice. % Or more, more preferably 7% by weight or more, still more preferably 10% by weight or more, still more preferably 20% by weight or more, still more preferably 30% by weight or more, still more preferably 40% by weight or more, and From the viewpoint of making the granules easy to disintegrate during brushing and increasing the amount of fluorine adsorption, it is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

  In this invention, the calculated value calculated | required from the compounding quantity at the time of granule manufacture can be used for content and mass ratio of each component in the granule for dentifrice. The solid content of the silicate (C) is the solid content determined by the method described in the examples.

  The water content in the dentifrice granules is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2.5% by mass or less, and still more preferably 2% by mass from the viewpoint of increasing wet disintegration strength. From the viewpoint of productivity, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more. The amount of water in the granules can be determined by the method described in the examples. The wet disintegration strength depends on the type of the water-insoluble powder material (B), but in the same type, the wet disintegration strength increases as the water content decreases.

  Mass ratio [(A) / (B)] of the water-soluble calcium salt (A) and the water-insoluble powder material (B), and the total of the water-soluble calcium salt (A) and the water-insoluble powder material (B) Ratio of silicate (C) (solid content) to amount [(C) / {(A) + (B)}], and the water-soluble calcium salt (A), water-insoluble powder material (B) and silicate The mass ratio [(D) / {(A) + (B) + (C)}] of the solid coating agent (D) at the normal temperature (20 ° C.) with respect to the total amount of (C) (solid content) is: As described above, the preferred range is also the same.

<Other ingredients>
As long as it does not impair the object of the present invention, the dentifrice granule according to the present invention contains the water-soluble calcium salt (A), the water-insoluble powder material (B), the silicate (C), room temperature. In addition to the solid coating agent (D) at (20 ° C.), a water-insoluble inorganic binder, organic fiber, medicinal component, coloring agent and the like can be blended.

  The content of the optional component is preferably 0 mass with respect to 100 mass parts of the total solid content of the water-soluble calcium salt (A), the water-insoluble powder material (B) and the silicate (C) from the viewpoint of disintegration feeling. It is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1 part by mass or less, and still more preferably 0 parts by mass.

As the water-insoluble inorganic binder, a silicon-based compound, an aluminum-based compound, a calcium-based compound, a magnesium-based compound having a hydroxyl group can be suitably used. Specific examples include colloidal silica, magnesium aluminate metasilicate, synthetic aluminum silicate, calcium silicate, bentonite, montmorillonite, kaolin, alumina sol, synthetic hydrotalcite, magnesium oxide, and magnesium hydroxide.
Examples of the organic fiber include cellulose, hemicellulose, lignin, chitin, and the like. Among these, cellulose is particularly preferable from the viewpoint of removing plaque from the granules.

  Medicinal ingredients include caries preventive agents, antimicrobial agents, enzymes, anti-inflammatory agents, etc., specifically sodium fluoride, potassium fluoride, tin fluoride, sodium monofluorophosphate, vitamin E, vitamins C, dextranase, mutanase, sodium chloride and other anti-inflammatory agents; aluminum lactate, azulene, glycyrrhetinic acid, β-glycyrrhetinic acid, allantochlorohydroxyaluminum, lysozyme chloride, epsilon aminocaproic acid, copper chlorophyllin sodium, copper gluconate, acetic acid Antihypersensitivity agents such as dl-tocopherol and potassium nitrate; anticalculus agents such as sodium tripolyphosphate and ethanehydroxydiphosphonate; plaque formation inhibitors such as zinc compounds; dihydrcholesterol, chlorhexidine, epidihydrcholesterol, iso B pills methylphenol, trichlorocarbanilide, halocarban, hinokitiol, allantoin, tranexamic acid, propolis, benzethonium chloride, cetylpyridinium chloride, fungicides such as triclosan, polyethylene glycol, Tabakoyani removers such as polyvinylpyrrolidone and the like.

Examples of the colorant include titanium oxide and ultramarine blue, and an aesthetic effect can be added by adding these colorants.
The said other compounding component can be used individually or in combination of 2 or more types.

<Characteristics of dentifrice granules>
The wet disintegration strength of the dentifrice granules of the present invention according to the method described in the examples is improved in terms of enabling the palpability of the granules in the mouth and improving the plaque removal effect when used in a dentifrice. In view of the above, it is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more, and still more preferably 80% or more, and almost no foreign body sensation is felt. From the viewpoint, it is preferably 95% or less, more preferably 90% or less.

