JP2010275273A - Dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition which has moderate polishing property and high cleaning property and shows both, during its use, excellent toothbrushing feeling (brushing sense) and absence of stimulation to gingiva. <P>SOLUTION: The dentifrice composition includes: (A) a synthesized amorphous aluminum-bonded silicate which contains aluminum, as Al<SB>2</SB>O<SB>3</SB>, in a content of 0.5-7.5 mass% of SiO<SB>2</SB>and OH groups in a content of 2.0-3.5 mass% of SiO<SB>2</SB>; and (B) granular zeolite with an average particle size of 150-800 μm and an average collapse strength of 15-100 g/piece. The dentifrice composition is practically harmless to teeth, has moderate polishing property and high cleaning property without damaging teeth, and shows both, during its use, excellent toothbrushing feeling (brushing sense) and absence of stimulation to gingiva. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dentifrice composition having moderate polishing properties and high cleaning properties, and having both excellent sensation of brushing (brushing sensation) and no irritation to gingiva during use.

  As abrasives used in dentifrices, there are fine powder silicic acid, calcium carbonate, calcium phosphate, aluminum hydroxide, etc., but in recent years, fluorine-containing dentifrices are becoming mainstream, and among these abrasives, the phase with fluorine The fine powdered silicic acid having the most excellent solubility is the mainstream of abrasives.

  However, finely powdered silicic acid generally has a Mohs hardness of 4.5 to 5.0, so there is a concern of harm to teeth. In order to cover this defect, zirconium-bonded silicate or titanium-bonded silicate has been proposed as an abrasive having an appropriate polishing property that does not damage the teeth (see Patent Documents 1 and 2).

  However, in the techniques of Patent Documents 1 and 2, although an abrasive having an appropriate abrasiveness that does not damage teeth can be obtained, there is no description regarding cleaning properties. In addition, since expensive raw materials such as zirconium and titanium are used, there remains a problem as a general-purpose polishing base used for dentifrice.

  On the other hand, zeolite is known to have an effect of preventing tartar formation and bad breath in the oral cavity field (see Patent Document 3), and oral compositions containing acid-treated zeolite or specific metal ion-substituted zeolite are proposed. (See Patent Documents 4 and 5). Furthermore, zeolite is highly abrasive to teeth due to its powder properties compared to inorganic powders generally used as abrasives for dentifrices, and disintegrating granular zeolite is a composition for oral cavity such as dentifrice compositions. When blended into a product, it maintains its moderate polishability and high cleaning power, as well as a comfortable brushing feeling (brushing sensation) that recognizes the effect of removing dirt due to the feel of granules in the mouth until the end of brushing. Since it is possible, it is suitably blended in the dentifrice composition.

  As a method for improving the effect of removing calculus-like stubborn colored stains while controlling the abrasiveness, dentifrices containing disintegrating granular zeolite have been proposed (see Patent Documents 6 and 7). Furthermore, the dentifrice composition which not only removes colored stains but also can effectively remove stains adhering to the teeth, and has an effect of suppressing reattachment of stains to the teeth after removal of the stains (Patent Document 8). And a dentifrice composition (see Patent Document 9) having a comfortable brushing feeling and feeling of use (see Patent Document 9) and a dentifrice containing granules that do not give an unpleasant foreign body feeling (see Patent Document 10).

  Today, as consumer needs are diversifying, there are voices for dentifrices that require an excellent feeling of brushing (brushing sensation), but for people with sensitive oral mucosa, infants and children, etc. The present situation is that it may be felt that is too strong, and a less irritating one is desired. Thus, it cannot be said that the conventional technology has a sufficient effect of achieving both a comfortable sensation of brushing and a lack of irritation to the gingiva.

  Therefore, it is desired to develop a dentifrice composition that has moderate polishing properties and high cleaning properties, and that has both a comfortable brushing feeling and no irritation to the gums.

