JP2015120686A - Dentifrice granules - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide dentifrice granules having excellent wet disintegration strength and excellent storage stability.SOLUTION: Dentifrice granules comprise one or more inorganic powder (A) selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide, water-insoluble powder material (B) excluding the inorganic powder (A), and one or more silicate (C) of sodium silicate and potassium silicate.

Description

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

For example, Patent Document 1 discloses dentifrice granules in which zeolite is bound with sodium silicate, which is a water-soluble binder, and has a certain size and strength by spray drying.
Patent Document 2 discloses a dentifrice composition containing a granular zeolite having an average particle size of 150 to 800 μm and an average disintegration strength of 15 to 100 g / piece, modified mint oil, etc. Disclosed is a product containing silicic anhydride and titanium oxide and prepared in a granular form by sintering.

JP 2013-147431 A JP 2008-266251 A

Conventionally, various water-soluble binders and water-insoluble binders have been used as granule binders. However, granules prepared using a water-soluble binder have no problem when used in a dry state. However, the strength of a dentifrice containing a large amount of water decreases, and during the process of mixing the dentifrice, Since the granules collapsed or the granules softened, it was difficult to feel in the oral cavity, and the presence of the granules was not sufficient.
On the other hand, although the zeolite granule which used sodium silicate as the binder like patent document 1 is described, it cannot be said that storage stability is enough.
As in Patent Document 2, when granulated zeolite is produced by a sintering method, it is difficult to adjust the disintegration strength of the granules.

The inventors include one or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide, a water-insoluble powder material (B) excluding the inorganic powder (A), and silicic acid. It has been found that dentifrice granules containing one or more silicates (C) of sodium and potassium silicate have excellent wet disintegration strength and storage stability.
That is, the present invention provides the following [1] to [4].

[1] One or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide, water-insoluble powder material (B) excluding the inorganic powder (A), and sodium silicate and silicic acid A dentifrice granule containing at least one silicate (C) of potassium.
[2] One or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide, water-insoluble powder material (B) excluding the inorganic powder (A), and sodium silicate and silicic acid Dentifrice granules containing at least one potassium silicate (C).
[3] A method for producing dentifrice granules in which the inorganic powder (A), the water-insoluble powder material (B) and the silicate (C) are mixed and granulated using a container rotating granulator. The aqueous solution of silicate (C) is supplied as droplets to the mixture containing the inorganic powder (A) and the water-insoluble powder material (B) using a multi-fluid nozzle, [1] or [2] The manufacturing method of the granule for dentifrice of description.
[4] A dentifrice containing the dentifrice granule according to [1] or [2] and a surfactant.

  ADVANTAGE OF THE INVENTION According to this invention, the granule for dentifrice which has the outstanding wet disintegration strength and storage stability, the manufacturing method of the said granule for dentifrice, and the dentifrice containing the said granule for dentifrice can be provided.

[Granule for dentifrice]
The granule for dentifrice of the present invention comprises at least one inorganic powder (A) selected from zinc oxide, calcium silicate, magnesium oxide and calcium hydroxide, and a water-insoluble powder material (B) excluding the inorganic powder (A). And a dentifrice granule containing or blending one or more silicates (C) of sodium silicate and potassium silicate.
Hereinafter, in this specification, the dentifrice granule “containing” the essential three components of the inorganic powder (A), the water-insoluble powder material (B) and the silicate (C) will be described. In the present specification, “containing” in the present specification can be read as “compounding”.

Sodium silicate and / or potassium silicate is a water-soluble inorganic binder, and dentifrice usually contains water, so it can be granulated by adding water-soluble sodium silicate and / or potassium silicate to an aqueous dentifrice. Usually, it is difficult to maintain the stability of granules in dentifrice.
However, the granule for dentifrice of the present invention has excellent wet disintegration strength and excellent storage stability, and can retain strength even in dentifrice.
The reason for this is considered that the granule for dentifrice of the present invention has a strong structure because the dehydrated sodium silicate and / or potassium silicate has a network structure through the inorganic powder (A) having a specific structure. .
Furthermore, it is considered that one or more inorganic powders selected from the group consisting of zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide act as a reinforcing agent for the water-soluble silicate network structure.
Hereinafter, each component used for the dentifrice granule of this invention is demonstrated one by one.

<Inorganic powder (A)>
The inorganic powder (A) used in the present invention is at least one selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide.
One or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide may be used alone or in combination.
Among these, zinc oxide is preferable from the viewpoint of improving storage stability.
The average particle diameter of the inorganic powder (A) depends on the type of the inorganic powder (A), but is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably from the viewpoint of improving storage stability. From the viewpoint of reducing the feeling of foreign matter, the upper limit is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 25 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.

<Water-insoluble powder material (B)>
The water-insoluble powder material (B) used in the present invention is a water-insoluble powder material excluding the inorganic powder (A) described above. As this water-insoluble powder material (B), those usually used for tooth abrasives are preferable, and specifically, inorganic materials are preferable. Here, “water-insoluble” means that the amount dissolved in 100 g of water (20 ° C.) is 1 g or less.

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, 1 type, or 2 or more types chosen from magnesium carbonate, titanium oxide, etc. are mentioned. These can be used alone or in combination of two or more.
Among these, from the viewpoint of physical properties and cost when granulated, one or more selected from light calcium carbonate, heavy calcium carbonate, zeolite, and silica are preferable. From light calcium carbonate and heavy calcium carbonate 1 type or 2 types selected are more preferable, and heavy calcium carbonate is still more preferable.
The water-insoluble powder material excludes one or more inorganic powders selected from the group consisting of zinc oxide, calcium silicate, magnesium oxide, and calcium hydroxide.
The average particle diameter 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, and still more preferably, from the viewpoint of removing dirt on the teeth after the granule disintegration. From the viewpoint of reducing the feeling of foreign matter, the upper limit is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 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.

<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 and storage stability to the granules. As will be described later, the wet disintegration strength of the granules is further improved by appropriately drying the granules as necessary. The silicate which is a water-soluble inorganic binder is a silicate having a dissolution amount (20 ° C.) in 100 g of water of 30 g or more, and the dissolution amount is preferably 50 g or more.