The average particle size of the dentifrice granule of the present invention is preferably 50 μm or more, more preferably 100 μm or more, and further preferably 150 μm or more, from the viewpoint of imparting sufficient polishing power, and foreign body sensation in the oral cavity. From the viewpoint of suppressing, the thickness is preferably 500 μm or less, more preferably 400 μm or less, further preferably 350 μm or less, and still more preferably 300 μm or less.
In addition, an average particle diameter can be measured by the method as described in an Example.

  The diameter 0 contained in the dentifrice granules containing the water-soluble calcium salt (A), the water-insoluble powder material (B), the sodium silicate and one or more silicates (C) of potassium silicate according to the present invention. .1 to 1 μm pore volume is a viewpoint that when used as a dentifrice, the water-soluble calcium salt (A) quickly melts from the location where the granule collapses and enhances the mineral replenishment or remineralization promoting effect on the teeth. To 0.1 ml / g or more, preferably 0.2 ml / g or more, more preferably 0.3 ml / g or more, still more preferably 0.4 ml / g or more, and from the viewpoint of increasing wet disintegration strength Preferably, it is 1.0 ml / g or less, More preferably, it is 0.7 ml / g or less, More preferably, it is 0.6 ml / g or less, More preferably, it is 0.5 ml / g or less.

<Dentifrice>
The dentifrice granules of the present invention can be used together with a surfactant or the like as a component of a dentifrice. By using the dentifrice granule of the present invention together with a surfactant, it provides good foaming and sufficiently removes plaque or dirt to a narrow area such as a gap between teeth. It is possible to enhance the cleaning effect in combination with the surfactant, and to give a feeling of slipping on the tooth surface in the oral cavity after using the dentifrice, thereby enhancing the feeling of use.
In the dentifrice, the content of the dentifrice granules is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of enhancing the plaque or dirt removal effect and supplementing calcium or promoting remineralization. More preferably, it is 5% by mass or more, and from the viewpoint of exerting an effect of removing plaque or dirt, it is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably. Is 15% by mass or less.
As the surfactant, at least one selected from anionic surfactants, nonionic surfactants, and zwitterionic surfactants can be used. As the surfactant, anionic surfactants are preferable, alkyl sulfates are more preferable, and sodium lauryl sulfate is still more preferable from the viewpoint of providing good foamability and a feeling of use.
In addition to dentifrices such as sodium carboxymethylcellulose, wetting agents such as sorbit and polyethylene glycol, abrasives, excipients, sweeteners, preservatives, fragrances, medicinal ingredients, colorants, bactericides, and others Commonly used components can be included.

In relation to the above-described embodiment, the present invention further discloses the following method for producing dentifrice granules and dentifrice granules.
<1> A method for producing a dentifrice granule having the following steps 1 and 2.
Step 1: Water-soluble calcium salt (A), water-insoluble powder material (B), and one or more silicates (C) selected from sodium silicate and potassium silicate using a container rotating granulator. It is a step of mixing and granulating, and at least the water-insoluble powder material (B) is supplied with an aqueous solution containing at least one silicate (C) selected from sodium silicate and potassium silicate as droplets and granulated. Step Step 2: Step of coating the granule surface by supplying a solid coating agent (D) to the granule obtained in Step 1 at room temperature (20 ° C.)

<2> In step 2, the granules obtained in step 1 are coated with a solid coating agent (D) at room temperature (20 ° C.), preferably at a temperature equal to or higher than the melting point, preferably in the container rotating granulator of step 1. The method for producing a dentifrice granule according to <1>, wherein the granule surface obtained in step 1 is coated.
<3> The water-soluble calcium salt (A) is preferably one or more selected from a water-soluble organic acid calcium salt and a water-soluble organic phosphate calcium salt, more preferably a water-soluble organic acid calcium salt. The manufacturing method of the granule for dentifrice as described in said <1> or <2>.
<4> The water-soluble organic acid calcium salt is preferably at least one selected from calcium lactate, calcium gluconate, calcium benzoate, calcium isobutyrate, calcium propionate, and calcium salicylate, and more preferably calcium lactate and glucone. The method for producing a dentifrice granule according to the above <3>, which is at least one selected from calcium acid, more preferably calcium lactate.
<5> The water-soluble organic phosphate calcium salt is preferably at least one selected from calcium glycerophosphate, glucose-1-calcium phosphate, glucose-6-calcium phosphate, calcium phosphorylated oligosaccharide calcium, more preferably calcium glycerophosphate, And the granule for dentifrice according to <3>, which is at least one selected from glucose-1-calcium phosphate, and more preferably calcium glycerophosphate.
<6> The average particle diameter of the water-soluble calcium salt (A) is preferably 0.1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 30 μm or more, and preferably 150 μm or less. The method for producing a dentifrice granule according to any one of <1> to <5>, preferably 100 μm or less, more preferably 70 μm or less.
<7> Water-insoluble powder material (B) is preferably light calcium carbonate, heavy calcium carbonate, zeolite, silica, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium phosphate, calcium pyrophosphate 1 or more selected from magnesium carbonate, titanium oxide, and the like, more preferably 1 or more selected from light calcium carbonate, heavy calcium carbonate, zeolite, and silica, and more preferably heavy calcium carbonate. The manufacturing method of the granule for dentifrice in any one of said <1>-<6>.