JP 2002-293530 A JP-A-11-140428 Japanese Patent Laid-Open No. 55-24112 JP-A-63-146809 JP-A-1-38017 JP 2004-123684 A, International Publication No. 2005/000260 Pamphlet JP 2006-111622 A JP 2008-266251 A JP-A-1-299211

  The present invention has been made in view of the above circumstances, and has a moderate polishing property and a high cleaning property, and has both excellent wiping feeling (brushing sensation) and no stimulation to the gums during use. An object is to provide an agent composition.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) aluminum is in the range of 0.5 to 7.5% by mass with respect to SiO ₂ as Al ₂ O ₃ , and the amount of OH groups is and synthetic amorphous aluminum bonded silicate to SiO ₂ is 2.0 to 3.5 wt%, and (B) an average particle size of 150～800Myuemu, and an average disintegration strength 15 to 100 / number of granules zeolite Incorporating, it has been found that it has moderate polishing properties and high cleaning properties, and that both a feeling of brushing (brushing sensation) and no irritation to the gums are compatible during use, and the present invention has been made. It is a thing.

  That is, in the present invention, the above-described synthesis method can be obtained by reacting water-soluble alkali metal silicate, water-soluble aluminum salt and mineral acid as essential raw materials in the presence of a water-soluble alkali metal mineral salt electrolyte. The regular aluminum bonded silicate has almost no harmful effect on the teeth, has moderate polishing properties that do not damage the teeth, and high cleanability, and it does not need to be manufactured using expensive raw materials. Useful as a polishing substrate, and by combining the synthetic amorphous aluminum-bonded silicate with a granular zeolite having the above average particle size and average disintegration strength, moderate polishing properties and high cleaning properties can be obtained. While being used, a dentifrice composition can be obtained in which both excellent brushing sensation (brushing sensation) derived from granular zeolite and no irritation to gingiva during use.

Accordingly, the present invention provides the following dentifrice composition.
Claim 1;
(A) Synthesis amorphous aluminum in the range of 0.5 to 7.5 wt% with respect to SiO ₂ as Al ₂ O _3, and OH group content is 2.0 to 3.5 wt% with respect to SiO ₂ A dentifrice composition comprising an aluminum-bonded silicate and (B) granular zeolite having an average particle size of 150 to 800 μm and an average disintegration strength of 15 to 100 g / piece.
Claim 2;
(A) Component Amorphous Aluminum Bonded Silicate reacts with water-soluble alkali metal silicate, water-soluble aluminum salt and mineral acid as essential raw materials in the presence of water-soluble alkali metal mineral salt electrolyte The dentifrice composition according to claim 1, wherein the dentifrice composition is obtained.
Claim 3;
The amount of the mineral electrolyte of the water-soluble alkali metal is 5 to 30% by mass with respect to SiO ₂ of the water-soluble alkali metal silicate as M ₂ O (where M represents an alkali metal). 2. The dentifrice composition according to 2.
Claim 4;
4. The granular zeolite as component (B) is a granular zeolite containing a zeolite, silicic acid anhydride, titanium oxide and / or aluminum oxide as raw material components and prepared in the form of granules. The dentifrice composition according to Item.
Claim 5;
The content of the synthetic amorphous aluminum-bonded silicate as the component (A) is 5 to 35% by mass, and the content of the granular zeolite as the component (B) is 3 to 20% by mass. The dentifrice composition according to Item.

  The dentifrice composition of the present invention has almost no harmful effect on the teeth, has an appropriate abrasiveness and high cleaning properties that do not damage the teeth, and has an excellent brushing feeling (brushing feeling) and gingival feeling during use. The lack of stimulation is compatible.

Hereinafter, the present invention will be described in more detail. In the dentifrice composition of the present invention, (A) aluminum is in the range of 0.5 to 7.5% (mass%, the same shall apply hereinafter) with respect to SiO ₂ as Al ₂ O ₃ and the OH group content is SiO _2. Synthetic amorphous aluminum-bonded silicate with respect to 2.0 to 3.5%, and (B) granular zeolite having an average particle size of 150 to 800 μm and an average disintegration strength of 15 to 100 g / piece .

Dentifrice composition of the present invention, aluminum in the range 0.5-7.5% with respect to SiO ₂ as Al ₂ O _3, and the amount of OH groups relative to SiO ₂ with 2.0% to 3.5% It contains some synthetic amorphous aluminum bonded silicate as an abrasive. Although the relationship between the physical properties of the synthetic amorphous aluminum-bonded silicate, the polishing properties, and the cleaning properties is not clear, it is considered that appropriate polishing properties and cleaning properties are exhibited by having the physical properties.

The synthetic amorphous aluminum-bonded silicate of component (A) contains aluminum as Al ₂ O _{3 in} a range of 0.5 to 7.5%, preferably 1.5 to 4.5% with respect to SiO _2. . If it is less than 0.5%, the abrasiveness exceeds an appropriate range and damage to the teeth increases, and if it exceeds 7.5%, sufficient cleaning properties cannot be obtained.