  The silicate (C) preferably contains sodium silicate from the viewpoint of improving wet disintegration strength and storage stability. The granule may contain a silicate other than the silicate (C). From the above viewpoint, the content of the silicate (C) in the silicate is preferably 95% by mass or more, more preferably 99% by mass. % Or more, more preferably 99.5% by mass or more, and still more preferably substantially 100%. From the same viewpoint, the content of sodium silicate in the 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 substantially 100%. .

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 the like. Of the hydrates.
Sodium silicate is generally represented by the molecular formula Na ₂ O.nSiO ₂ .mH ₂ O. The coefficient n (molecular ratio of SiO _{2 to} Na ₂ O) is called a molar ratio and can be expressed by the following formula (1).
Molar ratio = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × (Molecular weight of Na ₂ O / Molecular weight of SiO ₂ ) (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, still more preferably 3.0 or more, 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.

<Contents of components (A) to (C)>
The content of the inorganic powder (A) in the dentifrice granule is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5%, from the viewpoint of improving storage stability. It is at least mass%. From the viewpoint of cost and flavor, it is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably 1.5% by mass. It is as follows.

In the granule for dentifrice of the present invention, the content of the water-insoluble powder material (B) is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of improving wet disintegration strength, storage stability and polishing power. More preferably, it is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. From the viewpoint of suppressing damage to teeth, the upper limit is preferably 97% by mass or less, more Preferably it is 96 mass% or less, More preferably, it is 95 mass% or less.
From the viewpoint of improving storage stability, the mass ratio of the inorganic powder (A) / water-insoluble powder material (B) in the dentifrice granule is preferably 0.001 or more, more preferably 0.002 or more, and still more preferably. Is 0.005 or more, and from the viewpoint of cost and flavor, it is preferably 0.1 or less, more preferably 0.06 or less, still more preferably 0.03 or less, and even more preferably 0.02 or less. .

  In the dentifrice granule 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, from the viewpoint of improving wet disintegration strength and storage stability. More preferably 4% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, and from the viewpoint of increasing the yield, preferably 60% by mass or less, more preferably 50% by mass or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

  From the viewpoint of granulating the water-insoluble powder material (B) and enhancing the wet disintegration strength and storage stability, the mass ratio of the silicate (C) (solid content) to the water-insoluble powder material (B) (silicate (C) ( The solid content) / water-insoluble powder material (B)) is preferably 2/98 or more, more preferably 3/97 or more, still more preferably 4/96 or more, still more preferably 5/95 or more, and still more preferably. From the viewpoints of reducing coarse particles and increasing the plaque removal effect and improving the yield, the mass ratio is preferably 60/40 or less, more preferably 50/93 or more. 50 or less, more preferably 40/60 or less, even more preferably 30/70 or less, even more preferably 20/80 or less, and still more preferably 15/85 or less.

  The mass ratio of the inorganic powder (A) to the silicate (C) (solid content) (inorganic powder (A) / silicate (C) (solid content)) is preferably 0.01 from the viewpoint of enhancing storage stability. Above, more preferably 0.02 or more, still more preferably 0.05 or more, still more preferably 0.06 or more, still more preferably 0.08 or more, from the viewpoint of cost and flavor, preferably Is 1 or less, more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.2 or less, and even more preferably 0.15 or less.

  Further, from the viewpoint of enhancing the storage stability by strengthening the network structure of the silicate (C), the inorganic powder in the total amount of the inorganic powder (A), the water-insoluble powder material (B) and the silicate (C). The content of (A) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and even more. Preferably, it is 0.5% by mass or more, and from the viewpoint of cost and flavor, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and still more preferably 3% by mass. % Or less, even more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

  Further, from the viewpoint of improving wet disintegration strength and storage stability, the total amount of inorganic powder (A), water-insoluble powder material (B) and silicate (C) in the granule (solid content) is preferably 60. It is at least 80% by mass, more preferably at least 80% by mass, even more preferably at least 90% by mass, even more preferably at least 95% by mass, even more preferably at least 99% by mass, more preferably at least 100% by mass.

  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. Moreover, the amount of silicate is the amount of solid content calculated | required by the method of an Example description.

<Other ingredients>
As long as the object of the present invention is not impaired, the inorganic powder (A), the water-insoluble powder material (B) (abrasive), and the silicate (C) (binder) are used as necessary. Water-insoluble inorganic binders, water-insoluble organic binders, organic fibers, medicinal components, colorants and the like other than (A) can be blended.

  The content of the optional component is preferably 0 to 3 parts by mass, more preferably 0 to 2 parts by mass with respect to 100 parts by mass of the total amount of solids of the water-insoluble powder material and silicate, from the viewpoint of disintegration feel. More preferably, ˜1% by mass.

Examples of the fats and oils that can be used as the water-insoluble organic binder include higher fatty acids such as wax, paraffin, stearic acid, magnesium stearate, calcium stearate, and salts thereof.
Polymers and resins that can be used as water-insoluble organic binders include (i) polysaccharides such as xanthan gum, dextrin, gelatin, and derivatives thereof, (ii) rubber latex, (iii) acrylic acid, acrylic ester , Methacrylic acid, methacrylic acid ester, hydroxymethacrylic acid ester, styrene, vinyl acetate, vinyl pyrrolidone, maleic acid ester, methyl vinyl ether, α-olefin homopolymers, copolymers thereof and the like.
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 Antiperceptive 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 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 from the viewpoint of hardly feeling a foreign object, preferably 90% or less, More preferably, it is 80% or less.
Moreover, the preferable wet disintegration strength after a storage stability test is the same as the above.
Wet disintegration strength increases the content of silicate (C) (solid content), adjusts the content of inorganic powder (A), reduces the amount of water in the granule, water-insoluble powder material (B ) Can be enhanced by appropriately selecting the type.
The wet disintegration strength can be measured by the method described in the examples.

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. From the viewpoint of suppressing the above, it is preferably 500 μm or less, more preferably 350 μm or less, still more preferably 250 μm or less, and still more preferably 200 μm or less.
In addition, an average particle diameter can be measured by the method as described in an Example.
From the viewpoint of increasing wet disintegration strength, the pore volume of the dentifrice granule of the present invention is preferably 0.1 cc / g or more, more preferably 0.2 cc / g or more, and still more preferably. From the same viewpoint, it is preferably 0.7 cc / g or less, more preferably 0.6 cc / g or less, and still more preferably 0.5 cc / g or less. The volume of pores having a diameter of 0.1 to 1 μm can be increased by reducing the droplet diameter to the container rotating granulator or by reducing the fluid number of the container rotating granulator.