<8> The average particle size of the water-insoluble powder material (B) is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, still more preferably 3 μm or more, preferably 20 μm or less. More preferably, it is 15 micrometers or less, More preferably, it is 10 micrometers or less, More preferably, it is 7 micrometers or less, The manufacturing method of the granule for dentifrice in any one of said <1>-<7>.
<9> The mass ratio [(A) / (B)] of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably. Is 0.15 or more, preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.3 or less, for a dentifrice according to any one of <1> to <8> above Granule manufacturing method.

<10> The content of one or more silicates (C) selected from sodium silicate and potassium silicate in the total silicate is preferably 95% by mass or more, more preferably 99% by mass or more, and still more preferably 99.% by mass. The method for producing a dentifrice granule according to any one of <1> to <9>, wherein the content is 5% by mass or more, more preferably 100% by mass.
<11> The content of sodium silicate in the total silicate is preferably 95% by mass or more, more preferably 99% by mass or more, still more preferably 99.5% by mass or more, and still more preferably 100% by mass. The manufacturing method of the granule for dentifrice in any one of said <1>-<10>.
<12> sodium silicate is preferably _{Na 2 O · nSiO 2 · mH} 2 O ( molar ratio of SiO ₂ to the coefficient n (Na ₂ O) represents the molar ratio represented by the following formula (1)) molecular formula of The molar ratio is preferably 2.0 or more, more preferably 2.4 or more, still more preferably 2.8 or more, still more preferably 3.0 or more, preferably 4.0 or less, More preferably, it is 3.7 or less, More preferably, it is 3.5 or less, More preferably, it is 3.3 or less, The manufacturing method of the granule for dentifrice in any one of said <1>-<11>.
Molar ratio = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × Na ₂ O molecular weight / SiO ₂ molecular weight = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × 1.032 (1)
<13> The mass ratio [(C) / {(A) + (B)}] of the silicate (C) (solid content) to the total of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is , Preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less. The method for producing a dentifrice granule according to any one of <1> to <12>.

<14> The melting point of the coating material (D) which is solid at normal temperature (20 ° C.) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, preferably 90 ° C. or lower, more preferably. Is a method for producing a dentifrice granule according to any one of <1> to <13>, which is 80 ° C. or lower.
<15> The coating agent (D) which is solid at normal temperature (20 ° C.) is preferably one or more selected from fatty acids, fatty acid derivatives, fats and resins, and more preferably fatty acids and carbons having 16 to 22 carbon atoms. The fatty acid derivative (wax, higher alcohol, surfactant) of 16 to 22 and one or more selected from oils and fats, and more preferably a candelilla wax, according to any one of <1> to <14>. For producing granules for dentifrice.
<16> Mass ratio of coating agent (D) solid at normal temperature (20 ° C.) to the total of water-soluble calcium salt (A), water-insoluble powder material (B) and silicate (C) (solid content) [( D) / {(A) + (B) + (C)}] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and still more preferably 0.4 or more. More preferably, it is 0.5 or more, more preferably 0.6 or more, preferably 1.5 or less, more preferably 1.2 or less, still more preferably 1.0 or less, <1> The manufacturing method of the granule for dentifrice in any one of <15>.

<17> The container rotary granulator is preferably one or more selected from a drum granulator and a bread granulator, and more preferably a drum granulator having a plurality of baffle plates on the inner wall of the container. The method for producing a dentifrice granule according to any one of <1> to <16>, wherein the granule is one or more selected from a machine and a bread granulator.
<18> The fluid number defined by the following formula (2), which is the operating condition of the container rotating granulator, is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.05 or more. Yes, Preferably it is 1.0 or less, More preferably, it is 0.6 or less, More preferably, it is 0.4 or less, The manufacturing method of the granule for dentifrice in any one of said <1>-<17>.
Fluid number: Fr = V / {(R × g) ^1/2 } (2)
V: Circumferential speed [m / s]
R: Radius from the center of rotation to the circumference of the rotating object [m]
g: Gravity acceleration [m / s ² ]
However, in a drum granulator or a bread granulator in which granulation proceeds by rotation of the main body, V and R use the values of the main body, and horizontal or vertical type with a main wing and a crushing wing. In the granulator, V and R use the values of the main shaft, and in a bread granulator equipped with crushing blades, V and R represent the values of the crushing blades.
<19> The operation time for premixing the water-soluble calcium salt (A) and the water-insoluble powder material (B) using a container rotating granulator is preferably 3 minutes or more, more preferably 5 Or more, more preferably 7 minutes or more, and preferably 90 minutes or less, more preferably 60 minutes or less, still more preferably 30 minutes or less, according to any one of <1> to <18> above. A method for producing dentifrice granules.