Moreover, OH group content of the synthetic amorphous aluminum bonded silicate 2.0% to 3.5% with respect to SiO _2, preferably in the range from 2.3 to 3.0%. If the OH group amount is less than 2.0%, the abrasiveness exceeds an appropriate range and the harmfulness to teeth increases, and if it exceeds 3.5%, sufficient cleaning properties cannot be obtained.

The silica compound has a structure in which a tetrahedral structure centering on a silicon atom is infinitely connected via an oxygen atom, and has a terminal structure of Si—OH.
The amount of OH group is a value measured by the following method.
OH group measurement method;
Using EXSTAR-6000 manufactured by Seiko Denshi Kogyo Co., Ltd., OH / SiO ₂ (mass%) was calculated from the following formula by mass change between 190 ° C. and 900 ° C., and this was defined as the OH group amount. The amount of OH groups is the same as the amount of water released between 190 ° C and 900 ° C.
OH / SiO ₂ (mass%) =
((Mass after firing at 190 ° C.−mass after firing at 900 ° C.) / Mass after firing at 190 ° C.) × 100

  The method for producing the silicate is not particularly limited. For example, a water-soluble alkali metal silicate is previously charged in a reaction vessel, and a water-soluble aluminum salt and a mineral acid are added thereto. When the obtained wet cake is dispersed and washed in several times the amount of water, a method of adjusting the slurry pH can be employed.

  The method for producing the synthetic amorphous aluminum-bonded silicate according to the present invention will be further described in detail.

  The synthetic amorphous aluminum-bonded silicate is produced by reacting water-soluble alkali metal silicate, water-soluble aluminum salt and mineral acid as essential raw materials in the presence of a water-soluble alkali metal mineral salt electrolyte. In this case, it is preferable to add a water-soluble aluminum salt and a mineral acid to an aqueous solution of a water-soluble alkali metal silicate, and to react, particularly, so that the 5% slurry pH becomes 8.0 to 10.0. It is preferable to adjust to.

Examples of the water-soluble alkali metal silicate used in the present invention include sodium, potassium and lithium silicates, and sodium silicate can be generally used from the viewpoint of relatively low cost. Furthermore, the molar ratio of SiO ₂ / M ₂ O (where M represents an alkali metal) is preferably in the range of 2 to 4.

  Further, as the acidifying agent for the water-soluble alkali metal silicate, a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid can be used.

The SiO ₂ concentration of the water-soluble alkali metal silicate solution is preferably in the range of 5 to 15%. If it is less than the lower limit, the production efficiency is inferior, and if it exceeds the upper limit, a synthetic amorphous aluminum-bonded silicate having the above properties may not be obtained. The mineral acid concentration is preferably 5 to 25%, particularly 10 to 20%. By appropriately selecting other conditions for these raw material concentrations, the intended synthetic amorphous aluminum-bonded silicate of the present invention can be obtained within this range.

  In the production of the synthetic amorphous aluminum-bonded silicate, it is important that the water-soluble alkali metal mineral salt electrolyte is present in the reaction system in the proportion described below. Moreover, it is desirable to add a water-soluble aluminum salt in the step of obtaining a fine powder silicate by reacting a water-soluble alkali metal silicate solution with a mineral acid. Furthermore, it is important to start these reactions from the alkali side. Further, it is desirable to adjust the 5% slurry pH obtained in the final product to be 8.0 to 10.0.

  In general, by adding an electrolyte described later in the step of obtaining a fine powder silicate by reacting a water-soluble alkali metal silicate solution with a mineral acid, the cleaning property for the teeth is improved, but at the same time, the polishing property is improved. Tend to be larger. In the synthetic amorphous aluminum-bonded silicate according to the present invention, in order to obtain desired polishing properties and cleanability, it is beneficial to interpose aluminum in the step of depositing the precipitated fine powder silicate. That is, as will be described later, when the amount of aluminum is increased, the cleanability is lowered without deteriorating the cleanability. A desired low-polishing / high-cleaning dentifrice silica base can be obtained by appropriately selecting the amount of the electrolyte and the amount of the water-soluble aluminum salt as the aluminum raw material.

  As the electrolyte, a water-soluble alkali metal mineral acid salt is preferably used, and specifically, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, and the like.