  Granules having the above average particle diameter, disintegration strength, and the like can be produced by appropriately changing the type, blending amount, and production conditions of silicate (C) (sodium silicate and / or potassium silicate). .

The granule for dentifrice of the present invention is preferably obtained by the production method described later.
As another production method, for example, after granulating the silicate, the water-insoluble powder material and the oil by rolling granulation or spray drying, granules are obtained by extracting the oil to a solvent and removing it. It is done.
In the dentifrice granule of the present invention, the dehydrated silicate solution acts as a binder for the water-insoluble powder material and is a granulated granule, but the dehydrated product is considered to be partially condensed.

[Method for producing granules for dentifrice]
Examples of the production method of the present invention include the following production method 1 or production method 2.
<Manufacturing method 1>
The inorganic powder (A), the water-insoluble powder material (B) excluding the inorganic powder (A) and the silicate (C) are mixed and granulated using a container rotary granulator. A manufacturing method for supplying an aqueous solution of silicate (C) as droplets to a mixture containing the inorganic powder (A) and the water-insoluble powder material (B) using a multi-fluid nozzle. .
In general, according to the granulation method using a container rotating granulator, it is possible to make the powder flow uniformly, and further, by the mixing mechanism involving lifting of particles by rotation and sliding and dropping by its own weight, The shear force applied to the powder is suppressed. Therefore, it can be said that the granulation method using the container rotating granulator is a non-consolidated granulation method.
Here, the silicate is a water-soluble inorganic binder, and the dentifrice usually contains moisture, so even if it is granulated by adding a water-soluble silicate to the aqueous dentifrice, usually in the dentifrice, It is difficult to maintain the stability of the granules.
However, the dentifrice granules obtained in the present invention have excellent wet disintegration strength. This is because the dentifrice granule of the present invention is a granulated product obtained by a non-consolidated manufacturing method and is porous, so that the aqueous solution of silicate present inside the granule is easily dried, This is probably because the salt dehydrated product has a network structure, and the granules are strengthened.
In the present invention, after the inorganic powder (A) and the water-insoluble powder material (B) are premixed, the silicate (C) is supplied as aqueous solution droplets to the premix using a multi-fluid nozzle. Since the inorganic powder (A) is uniformly dispersed, it is preferable from the viewpoint of storage stability.

The preferable ranges of the average particle diameter of the inorganic powder (A) that is the raw material of the dentifrice granules and the average particle diameter of the water-insoluble powder material (B) that is the raw material of the dentifrice granules are as described above.
In the production method of the present invention, the inorganic powder (A), the water-insoluble powder material (B), and the silicate (C) are contained in the toothpaste granule according to the present invention, and the inorganic powder (A ) / Water-insoluble powder material (B), inorganic powder (A) / silicate (C), silicate (C) / water-insoluble powder material (B) are preferably added so as to have the above-mentioned mass ratios. The preferred range is also the same.

<Container rotating granulator>
In the present invention, it is preferable to use a container rotating granulator so that the granules are not subjected to compaction by giving a strong shear during the production of the granules.
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.
In addition, the wall friction coefficient between the powder (mixture) containing the inorganic powder (A) and the water-insoluble powder material (B) and the inner wall of the container rotary granulator is small, and the powder has sufficient ascending kinetic force. When it is difficult to add, it is preferable to provide a plurality of baffles (baffles) on the inner wall of the container to assist mixing. 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 condition of the container rotating granulator is not particularly limited as long as the powder containing the inorganic powder (A) and the water-insoluble powder material (B) in the granulator can be flowed as uniformly as possible and stirred. From the viewpoint of obtaining granules having good disintegration strength and the like, the fluid number defined by the following formula (1) is preferably 0.005 or more, more preferably 0.01 or more, and 0.05 or more. From the viewpoint of obtaining non-consolidated granules, the upper limit is preferably 1.0 or less, more preferably 0.6 or less, and further preferably 0.4 or less. preferable.

The preferred fluid number is the same in the premixing. The operation time for the premixing is preferably 5 minutes or more, more preferably 7 minutes or more, still more preferably 10 minutes or more, and preferably 90 minutes or less, more preferably 60 minutes or less.
Fluid number: Fr = V ² / (R × g) (1)
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 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 value of the main shaft, and in the bread granulator equipped with the crushing blade, V and R use the value of the crushing blade.

<Multi-fluid nozzle>
In the present invention, an aqueous solution of silicate (C) is supplied using a multi-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 channel to the vicinity of the nozzle tip. Examples include fluid nozzles. Moreover, the mixing part of the silicate (C) aqueous solution and the atomizing gas may be either an internal mixing type for mixing inside the nozzle tip or an external mixing type for mixing outside the nozzle tip.
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.

Moreover, the droplet diameter of the aqueous solution of silicate (C) can be adjusted to a desired range by adjusting the balance between the flow rate of the aqueous solution of silicate (C) and the flow rate of the atomizing gas. That is, in order to reduce the droplet diameter, the flow rate of the atomizing gas may be increased with respect to the silicate (C) aqueous solution having a constant flow rate. What is necessary is just to reduce the flow volume of salt (C) aqueous solution.
For example, when a two-fluid nozzle is used, it is easy to adjust the flow rate of the atomizing gas by adjusting the atomizing pressure of the atomizing gas. The atomizing gas spray pressure is preferably 0.05 MPa or more from the viewpoint of liquid dispersion, more preferably 0.1 MPa or more, still more preferably 0.15 MPa or more, and preferably 1.0 MPa or less from the viewpoint of equipment load. Preferably it is 0.5 MPa or less, More preferably, it is 0.3 MPa or less. Moreover, there is no restriction | limiting in particular as spray pressure of silicate (C) aqueous solution, However, From a viewpoint of equipment load, 1.0 MPa or less is preferable, for example.

  As a result of examining the influence of the difference in the droplet size of the silicate (C) aqueous solution on the yield and coarse particle ratio of the resulting granule, the wet disintegration strength was increased and a granule with a suitable particle size as a dentifrice granule was obtained. From the viewpoint of obtaining a good yield, the average particle diameter of the droplet size of the silicate (C) aqueous solution is preferably 210 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, and even more preferably 80 μm or less. From the viewpoint of productivity, it is 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 even more preferably 50 μm or more.