<20> In step 1, the aqueous solution containing silicate (C) is supplied as droplets, preferably using a nozzle, more preferably using a multi-fluid nozzle, and even more preferably using a two-fluid nozzle. The method for producing a dentifrice granule according to any one of <1> to <19>.
<21> In Step 2, the coating agent (D) that is solid at room temperature (20 ° C.) is preferably supplied as a melt or solution, more preferably as a melt, preferably using a nozzle, more preferably The method for producing a dentifrice granule according to any one of <1> to <20>, wherein the granule is supplied using a fluid nozzle, more preferably supplied using a two-fluid nozzle.
<22> A multifluid nozzle is a mixing part of an aqueous solution containing silicate (C) and a spraying gas, or a mixing part of a melt or solution of a coating material (D) solid at normal temperature (20 ° C.) and a spraying gas However, the method for producing a dentifrice granule according to any one of the above <1> to <21>, which is preferably an internal mixing type that mixes within the nozzle tip or an external mixing type that mixes outside the nozzle tip.
<23> In step 1, the average droplet diameter of the aqueous solution containing silicate (C) is preferably 210 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, still more preferably 80 μm or less, preferably The dentifrice granule according to any one of <1> to <22>, which is 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, still more preferably 20 μm or more, and even more preferably 50 μm or more. Production method.
<24> In step 2, the average droplet diameter of the melt or solution of the coating agent (D) that is solid at room temperature (20 ° C.) is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. More preferably, it is 80 μm or less, preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 20 μm or more, and still more preferably 30 μm or more, <1> to <23> The manufacturing method of the granule for dentifrice in any one.
The temperature of the aqueous solution containing the silicate (C) when the aqueous solution containing <25> silicate (C) is supplied as droplets is preferably 5 ° C or higher, more preferably 10 ° C or higher, still more preferably 15 ° C. It is above, Preferably it is 50 degrees C or less, More preferably, it is 30 degrees C or less, More preferably, it is 25 degrees C or less, The manufacturing method of the granule for dentifrice in any one of said <1>-<24>.
The addition rate of the aqueous solution of silicate (C) with respect to a total of 100 parts by mass of <26> water-soluble calcium salt (A) and water-insoluble powder material (B) is preferably 35 parts by mass / min or less, more preferably 20 Parts by mass / min or less, more preferably 10 parts by mass / min or less, still more preferably 5 parts by mass / min or less, still more preferably 3 parts by mass / min or less, preferably 0.2 parts by mass / min or more. More preferably 0.5 parts by mass / min or more, more preferably 1 parts by mass / min or more, and even more preferably 1.5 parts by mass / min or more, in any one of the above items <1> to <25> The manufacturing method of the granule for dentifrice of description.

<27> The method for producing a dentifrice granule according to any one of the above <1> to <26>, which preferably has a drying step between step 1 and step 2.
<28> The drying method is preferably one or more selected from shelf drying, fluidized bed drying, vacuum drying, and microwave drying, more preferably one or more selected from shelf drying and fluidized bed drying, The method for producing a dentifrice granule according to the above <27>, which is preferably fluidized bed drying.
<29> The drying temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, still more preferably 90 ° C. or higher, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, More preferably, it is 110 degrees C or less, The manufacturing method of the granule for dentifrices as described in said <27> or <28>.
<30> Drying time is preferably 10 minutes or more, more preferably 20 minutes or more, further preferably 30 minutes or more, preferably 24 hours or less, more preferably 10 hours or less, and even more preferably 3 hours or less. The method for producing a dentifrice granule according to any one of <27> to <29>.