The amount of the electrolyte used is preferably 5 to 30% with respect to SiO ₂ of the water-soluble alkali metal silicate as M ₂ O (where M represents an alkali metal). If the amount used is less than the lower limit, the blending effect cannot be obtained sufficiently, and if it exceeds the upper limit, the abrasiveness may be too high. The electrolyte is preferably used by previously containing the electrolyte in a water-soluble alkali metal silicate solution. However, the electrolyte may be added to the mineral acid and reacted.

  As the aluminum donor material, a water-soluble aluminum salt described later can be used. The aluminum donor material may be used by diluting a water-soluble aluminum salt solution to a predetermined concentration and directly reacting it. In particular, a water-soluble aluminum salt is previously added to a mineral acid to obtain an aluminum-containing mineral acid. A method of reacting with a water-soluble alkali metal silicate solution is recommended. By adopting this method, it is possible to produce aluminum in a state in which aluminum is dispersed more uniformly in silica as compared with other methods.

Examples of the water-soluble aluminum salt include, but are not limited to, aluminum chloride, aluminum sulfate, and aluminum nitrate. The use amount of the water-soluble aluminum salt is preferably 0.5 to 7.5%, particularly 1.0 to 6.0% with respect to SiO ₂ of the water-soluble alkali metal silicate as Al ₂ O _3. . If the amount used is less than the lower limit, the high abrasiveness associated with the addition of the electrolyte cannot be sufficiently reduced, and if it exceeds the upper limit, the abrasiveness required as a dentifrice base may be lowered. When a mineral acid containing aluminum is used, it may be appropriately adjusted within the above range and used for the reaction.

  Furthermore, it is important that the reaction of the water-soluble alkali metal silicate, the water-soluble aluminum salt and the mineral acid is started from the alkali side as described above. When the reaction is started from the acidic side, the target product may not be obtained because a gel-like substance is formed.

  Note that starting the reaction from the alkali side means that nucleation is carried out on the alkali side. Specifically, for example, (1) a water-soluble alkali metal silicate is previously charged in a reaction vessel, and A method of adding and reacting a water-soluble aluminum salt and a mineral acid; and (2) a method of simultaneously adding a water-soluble aluminum salt-containing mineral acid and a water-soluble alkali metal silicate to a reaction vessel. (3) A water-soluble alkali metal silicate is charged in advance in a reaction tank, and a desired amount of mineral acid and water-soluble aluminum salt are added simultaneously or separately. Examples of such a method include addition of silica, and a method of causing silica nucleation on the alkali side.

  The reaction temperature is preferably 60 ° C to 100 ° C. When other reaction conditions are the same, when the reaction temperature is less than 60 ° C., the cohesion of secondary particles is weak, and synthetic amorphous aluminum-bonded silicic acid suitable as a silica base for low polishing and high cleaning by adding aluminum Salt may not be obtained.

  The reaction completion pH is preferably 6-9. When the other reaction conditions are the same, if the reaction end pH exceeds 9, precipitation of the synthetic amorphous silicate will not be performed completely, resulting in a poor reaction yield. There is a case where a regular aluminum bonded silicate cannot be obtained.

Furthermore, in the said manufacturing method, it is desirable to manufacture so that 5% slurry pH may be 8.0-10.0. The best way to manufacture so that the 5% slurry pH is in the above range is to adjust the pH in a repulping process in which a wet cake obtained by filtration is dispersed in several times the amount of water and washed. In the adjustment, when the pH is higher than the desired pH, the same mineral acid as described above may be used. When the pH is too low, a water-soluble alkali metal salt may be added separately. As the water-soluble alkali metal salt used for this, sodium hydroxide, carbonate, bicarbonate and the like are suitable.
The 5% slurry pH is a value measured by the following method.
5 g of sample is put in 95 ml of deionized water, and a suspension is prepared by stirring, and the reading at 25 ° C. after 2 minutes of stirring by the pH measurement method of the quasi-drug raw material standard test method is 5% slurry pH. It was.

  The synthetic amorphous aluminum-bonded silicate produced in this way has a suitable polishing property and high cleaning properties, and is suitable as a dentifrice silica base.

  In general, the RDA method and the Tobacco Jani method have been proposed and used as methods for evaluating the polishing properties and cleaning properties of dentifrice abrasives, respectively, but the evaluation methods are complicated and costly. Therefore, it can be evaluated by the measurement method described later.