The smaller the droplet diameter, the lower the flow rate of the aqueous silicate (C) solution and the lower the productivity. For example, by using multiple multi-fluid nozzles and reducing the flow rate per nozzle, droplets can be made finer. The rate of addition can be increased while maintaining One or more multi-fluid nozzles may be used, but 2 to 20 nozzles may be used.
In addition, the average particle diameter of the droplet diameter of the silicate (C) aqueous solution is calculated on a volume basis, and is measured using, for example, a laser diffraction type particle size distribution measuring device (Malburn, Spraytec). Value. Specifically, it can be measured by the method described in the examples.

Silicate (C) (solid content) in silicate (C) aqueous solution supplied as droplets granulates powder containing inorganic powder (A) and water-insoluble powder material (B) as water-soluble inorganic binder From the viewpoint of making it preferable, it is 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 suppressing and increasing 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 silicate (C) aqueous solution can be calculated | required by the method of an Example description.
In addition, the silicate (C) aqueous solution may contain a polymer, inorganic particles, or the like, or may contain a lower alcohol having 1 to 3 carbon atoms, as long as the present invention is not inhibited.

The temperature of the aqueous solution of silicate (C) when the aqueous solution of silicate (C) is supplied using a multi-fluid nozzle is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of spray stability. In addition, it is preferably 50 ° C. or lower, more preferably 30 ° C. or lower.
The addition rate of the aqueous solution of silicate (C) is preferably 35 masses with respect to 100 mass parts of the water-insoluble powder material (B) from the viewpoint of suppressing the formation of coarse particles and imparting excellent wet disintegration strength. Part / min or less, more preferably 20 parts by mass / min or less, further preferably 10 parts by mass / min or less, still more preferably 3 parts by mass / min or less, and the lower limit thereof is preferably 0.2 parts by mass / min. As mentioned above, More preferably, it is 0.5 mass part / min or more, More preferably, it is 1 mass part / min or more, More preferably, it is 1.5 mass part / min or more. The above range is suitable when using sodium silicate No. 1, 2 or 3 described in JIS K1408.

<Manufacturing method 2>
In the production method, the inorganic powder (A), the water-insoluble powder material (B) excluding the inorganic powder (A), and the silicate (C) are stirred and mixed using a stirring granulator having a stirring blade to obtain granules. is there.
In the present invention, after the inorganic powder (A) and the water-insoluble powder material (B) are premixed, the silicate (C) is supplied as aqueous solution droplets to the premix using a short tube nozzle or the like. In view of storage stability, the inorganic powder (A) is preferably dispersed uniformly.

The preferable ranges of the average particle diameter of the inorganic powder (A) that is the raw material of the dentifrice granules and the average particle diameter of the water-insoluble powder material (B) that is the raw material of the dentifrice granules are as described above.
In the production method of the present invention, the inorganic powder (A), the water-insoluble powder material (B), and the silicate (C) are contained in the content or blended amount in the dentifrice granules of the present invention, and the inorganic powder ( A) / water-insoluble powder material (B), inorganic powder (A) / silicate (C), silicate (C) / water-insoluble powder material (B) may be added so as to have the above-mentioned mass ratios. The preferred range is also the same.

As an agitation granulator having an agitating blade preferably used in the present invention, the tip of a rotating shaft that is rotationally driven by a driving means is made to penetrate the wall of the agitating tank and protrude into the agitating tank, and the protruding of the rotating shaft An agitation granulator constructed by attaching an agitating blade to the tip is preferred. As the agitation granulator, either a batch type or a continuous type can be used.
Commercially available batch-type granulators include Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), high speed mixer (manufactured by Earth Technica Co., Ltd.), vertical granulator (manufactured by Paulek, Inc.), Redige mixer (Matsusaka Giken Co., Ltd.) Company-made), Pro-share mixer (made by Taiheiyo Kiko Co., Ltd.) Among these, a stirring granulator having a crushing blade (chopper blade) in addition to the stirring blade (main blade) is more preferable.

Examples of the stirring granulator having a crushing blade include the following (i) to (iii).
(I) The rotating shaft protrudes into the stirring tank from the bottom wall of the substantially cylindrical stirring tank, the stirring blade is attached to the tip of the rotating shaft, and the chopper shaft protrudes horizontally from the lower half peripheral wall of the stirring tank. A mechanical stirring granulator with a chopper blade attached to the tip of the chopper shaft.
(ii) The chopper shaft is supported in a state where both ends are supported between the lower half peripheral walls from which the central mounting portion of the stirring blade is removed, the inner blade is fixed to the chopper shaft in the inner region of the stirring tank, and the chopper is placed on one side of the chopper shaft. A mechanical stirring granulator provided with a driving means for rotating the shaft.
(iii) An outer blade driven by a short-axis chopper shaft projecting from the lower half peripheral wall of the stirring tank toward the center of the stirring tank to the outer region of the stirring tank, and the stirring tank from the lower half peripheral wall of the stirring tank A mechanical stirring granulator provided with an inner blade that is driven to rotate by a long-axis chopper shaft that protrudes toward the inner region of the stirring tank toward the center.
The stirring blades of the mechanical stirring granulators (i) to (iii) are preferably provided with a flip-up surface that is inclined so that the water-insoluble powder material jumps up by the rotation of the rotating blades.

Among the agitation granulators having the above-mentioned crushing blades, Redige mixer (Matsuzaka Giken Co., Ltd., granulator using a special ski shovel, chopper blades can be installed), high speed mixer (Made by Earth Technica Co., Ltd.) , Granulating machine using a combination of rolling action by agitator and crushing function by chopper), and pro-shear mixer (manufactured by Taiheiyo Kiko Co., Ltd., floating diffusion mixing with uniquely shaped shovel blades and high-speed shear dispersion by multistage chopper blades One type or two or more types selected from granulators having two functions are more preferable.
As continuous granulators, continuous ladige mixers (medium speed mixers: relatively long residence time), CB recyclers (manufactured by Loedige) with relatively short residence times as high speed mixers, turbulizers (Hosokawa Micron Corporation) 1 type or 2 types or more selected from a company-made), Shugi mixer (manufactured by Powrec Co., Ltd.), a flow jet mixer (manufactured by Powder Research Powtex Co., Ltd.) and the like.
The granulator used in the present invention preferably forms an average clearance of 1 to 50 mm between the stirring blade and the wall surface of the stirring tank when the stirring blade rotates.