<31> The water content in the dentifrice granules obtained is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2.5% by mass or less, and still more preferably 2% by mass or less. The method for producing a dentifrice granule according to any one of <1> to <30>, preferably 0.1% by mass or more, more preferably 0.2% by mass or more.
<32> In step 2, the temperature of the coating agent (D) when supplying the solid coating agent (D) at room temperature (20 ° C.) is preferably the melting point or more, more preferably 70 ° C. or more, and still more preferably. 80 degrees C or more, More preferably, it is 90 degrees C or more, Preferably it is 110 degrees C or less, More preferably, it is 105 degrees C or less, More preferably, it is 100 degrees C or less, Any one of said <1>-<31>. A method for producing dentifrice granules.
<33> The addition rate of the solid coating material (D) at normal temperature (20 ° C.) with respect to a total of 100 parts by mass of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is preferably 35 parts by mass / min. Or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less, still more preferably 5 parts by mass / min or less, still more preferably 3 parts by mass / min or less, preferably 2 parts by mass / min or more, more preferably 0.5 parts by mass / min or more, further preferably 1 part by mass / min or more, and still more preferably 1.5 parts by mass / min or more, <1> to <32> The manufacturing method of the granule for dentifrices in any one of.

<34> Dentifrice granules obtained by the production method according to any one of <1> to <33>.
<35> Granules containing one or more silicates (C) selected from water-soluble calcium salt (A), water-insoluble powder material (B), sodium silicate and potassium silicate, wherein the diameter is 0 A dentifrice in which the pore volume of 0.1 to 1 μm is preferably 0.1 ml / g or more, and a coating layer made of a solid coating agent (D) is formed on the surface of the granules at room temperature (20 ° C.) Granules for preparations.
<36> The dentifrice granule according to <34>, obtained by the production method according to any one of <1> to <33>.
<37> In the dentifrice granule, the content of the water-soluble calcium salt (A) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and still more preferably 7% by mass. % Or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 13% by mass or less, and still more preferably. The granule for dentifrice according to any one of <34> to <36>, which is 12% by mass or less, more preferably 10% by mass or less.
The content of the water-insoluble powder material (B) in the <38> dentifrice granule is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 92% by mass. % Or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less, and still more preferably 45% by mass or less. 34>-<37> The dentifrice granule in any one of.
<39> In the dentifrice granule, the content of silicate (C) (solid content) is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and still more preferably. 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, and still more. The granule for dentifrice according to any one of <34> to <38>, preferably 7% by mass or less, and more preferably 6% by mass or less.
In the granules for <40> dentifrice, the content of the coating agent (D) solid at normal temperature (20 ° C.) is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more. More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more, More preferably, it is 40 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% The dentifrice granule according to any one of <34> to <39>, which is the following.

The wet disintegration strength of <41> dentifrice granules is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more, and still more preferably 80% or more. The dentifrice granules according to any one of <34> to <40>, preferably 95% or less, more preferably 90% or less.
<42> The average particle size of the dentifrice granules is preferably 50 μm or more, more preferably 100 μm or more, still more preferably 150 μm or more, preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 350 μm or less, more The dentifrice granule according to any one of <34> to <41>, more preferably 300 μm or less.
<43> The volume of pores having a diameter of 0.1 to 1 μm contained in the dentifrice granule is 0.1 ml / g or more, preferably 0.2 ml / g or more, more preferably 0.3 ml / g or more, and more. More preferably, it is 0.4 ml / g or more, Preferably it is 1.0 ml / g or less, More preferably, it is 0.7 ml / g or less, More preferably, it is 0.6 ml / g or less, More preferably, it is 0.5 ml / g. The dentifrice granule according to any one of the above <34> to <42>.

<44> A dentifrice comprising the dentifrice granules according to any one of <34> to <43>.

  In the following Examples and Comparative Examples, “%” is “% by mass” unless otherwise specified. Each physical property value was measured by the following method.

(1) Solid content in an aqueous solution of silicate (C) Using a dropper, 2.5 g of a sample is placed on an aluminum 11.5 cm diameter container so that one drop becomes a droplet of about 5 to 10 mm in diameter (liquid Drops are sprayed onto the droplets so that they do not overlap as much as possible. Then, using an infrared moisture meter (FD240, manufactured by Kett Science Laboratory Co., Ltd.), the temperature is 105 ° C. and the conditions of Auto (measured value) in the moisture reference moisture measurement mode. The amount of volatilization was determined by measuring the amount of volatilized free water when the amount of change was within 0.05% within 30 seconds, and the measurement was terminated.

(2) Moisture content of granule 2 g of sample was uniformly sprayed on a container made of aluminum with a diameter of 11.5 cm, and then the volatilization free moisture content under the same conditions as the measurement of the solid content of (1) silicate (C). Was measured as the moisture content of the granules.