  As for the abrasiveness of the synthetic amorphous aluminum-bonded silicate, a gold plate is used as the polishing plate, and the polishing amount is preferably in the range of 0.4 to 1.1 mg. If it is less than the lower limit, the function as an abrasive cannot be expected, and if it exceeds the upper limit, the abrasiveness may be too strong.

As noted above, the precautions for the production of the synthetic amorphous aluminum-bonded silicate of the present invention include silica (SiO ₂ ) in a water-soluble alkali metal silicate solution in addition to starting the reaction on the alkali side. In this process, the water-soluble aluminum salt is added and reacted in the process until the components are completely precipitated. Preferably, the water-soluble aluminum salt is previously contained in the mineral acid. That is, even if a water-soluble aluminum salt is added from the time when all the silica has been precipitated, the desired synthetic amorphous aluminum-bonded silicate cannot be obtained. For example, in a method in which a water-soluble alkali metal silicate solution and a mineral acid are added simultaneously, the water-soluble aluminum salt should be added by the end of the addition of both. After the addition of the water-soluble aluminum salt, the mineral acid may be added to a desired pH depending on the application.

The obtained synthetic amorphous aluminum-bonded silicate can have an aluminum elution rate measured by the following method of 100 ppm or less, and is considered to form a silicate in which aluminum is firmly bonded. As described above, it is desirable to add and react the water-soluble aluminum salt in the process until the silica (SiO ₂ ) content in the water-soluble alkali metal silicate solution is completely precipitated, and all the silica has been precipitated. When a water-soluble aluminum salt is added from the time point, the bond with silica is insufficient, and the aluminum elution rate exceeds 100 ppm, and the target silicate may not be obtained.

Method for measuring aluminum elution amount;
1 g of the sample was placed in a 100 ml Erlenmeyer flask, 80 g of 1M sulfuric acid was added, and the mixture was heated and stirred at 95 ° C. for 3 hours. After cooling, the filtrate, which was filtered using a membrane filter (ADVANTEC Cellulose Nitrate 0.3 μm), was taken up in a 100 ml volumetric flask and the volume was increased to prepare a test solution. Next, the amount of aluminum in this test solution was measured using ICP-AES manufactured by Jarrel-Ash, and the amount of aluminum eluted per gram of the sample was determined.

  After completion of the reaction / repulp washing, the slurry is filtered and washed by a normal method, and the resulting synthetic amorphous aluminum-bonded silicate is separated from the liquid, dried and crushed and used as an abrasive. be able to.

The synthetic amorphous aluminum-bonded silicate produced in this manner is amorphous in powder X-ray diffraction by the following method, and has a pore diameter of 1.85 to 2.10 nm.
Measuring method of pore diameter;
Using BELSORP MINI manufactured by Nippon Bell Co., Ltd., using liquid nitrogen as a coolant, adsorbing nitrogen gas at -196 ° C, and calculating the pore size distribution by the Dollimore-Heal method from the desorption amount of the nitrogen gas The maximum frequency diameter was defined as the pore diameter. The sample was degassed at 120 ° C. for 60 minutes.
Method for measuring powder X-ray diffraction;
X-ray diffraction was performed under the conditions of 30 kV and 40 mA using a Cu tube using Shimadzu Corporation XRD-7000.

  (A) The compounding quantity of the synthetic amorphous aluminum bond silicate of a component is 5 to 35% of the whole composition, It is preferable to set it as 10 to 25% especially. If it is less than 5%, sufficient cleanability may not be obtained, and if it exceeds 35%, the abrasiveness may exceed an appropriate range and the damage to the teeth may be increased.

  The (B) component granular zeolite has a specific range of average particle size and average disintegration strength, and contains zeolite and silicic anhydride as a raw material component, and more preferably titanium oxide and / or aluminum oxide. Granule zeolite prepared in a granular form is preferably used.

  The average particle size of the granular zeolite is determined by sieving with a JIS sieve and then measuring the mass of the granular zeolite remaining on each sieve. When calculating the 50% particle size from this mass distribution, the average particle size is in the range of 150 to 800 μm, preferably 200 to 500 μm. If the average particle size of the granular zeolite is smaller than 150 μm, sufficient cleaning properties and brushing feeling cannot be obtained, and if it exceeds 800 μm, irritation to the gingiva increases and the gingiva may be damaged.