The peripheral speed of the tip of the agitation blade (main wing) of the granulator in the agitation granulation is preferably 1 m / s or more, more preferably 2 m / s or more, and even more preferably 5 m / s from the viewpoint of agglomerating the water-insoluble powder material. From the viewpoint of reducing the consolidation and increasing the wet disintegration strength, it is preferably 20 m / s or less, more preferably 10 m / s or less. By granulating at such a peripheral speed, the granulated dentifrice granules have moderate voids, and compaction is reduced and at the same time sufficient aggregation and sizing of the water-insoluble powder material can be achieved. A dentifrice granule having performance can be obtained.
The peripheral speed at the tip of the stirring blade means the moving speed (tip speed) of the tip of the stirring blade and is calculated by the following formula (I).
Stirring blade tip peripheral speed [m / s] = stirring blade diameter [m] × circumferential rate × rotational speed [1 / s] (I)
Moreover, when performing agitation granulation with the granulator provided with the crushing blade in addition to the stirring blade, the crushing blade may be used. The peripheral speed at the tip of the crushing blade is preferably 0.1 m / s or more, more preferably 0.2 m / s or more, more preferably 0.3 m / s or more from the viewpoint of reducing consolidation and increasing wet disintegration strength. And preferably 10 m / s or less, more preferably 1 m / s or less, and still more preferably 0.8 m / s or less.
The peripheral speed at the tip of the crushing blade is calculated by replacing the stirring blade with the crushing blade in the above formula (I).

  As a result of examining the influence of the difference in the droplet size of the silicate (C) aqueous solution on the yield and coarse particle ratio of the resulting granule, the wet disintegration strength was increased and a granule with a suitable particle size as a dentifrice granule was obtained. From the viewpoint of obtaining a good yield, the average particle diameter of the silicate (C) aqueous solution is preferably 10,000 μm or less, more preferably 8000 μm or less, still more preferably 6000 μm or less, and even more preferably 5000 μm or less. From the viewpoint of productivity, it is preferably 1 μm or more, more preferably 10 μm or more, still more preferably 100 μm or more, still more preferably 1000 μm or more, and even more preferably 2000 μm or more. Although the droplet diameter is larger than that of production method 1, in production method 2, the silicate (C) aqueous solution is dispersed by the rotational motion of the stirring blades and crushing blades, so that granules having a suitable particle size can be obtained.

The smaller the droplet diameter, the lower the flow rate of the aqueous silicate (C) solution and the lower the productivity. For example, by using multiple nozzles and reducing the flow rate per nozzle, maintaining finer droplets However, the addition rate can be increased. One or more nozzles may be used, but 2 to 20 nozzles may be used.
In addition, the average particle diameter of the droplet diameter of the silicate (C) aqueous solution in the production method 2 is a value measured by, for example, photographing a droplet with a scale. Specifically, it can be measured by the method described in the examples.

Silicate (C) (solid content) in silicate (C) aqueous solution supplied as droplets granulates powder containing inorganic powder (A) and water-insoluble powder material (B) as water-soluble inorganic binder From the viewpoint of making it preferable, it is 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 suppressing and increasing 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 silicate (C) aqueous solution can be calculated | required by the method of an Example description.
In addition, the silicate (C) aqueous solution may contain a polymer, inorganic particles, or the like, or may contain a lower alcohol having 1 to 3 carbon atoms, as long as the present invention is not inhibited.

The temperature of the aqueous solution of the silicate (C) when supplying the aqueous solution of the silicate (C) using a nozzle is preferably 5 ° C or higher, more preferably 10 ° C or higher, from the viewpoint of spray stability. Moreover, Preferably it is 50 degrees C or less, More preferably, it is 30 degrees C or less.
The addition rate of the aqueous solution of silicate (C) is preferably 35 masses with respect to 100 mass parts of the water-insoluble powder material (B) from the viewpoint of suppressing the formation of coarse particles and imparting excellent wet disintegration strength. Parts / min or less, more preferably 20 parts by mass / min or less, further preferably 15 parts by mass / min or less, still more preferably 10 parts by mass / min or less, and the lower limit thereof is preferably 0.5 parts by mass / min. As mentioned above, More preferably, it is 1 mass part / min or more, More preferably, it is 3 mass part / min or more, More preferably, it is 5 mass part / min or more. The above range is suitable when using sodium silicate No. 1, 2 or 3 described in JIS K1408.

(Dry)
In the present invention, it is preferable to further dry the obtained granules from the viewpoint of improving wet disintegration strength and storage stability. By using the silicate (C), which is a water-soluble binder, by performing a drying operation, it is confirmed that the wet disintegration strength of the granules is 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, examples include a method of drying with an electric shelf dryer or a hot air dryer, a method of drying in a batch type fluidized bed, and the continuous type includes a fluidized bed, a rotary dryer, a steam tube dryer, and the like. It is done.

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 a heat load, 200 degrees C or less is preferable, 150 degrees C or less is more preferable, and 110 degrees C or less is still more preferable.
The drying time varies depending on the effective amount and amount of the silicate aqueous solution 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 usually 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 20 hours or less, still more preferably 3 hours or less. is there. In the case of electrodrying, it is preferably 20 minutes or longer, more preferably 30 minutes or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter. In the case of fluidized bed drying, it is preferably 10 minutes or more, more preferably 20 minutes or more, and preferably 5 hours or less, more preferably 2 hours or less.

  The water content in the resulting granules is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of increasing wet disintegration strength. From the viewpoint of productivity, it is preferably 0.1% by mass or more, and preferably 0.2% by mass or more. The amount of water in the granules can be determined by the method described in the examples. Although the wet disintegration strength depends on the type of the water-insoluble powder material, the wet disintegration strength is higher for the same type when the water content is smaller.

[Dentifrice]
The dentifrice of the present invention contains the above-mentioned dentifrice granules and a surfactant. By containing the dentifrice granule together with a surfactant, it can provide good foaming and can sufficiently remove plaque or dirt even in a narrow area such as a gap between teeth. In combination with the surfactant, the cleaning effect can be enhanced, and the feeling of use can be enhanced by giving a feeling of slipping on the tooth surface in the oral cavity after using the dentifrice of the present invention. Here, the smooth touch means that when the tooth surface is touched with the tongue, it is possible to smoothly slide the tongue on the surface of the tooth without obtaining a touch of plaque or dirt. Say the touch.