(3) Measuring method of average particle diameter of water-soluble calcium salt (A) and water-insoluble powder material (B) The average particle diameter of water-soluble calcium salt (A) and water-insoluble powder material (B) is a laser diffraction / scattering formula. It measured with the particle size distribution measuring apparatus (the product made by HORIBA, LA-920) on the conditions of solvent; ion-exchange water, refractive index; 1.2, circulation speed; 4, circulation time;

(4) Average droplet diameter of an aqueous solution of a silicate (C) and a melt of a coating material (D) solid at room temperature (20 ° C.) An aqueous solution of a silicate (C) and a coating agent solid at room temperature (20 ° C.) The average droplet diameter (median diameter) of the melt of (D) was measured using a laser diffraction type particle size distribution measuring apparatus (Malvern, Spray Tech). Specifically, a spray nozzle tip is installed at a location 30 cm away from the laser, and an aqueous solution of silicate (C) and normal temperature (20 ° C.) so that the laser penetrates the center of the spray droplet group perpendicular to the laser. ) Was sprayed with a melt of the solid coating agent (D), and the spraying was continued for 30 seconds for measurement.

(5) Average particle diameter and coarse particle ratio (2000 μm) of granules
Using sieves of 2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90, 63, 45 μm of JISZ8801-1 (established on May 20, 2000, final revised on November 20, 2006) Then, 50% average diameter was calculated for the under-sieving mass distribution by the sieving method, and this was used as the average particle diameter. Specifically, 2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90, 63 of JISZ8801-1 (enacted on May 20, 2000, final amendment on November 20, 2006), Using a 45 μm sieve, stack in order from a sieve with a small mesh on the tray, add 100 g of granules from the top of the top 2000 μm sieve, cover and a low-tap type sieve shaker (manufactured by HEIKO Seisakusho, tapping) 156 times / minute, rolling: 290 times / minute), and after shaking for 5 minutes, the mass of the granules remaining on each sieve and the saucer was measured, and the mass ratio of the granules on each sieve (% ) Was calculated. Next, the mass ratio of the granules remaining on the tray and the mass ratio of the granules on the sieve in order from the sieve with the smallest opening were integrated, and the particle diameter at which the total was 50% was defined as the average particle diameter. Moreover, the mass ratio of the particle | grains 2000 micrometers or more was computed and it was set as the coarse particle ratio. A lower crude yield means a higher yield as a toothpaste granule.

(6) Wet disintegration strength of granules The granules obtained by Examples and Comparative Examples were vibrated for 5 minutes using sieves of 500, 355, 250, 180, 150, 125, 90, 63, and 45 μm defined in JISZ8801-1. Then, granules having a particle size of 150 to 180 μm were used as initial samples. Next, 15 g of a stainless steel sphere (diameter 4 mm), 3 g of an initial sample, and 30 mL of ion-exchanged water are charged into a screw tube (manufactured by Maruemu Co., Ltd., No. 6), and the screw tube is inverted once and returned. It was. Then, it was left still for 30 minutes, and rotated for 2 minutes 30 seconds at 75 r / min with a tablet wear tester (manufactured by Higaki Medical Science Co., Ltd.).
The obtained granule sample was filtered through a 150 μm sieve, dried at 105 ° C. for 30 minutes, then cooled to room temperature (20 ° C.) with a desiccator, and the 150 μm sieve was made into a micro-type electromagnetic vibrator (manufactured by Tsutsui Riken Kikai Co., Ltd. The sample was shaken for 1 minute at a vibration intensity of 5.5 with a type electromagnetic vibration sieve, M-2), and then weighed. The value calculated by the following formula was defined as the wet disintegration strength.
Wet disintegration strength (%) = (granule mass remaining on 150 μm sieve ÷ initial sample mass) × 100

(7) Calcium ion elution rate 1 g of the granules obtained in Examples and Comparative Examples are put into a beaker containing 100 ml of ion-exchanged water. Subsequently, it stirred with the stirrer (Shinto Scientific Co., Ltd. three-one motor, rotation speed 30r / min), filtered after 10 minutes, and the calcium ion in a filtrate was quantified by the analytical curve method by ion chromatography. As the ion chromatograph, DX320 (equipped with EG40, separation column IonPac AS-16, guard column IonPac A0-70 mmol / L (0-20 min), suppressor ASRS (200 mA), conductivity detector)) was used as the ion chromatograph. Measurement was performed under the conditions of a column temperature of 30 ° C. and an eluent flow rate of 1.5 m / min. The calcium ion elution rate (%) was determined from the theoretical value of calcium ion blended in the granule and the value obtained by quantification. Granules with a lower calcium ion elution rate quantified by this method can suppress calcium ion elution from the granule before disintegration, and the storage stability of calcium ions in the granule when blended into a dentifrice is high. means.