<Granule for dentifrice>
The content of the dentifrice granule is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 3% by mass or more in the dentifrice of the present invention, from the viewpoint of enhancing the plaque or dirt removal effect and improving the feeling of use. Preferably it is 5 mass% or more. The content of the dentifrice granule is preferably 50% by mass in the dentifrice of the present invention from the viewpoint of exerting the plaque or dirt removing effect without feeling a foreign body and without damaging the tooth enamel. Or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

<Surfactant>
As the surfactant, one or more selected from anionic surfactants, nonionic surfactants, and zwitterionic surfactants can be used. Examples of such an anionic surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; N-acyl sarcosine salts such as sodium N-lauroyl sarcosine and sodium N-myristoyl sarcosine; N-palmitoyl glutamic acid. Examples thereof include N-acyl glutamate such as sodium, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate, sodium dioctyl sulfosuccinate and the like.

  Nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid esters; sugar alcohol fatty acid esters such as maltitol fatty acid esters and lactitol fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate Oxyethylene sorbitan fatty acid ester; fatty acid mono or diethanolamide such as lauric acid mono or diethanolamide, myristic acid mono or diethanolamide; sorbitan fatty acid ester, fatty acid monoglyceride, polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene copolymer Etc.

  As the zwitterionic surfactant, N-alkyldiaminoethylglycine such as N-lauryldiaminoethylglycine, N-myristyldiaminoethylglycine, N-alkyl-N-carboxymethylammonium betaine, 2-alkyl-1-hydroxyethylimidazoline Betaine sodium or the like is used.

  As the surfactant, anionic surfactants are more preferable, alkyl sulfates are more preferable, and sodium lauryl sulfate is even more preferable from the viewpoint of providing good foaming properties and feeling of use.

The content of the surfactant is preferably 0.2% by mass or more in the dentifrice of the present invention from the viewpoint of providing a good flavor while ensuring good foaming and enhancing the cleaning effect and feeling of use. Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. In addition, the content of the surfactant is preferably 2.0% by mass or less, more preferably 1.7% by mass or less, and further preferably from the viewpoint of suppressing the loss of flavor in the dentifrice of the present invention. Is 1.5 mass% or less.
The content ratio of dentifrice granules and surfactant in the dentifrice of the present invention (dentifrice granules / surfactant content) is preferably 0.5 or more, more preferably 2 or more, and still more preferably. 4 or more, preferably 250 or less, more preferably 100 or less, still more preferably 40 or less, and still more preferably 30 or less.

<Other ingredients>
The dentifrice of the present invention may further contain a binder. As the binder, one or more selected from sodium carboxymethyl cellulose, sodium polyacrylate, hydroxyethyl cellulose, thickening silica, montmorillonite, carrageenan, sodium alginate, guar gum, and pectin are preferably used. Among these, sodium carboxymethylcellulose is more preferable.

  The content of the binder in the dentifrice of the present invention is such that the above-mentioned granule for dentifrice and the surfactant are effectively diffused in the oral cavity, and the plaque or dirt removing effect is effectively exhibited, and the feeling of slipperiness and dirt In the dentifrice of the present invention, it is possible to improve the feeling of falling, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.7% in the dentifrice of the present invention. It is at least 5% by mass, preferably at most 5% by mass, more preferably at most 3% by mass, still more preferably at most 2.5% by mass.

  The content ratio of dentifrice granules and binder in the dentifrice of the present invention (dentifrice granules / binder content) effectively diffuses the dentifrice granules in the oral cavity, From the viewpoint of effectively exhibiting the dirt removing effect, improving the smooth feeling and the feeling of removing dirt, and providing good foaming, it is preferably 0.2 or more, more preferably 1 or more, still more preferably 2.5 or more. Moreover, it is preferably 500 or less, more preferably 60 or less, and still more preferably 30 or less.

  The dentifrice of the present invention may further contain a wetting agent. Examples of the wetting agent include sorbit, glycerin, propylene glycol, 1,3 butylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, xylitol, maltite, lactit, erythritol and the like. These may be used alone or in combination of two or more. Among these, at least one of sorbit and polyethylene glycol is preferable, and two of them are more preferable.

  The content of the wetting agent in the dentifrice of the present invention is such that it effectively diffuses in the oral cavity while dissolving or dispersing the dentifrice granules and surfactant, effectively exerting plaque or dirt removal effect, and good foaming In the dentifrice of the present invention, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 70% by mass or less, more preferably 60% by mass. % Or less, more preferably 50% by mass or less.

  The dentifrice of the present invention may further contain water. The content of water in the dentifrice of the present invention is effectively diffused in the oral cavity while dissolving or dispersing the dentifrice granules and surfactant, effectively exerting plaque or dirt removal effect, and the number of strokes during brushing In the dentifrice of the present invention, it is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass, from the viewpoint of exhibiting high dirt removing ability even at an early stage with a small amount of It is above, Preferably it is 50 mass% or less, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

  In addition, although this moisture content can also be calculated by calculation from the mix | blended moisture content and the moisture content in the mix | blended component, it can measure with a Karl Fischer moisture meter, for example. As the Karl Fischer moisture meter, for example, a trace moisture measuring device (Hiranuma Sangyo Co., Ltd.) can be used. In this apparatus, 5 g of dentifrice is taken and suspended in 25 g of anhydrous methanol, and 0.02 g of this suspension is fractionated and the amount of water can be measured. The content ratio of dentifrice granules and water in the dentifrice of the present invention (dentifrice granules / water content) is from the viewpoint of providing good solubility and dispersibility, and plaque or dirt removal ability. Preferably it is 0.02 or more, More preferably, it is 0.1 or more, More preferably, it is 0.2 or more, Preferably it is 15 or less, More preferably, it is 6 or less, More preferably, it is 5 or less.

The dentifrice of the present invention contains components other than those described above, such as abrasives, excipients, sweeteners, preservatives, fragrances, medicinal ingredients, colorants, bactericides, and other commonly used ingredients. Can do.
The other components described above may be used alone or in combination of two or more. In addition, the dentifrice of this invention can be manufactured by a conventional method using the said component.

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 of silicate Using a dropper, 2.5 g of a sample is placed on an aluminum 11.5 cm diameter container so that one drop is about 5 to 10 mm in diameter (droplets do not overlap as much as possible) And after that, using an infrared moisture meter (FD240, manufactured by Kett Science Laboratory Co., Ltd.), in a moisture reference moisture measurement mode, the temperature is 105 ° C. and the Auto condition (change in measured value is 30). It was calculated by removing the volatilized free water measured at the time when it was within 0.05% in the second as the final measured value and the measurement was completed.
(2) Moisture content of granules 2 g of a sample was uniformly sprayed on an aluminum 11.5 cm diameter container, and then measured under the same conditions as described above.

(3) Average droplet diameter of silicate aqueous solution <Measurement method of droplet diameter in production method 1 (Examples 1 to 4 and Comparative Examples 1 to 2)>
The average droplet diameter (volume average particle diameter) of the silicate aqueous solution was measured using a laser diffraction particle size distribution measuring apparatus (Malburn, Spraytec). Specifically, the tip of the spray nozzle is installed at a location 30 cm away from the laser, the silicate aqueous solution is sprayed so that the laser penetrates the center of the spray droplet group perpendicular to the laser, and spraying is continued for 30 seconds. And measured.
<Measurement Method of Droplet Diameter in Production Method 2 (Examples 5 to 6 and Comparative Example 3)>
The average droplet diameter of the sodium silicate aqueous solution was obtained by taking a photograph of the droplet of the sodium silicate aqueous solution together with the scale and measuring the droplet diameter from the scale reading. This was performed for 10 droplets, and the average value was taken as the average droplet diameter.
(4) Measuring method of average particle diameter of water-insoluble powder The average particle diameter of water-insoluble powder was measured with a laser diffraction / scattering particle size distribution measuring apparatus (LA-920, manufactured by HORIBA), solvent: ion-exchanged water, refractive index. : Measured under the conditions of 1.2, circulation rate 4 and circulation 3 min.

(5) Average particle diameter of granules 2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90 of JISZ8801-1 (established on May 20, 2000, final revised on November 20, 2006) , 63, and 45 μm, and 50% average diameter is calculated for the mass distribution under the sieve according to the sieving method, and this is 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 (% ) Is calculated. The mass ratio of the granules on the sieve with small openings is accumulated in order from the saucer, and the particle diameter at which the total becomes 50% is taken as the average particle diameter.

(6) Wet disintegration strength before storage of granule First, the granules obtained by Examples and Comparative Examples were sieved with 500, 355, 250, 180, 150, 125, 90, 63, and 45 μm sieves defined in JISZ8801-1. After being used and vibrated for 5 minutes, 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 is filtered through a 150 μm sieve, dried at 105 ° C. for 30 minutes, and then cooled to room temperature with a desiccator. The 150 μm sieve is made into a micro-type electromagnetic vibrator (manufactured by Tsutsui Riken Kikai Co., Ltd. And shaked for 1 minute at a vibration intensity of 5.5 in a container, 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) Wet disintegration strength after storage of granule Wet after storage of granule in the same manner as in (7) above, except that the screw tube was inverted once and returned to its original state, and then allowed to stand for 24 hours. The collapse strength was measured.

(8) Storage stability Using the values obtained in (6) and (7) above, the value calculated by the following formula was defined as storage stability.
Storage stability = (wet disintegration strength after storage of granules) / (wet disintegration strength before storage of granules) × 100

(9) 0.1 to 1 μm pore volume measurement method Using a mercury intrusion porosimeter (manufactured by Micromeritics, AutoPoreIV 9500), sample weight 0.16 g, low pressure: Evacuation Pressure 50 mmHg, Evacuation Time 1 min, Mercury Filling Pressure 0 .49 psia, Equilibration Time 5 sec, High Pressure: Equilibration Time 5 sec.

<Manufacturing method 1 (Examples 1-4 and Comparative Examples 1-2)>
Example 1
In the blending ratio shown in Table 1, heavy calcium carbonate (produced by Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) and zinc oxide (made by Sakai Chemical Industry Co., Ltd., trade name: fine zinc oxide, average) The particle size of about 0.3 μm) was put into a 75 L drum granulator (φ40 cm × L60 cm) having a baffle plate, and the drum rotation speed was 30 r. p. m, mixed with a fluid number of 0.2 and a drum angle of 12.6 °, 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, mol Ratio: 3.2, solid content: 55.1%) was sprayed and granulated using one external mixing type two-fluid nozzle (manufactured by Atmax Co., Ltd.). The batch size is 8 kg. The median diameter of the spray droplet diameter of the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the mixture was discharged from the drum granulator and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Example 2
Heavy calcium carbonate (produced by Calfine Co., Ltd., trade name: Christon SS, average particle size of about 5 μm) and calcium silicate (produced by Tomita Seiyaku Co., Ltd., trade name: Florite R, average grain size) shown in Table 1 About 25 μm in diameter) was put into a 75 L drum granulator (φ40 cm × L60 cm) having a baffle plate, and the drum rotation speed was 30 r. p. m, mixed with a fluid number of 0.2 and a drum angle of 12.6 °, 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, mol Ratio: 3.2, solid content: 55.1%) was sprayed and granulated using one external mixing type two-fluid nozzle (manufactured by Atmax Co., Ltd.). The batch size is 8 kg. The median diameter of the spray droplet diameter of the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the mixture was discharged from the drum granulator and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Example 3
Heavy calcium carbonate (product name: Kriston SS, average particle size of about 5 μm) and calcium hydroxide (made by Junsei Chemical Co., Ltd., product name: calcium hydroxide, mortar) with the mixing ratio shown in Table 1 ) And adjusted to an average particle size of 20 μm) is put into a 75 L drum granulator (φ40 cm × L60 cm) having a baffle plate, and the drum rotation speed is 30 r. p. m, mixed with a fluid number of 0.2 and a drum angle of 12.6 °, 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, mol Ratio: 3.2, solid content: 55.1%) was sprayed and granulated using one external mixing type two-fluid nozzle (manufactured by Atmax Co., Ltd.). The batch size is 8 kg. The median diameter of the spray droplet diameter of the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the mixture was discharged from the drum granulator and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Example 4
Heavy calcium carbonate (produced by Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) and magnesium oxide (produced by Junsei Chemical Co., Ltd., trade name: magnesium oxide, pulverized in a mortar at the blending ratio shown in Table 1 And adjusted to an average particle size of 20 μm) into a 75 L drum granulator (φ40 cm × L60 cm) having a baffle, and the drum rotation speed is 30 r. p. m, mixed with a fluid number of 0.2 and a drum angle of 12.6 °, 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, mol Ratio: 3.2, solid content: 55.1%) was sprayed and granulated using one external mixing type two-fluid nozzle (manufactured by Atmax Co., Ltd.). The batch size is 8 kg. The median diameter of the spray droplet diameter of the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the mixture was discharged from the drum granulator and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Comparative Examples 1-2
Heavy calcium carbonate (Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) is added to a 75 L drum granulator (φ40 cm × L60 cm) having a baffle at the mixing ratio shown in Table 1. Drum rotation speed 30r. p. m, mixed with a fluid number of 0.2 and a drum angle of 12.6 °, sodium silicate aqueous solution (manufactured by Fuji Chemical Industry Co., Ltd., trade name: No. 3 sodium silicate: Na ₂ O.3SiO ₂ aqueous solution, molar ratio: 3.2, solid content: 55.1%) was sprayed and granulated using one external mixing type two-fluid nozzle (manufactured by Atmax Co., Ltd.). The batch size is 8 kg. The median diameter of the spray droplet diameter of the sodium silicate aqueous solution was about 60 μm.
After spraying the sodium silicate aqueous solution, mixing was continued for 1 minute, and then the mixture was discharged from the drum granulator and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