(8) Fluorine adsorption (mineral supplementation or remineralization promoting effect on teeth)
The mineral replenishment or remineralization promoting effect on the teeth of the granules obtained in Examples and Comparative Examples was evaluated by the following method. 50 mg of granules obtained in Examples and Comparative Examples and NaF aqueous solution (fluorine ion concentration 1000 ppm) were placed on hydroxyapatite (HAP) pellets (PENTAX, trade name: APP-100) and brushed with a toothbrush for 20 seconds. . Thereafter, the HAP pellet was washed with ion-exchanged water. This HAP pellet was treated with 1N hydrochloric acid for 30 seconds to extract the adsorbed fluorine, and a fluorine ion electrode (ionplus-fluoride (manufactured by ORION)) was used and an ion analyzer (Expandable ion Analyzer EA940 (manufactured by ORION)) was used. The amount of fluorine adsorption was quantified. The granule collapses by brushing, and calcium ions are eluted in the NaF aqueous solution to form calcium fluoride, which is adsorbed on the HAP pellet. As the calcium ion elution amount increases, the fluorine adsorption amount determined by the present method increases. Granules with a higher amount of fluorine adsorbed by this method are more likely to disintegrate when used as a dentifrice, and calcium ions are eluted, increasing the mineral replenishment or remineralization promoting effect on the teeth. Means that.

(9) 0.1 to 1 μm pore volume measurement method Using mercury intrusion porosimeter (manufactured by micromeritics, AutoPoreIV 9500), sample weight 0.16 g, low pressure: Evacuation Pressure 50 mmHg (6.67 kPa), Evacuation Time 1 min , Mercury Filling Pressure 0.49 psia (3.38 kPa), Equilibration Time 5 sec, High pressure: Max Pressure 30144 psia (20784.88 kPa), Equilibration Time 5 sec.

Examples 1-4
(Process 1)
Calcium lactate (produced by Showa Kako Co., Ltd., average particle size of about 52 μm) and heavy calcium carbonate (produced by Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) with the blending ratio and conditions shown in Table 1 Are put into a 75 L drum granulator (φ40 cm × L60 cm) having a baffle plate, mixed for 10 minutes under the conditions of a drum rotation speed of 30 r / min, a fluid number of 0.2, and a drum angle of 12.6 °, and then mixed. Sodium silicate aqueous solution (manufactured by Fuji Chemical Industry Co., Ltd., trade name: No. 3 sodium silicate: Na ₂ O.3.2SiO ₂ aqueous solution, molar ratio: 3.2, solid content: 55.1%) Using one type two-fluid nozzle (manufactured by Atmax Co., Ltd.), the mixture was sprayed and granulated for the time shown in Table 1. The average droplet diameter (median diameter) at the time of spraying the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, the mixing was continued for 1 minute, and then the granules after Step 1 were discharged from the drum type granulator.
(Drying process)
The granules obtained in step 1 were dried at 105 ° C. for 120 minutes using an electric shelf dryer.
(Process 2)
Next, the dried granule is put into the drum type granulator, and mixed with candelilla wax (Yokoseki Oil & Fats Industry Co., Ltd.) while mixing under the conditions of a drum rotation speed of 30 r / min, a fluid number of 0.2, and a drum angle of 12.6 °. The time shown in Table 1 is obtained by using a single externally mixed two-fluid nozzle (manufactured by Atmax Co., Ltd.) with a melt of a product manufactured by Co., Ltd., trade name: refined candelilla wax MK-2, melting point 68-72 ° C. Were added by spraying to obtain granules whose surface was coated with candelilla wax. The average droplet diameter (median diameter) when spraying the melt of the candelilla wax was about 60 μm.
After spraying the melt of the candelilla wax, mixing was continued for 1 minute, and then the granules were discharged from the drum granulator. About the obtained granule, physical property evaluation was performed as mentioned above. The results are shown in Table 2.

Comparative Example 1
Granules were obtained in the same manner as in Example 1 except that Step 2 was not performed with the blending ratio and conditions shown in Table 1. The physical properties of the granules were evaluated as described above. The results are shown in Table 2.