<Production Method 2 (Examples 5 to 6 and Comparative Example 3)>
Example 5
In the blending ratio shown in Table 2, heavy calcium carbonate (product of Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) and zinc oxide (product of Sakai Chemical Industry Co., Ltd., trade name: fine zinc oxide, average) Sodium silicate aqueous solution while mixing under conditions of agitator peripheral speed 7m / s and chopper peripheral speed 0.5m / s. (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 a short tube nozzle (2 mmφ) Added dropwise and granulated. The batch size is 0.2 kg. The average droplet diameter of the aqueous sodium silicate solution was about 3500 μm.
After addition of the aqueous sodium silicate solution, mixing was continued for 1 minute, and then the mixture was discharged from a 2 L high speed mixer and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Example 6
In the blending ratio shown in Table 2, heavy calcium carbonate (product of Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) and calcium silicate (product of Tomita Pharmaceutical Co., Ltd., trade name: Florite R, average grain) Sodium silicate aqueous solution (Fuji Chemical Co., Ltd.) while mixing at a high speed mixer (2L high speed mixer, manufactured by Earth Technica Co., Ltd.) and mixing under conditions of agitator peripheral speed 7m / s and chopper peripheral speed 0.5m / s. Made by Kogyo 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 short tube nozzle (2 mmφ). Then granulated. The batch size is 0.2 kg. The average droplet diameter of the aqueous sodium silicate solution was about 3500 μm.
After addition of the aqueous sodium silicate solution, mixing was continued for 1 minute, and then the mixture was discharged from a 2 L high speed mixer and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

Comparative Example 3
In the blending ratio shown in Table 2, heavy calcium carbonate (Calfine Co., Ltd., trade name: Criston SS, average particle size of about 5 μm) was charged into a high-speed mixer (2 L high-speed mixer, manufactured by Earth Technica Co., Ltd.) While mixing under conditions of agitator peripheral speed 7 m / s, chopper peripheral speed 0.5 m / s, 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%) was added dropwise using a short tube nozzle (2 mmφ) and granulated. The batch size is 0.2 kg. The average droplet diameter of the aqueous sodium silicate solution was about 3500 μm.
After addition of the aqueous sodium silicate solution, mixing was continued for 1 minute, and then the mixture was discharged from a 2 L high speed mixer and dried at 105 ° C. for 120 minutes using an electric shelf dryer to obtain granules. The physical properties of the granules were evaluated as described above.

From the results in Table 1, the granules of Examples 1 to 4 have little decrease in wet disintegration strength even after the storage stability test, whereas the granules of Comparative Examples 1 to 2 have a lower storage stability test. It can be seen that the wet disintegration strength is significantly reduced.
Moreover, from the results of Table 2, the granules of Examples 5 to 6 have little decrease in wet disintegration strength even after the storage stability test, whereas the granules of Comparative Example 3 have a lower storage stability test. It can be seen that the wet disintegration strength is significantly reduced.

Test Example: Evaluation of Usability Using the granules obtained in Examples 1 to 4 and Comparative Examples 1 and 2, each component was mixed according to the formulation shown in Table 3 to prepare a dentifrice. The obtained dentifrice was stored at 50 ° C. for 1 month. 1 g of the dentifrice after the storage test was applied to a toothbrush (Check, manufactured by Kao Corporation), brushed, and the granular feel was evaluated by a skilled evaluator.
The results are shown in Table 4.

  From the results in Table 4, it can be seen that the dentifrice using the granules of Examples 1 to 4 provides an excellent granule feel compared to the dentifrice using the granules of Comparative Examples 1 and 2.

Claims (8)

  One or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide and calcium hydroxide, water-insoluble powder material (B) excluding the inorganic powder (A), and 1 of sodium silicate and potassium silicate A dentifrice granule containing at least a seed silicate (C).   One or more inorganic powders (A) selected from zinc oxide, calcium silicate, magnesium oxide and calcium hydroxide, water-insoluble powder material (B) excluding the inorganic powder (A), and 1 of sodium silicate and potassium silicate Granules for dentifrices, containing at least seeds of silicate (C).   The 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 dentifrice granule according to any one of claims 1 to 3, wherein the content or blending amount of the inorganic powder (A) is 0.1 to 7% by mass.   The mass ratio of the inorganic powder (A) to the silicate (C) [inorganic powder (A) / silicate (C)] is 0.01 to 1, according to any one of claims 1 to 4. Dentifrice granules.   A method for producing a dentifrice granule in which the inorganic powder (A), the water-insoluble powder material (B) and the silicate (C) are mixed and granulated using a container rotating granulator. The aqueous solution of silicate (C) is supplied as droplets to the mixture containing the inorganic powder (A) and the water-insoluble powder material (B) using a nozzle. A method for producing dentifrice granules.   The method for producing a dentifrice granule according to claim 6, wherein the obtained granule is further dried.   The dentifrice containing the granule for dentifrices in any one of Claims 1-5, and surfactant.