Comparative Example 2
(Process 1)
Calcium lactate (produced by Showa Kako Co., Ltd., average particle size of about 52 μm) and heavy calcium carbonate (produced by Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) with the blending ratio and conditions shown in Table 1 Is added to a 2 L high-speed mixer (trade name: High Speed Mixer, manufactured by Fukae Powtech Co., Ltd.), mixed for 1 minute under the conditions of an agitator rotation speed of 850 r / min and a chopper rotation speed of 1350 r / min, and sodium silicate while continuing mixing. Aqueous solution (manufactured by Fuji Chemical Industry Co., Ltd., trade name: No. 3 sodium silicate, Na ₂ O · 3.2SiO ₂ aqueous solution, molar ratio: 3.2, solid content: 55.1%) was added dropwise using a dropper. Rolled and granulated. The average droplet diameter (median diameter) at the time of dropping the aqueous sodium silicate solution was about 500 μm.
After dropwise addition of the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the granules passed through Step 1 were discharged from the 2 L high-speed mixer.
(Drying process)
The granules obtained in step 1 were dried at 105 ° C. for 120 minutes using an electric shelf dryer.
(Process 2)
Next, the dried granules are put into the 2 L high-speed mixer and mixed under the conditions of an agitator rotational speed of 850 r / min and a chopper rotational speed of 1350 r / min, while a candelilla wax (manufactured by Yokoseki Oil & Fat Co., Ltd., trade name: Refinement) The melt of the candelilla wax MK-2) was added dropwise using a dropper to obtain granules whose surface was coated with the candelilla wax. The average droplet diameter (median diameter) when the melt of the candelilla wax was dropped was about 500 μm.
After dripping the melt of the candelilla wax, mixing was continued for 1 minute, and then the granules were discharged from the 2 L high-speed mixer. The obtained granules were evaluated for physical properties as described above. The results are shown in Table 2.

From the results shown in Table 2, the dentifrice granules of Examples 1 to 4 have high wet disintegration strength and the amount of fluorine adsorbed despite the relatively low calcium ion elution rate before granule disintegration. It can be seen that there is a high effect of calcium supplementation or remineralization on teeth after granule disintegration.
When Example 1 is compared with Example 2, in Example 2, since the amount of the component (D) is large, the elution rate of calcium ions before granule collapse is low, but the amount of fluorine adsorption after granule decay is also slightly reduced. .
When Example 1 is compared with Examples 3 and 4, in Examples 3 and 4, since the amount of component (D) is small, the elution rate of calcium ions before granule breakdown increases, but fluorine after granule collapse The amount of adsorption also increases.
Comparing Example 1 and Comparative Example 1, it can be seen that Example 1 has a slightly low fluorine adsorption amount after granule collapse, but the calcium ion elution rate before granule decay is considerably low.
When Example 1 and Comparative Example 2 are compared, the amount of component (D) is the same and the calcium ion elution rate before granule disintegration is almost the same, but Example 1 shows the amount of fluorine adsorption after granule disintegration. You can see that there are many.

Claims (8)

A method for producing a dentifrice granule having the following steps 1 and 2.
Step 1: Water-soluble calcium salt (A), water-insoluble powder material (B), and one or more silicates (C) selected from sodium silicate and potassium silicate using a container rotating granulator. It is a step of mixing and granulating, and at least the water-insoluble powder material (B) is supplied with an aqueous solution containing at least one silicate (C) selected from sodium silicate and potassium silicate as droplets and granulated. Step Step 2: Step of coating the granule surface by supplying a solid coating agent (D) to the granule obtained in Step 1 at room temperature (20 ° C.)   The method for producing a dentifrice granule according to claim 1, wherein the water-soluble calcium salt (A) is at least one selected from a water-soluble organic acid calcium salt and a water-soluble organic phosphate calcium salt.   The method for producing a dentifrice granule according to claim 1 or 2, wherein the water-insoluble powder material (B) is at least one selected from light calcium carbonate, heavy calcium carbonate, zeolite, and silica.   The manufacturing method of the granule for dentifrice in any one of Claims 1-3 which has a drying process between the process 1 and the process 2.   The mass ratio [(C) / {(A) + (B)}] of the silicate (C) to the total of the water-soluble calcium salt (A) and the water-insoluble powder material (B) is 0.05 or more, 0 The manufacturing method of the granule for dentifrice in any one of Claims 1-4 which is 0.5 or less.   Mass ratio of coating agent (D) solid at normal temperature (20 ° C.) to total of water-soluble calcium salt (A), water-insoluble powder material (B), and silicate (C) [(D) / {(A ) + (B) + (C)}] is 0.1 or more and 1.5 or less, the method for producing a dentifrice granule according to any one of claims 1 to 5.   The manufacturing method of the granule for dentifrice in any one of Claims 1-6 which supplies a coating material (D) using a multifluid nozzle in the process 2.   A granule containing at least one silicate (C) selected from a water-soluble calcium salt (A), a water-insoluble powder material (B), sodium silicate and potassium silicate, A dentifrice granule having a 1 μm pore volume of 0.1 ml / g or more and a coating layer of a solid coating agent (D) formed on the surface of the granule at room temperature (20 ° C.).