  The average disintegration strength of the granule zeolite was measured by automatic breaking strength measurement for 30 granules one by one with a rheometer (Sun Rheometer CR-200D) manufactured by Sun Science Co., Ltd. (one granule was compressed at a speed of 10 mm / min). When the average value of the load when the granular zeolite disintegrates is taken as the average disintegration strength, it is 15 to 100 g / piece, and particularly preferably in the range of 20 to 50 g / piece. . When the average disintegration strength is less than 15 g / piece, the granular zeolite easily disintegrates, and the cleaning property and the brushing feeling cannot be sufficiently obtained. When the average disintegration strength exceeds 100 g / piece, the abrasiveness becomes too high and the teeth are damaged. There is a case.

  In the granular zeolite according to the present invention, silicic anhydride and, more preferably, titanium oxide and / or aluminum oxide are added to the zeolite, and optional components as described later are added if necessary, and a specific average particle size is added. And can be obtained by granulating and drying so as to have a specific average disintegration strength.

Here, zeolite used as a raw material for granulate _{zeolite, W m Z n O 2n ·} sH 2 O (W is Na, Ca, K, with Ba or Sr, Z is Si + Al (Si: Al> 1), s is Unlike the synthetic amorphous aluminum-bonded silicate of component (A), it is a crystalline inorganic polymer. There are both natural ones and synthetic ones. About 40 kinds of natural ones and more than 200 kinds of synthetic ones are already known.

  In the present invention, any of these zeolites can be used. Examples of natural zeolite and synthetic zeolite include clinoptilolite, mordenite, analcite, shabasite, erionite, rhomontite, philipite, ferrierite, and wailakite. Synthetic zeolites include A (3A, 4A, 5A, etc.) type zeolite, L type zeolite, faujasite (X type zeolite, Y type zeolite), offretite, erionite, mordenite and the like. Since natural zeolite contains impurities and lacks homogeneity, synthetic zeolite is more preferably used. Of the synthetic zeolites, A (3A, 4A, 5A) type zeolite, X type zeolite, Y type zeolite, and L type zeolite are preferable. Is more preferable. Further, among the A-type zeolites, 4A-type zeolites are particularly preferable from the viewpoint of calculus-preventing effect because they are superior in calcium scavenging ability compared to other A-type zeolites. 4A-type zeolite is commercially available, and examples thereof include Sasil manufactured by Degussa, Toyobuilder manufactured by Tosoh Corporation, Zeorum, Shilton manufactured by Mizusawa Chemical Co., Ltd., and the like.

The average particle size of the zeolite used as a raw material for the granular zeolite according to the present invention is not particularly limited, but is preferably 1 to 100 μm, particularly preferably 20 to 80 μm. If the average particle size is less than 1 μm, the strength of the granular zeolite may be low, and an appropriate disintegration strength may not be maintained. If the average particle size exceeds 100 μm, the granule particle size may be increased and may not be prepared to an appropriate particle size. is there.
The average particle size is a measured value of 50% particle size in a volume-based particle size distribution using a Nikkiso Co., Ltd. Microtrac particle size analyzer (the same applies hereinafter).

  The content of the zeolite in the granular zeolite is preferably 50 to 99%, particularly 70 to 90%, from the viewpoint of brushing feeling, in order to sufficiently exhibit the brushing feeling derived from zeolite.

  Moreover, although silicic acid anhydride has two types of manufacturing methods, a dry method and a wet method industrially, it is preferable to use the precipitation silica by a wet method especially in this invention. For example, as the precipitated silica produced by a wet method, TIXOSIL43 manufactured by Rhodia Co., etc. can be mentioned and can be suitably used.

  The average particle size of silicic anhydride (average particle size by the same measurement method as in the case of the above zeolite) is preferably 0.1 to 50 μm, more preferably 1 to 25 μm from the viewpoint of brushing feeling. If the average particle size exceeds 50 μm or less than 0.1 μm, the disintegration strength of the granular zeolite becomes weak, and the brushing feeling may not be sufficiently obtained. In addition, when the silicic acid anhydride obtained by the dry method is used, the abrasiveness exceeds an appropriate range, and the harmfulness to the teeth may increase.

  The content of silicic acid anhydride is preferably 0.5 to 25%, particularly 1 to 20%, particularly 1 to 10% of the whole granular zeolite from the viewpoint of brushing feeling. If the content is less than 0.5%, the disintegration strength of the granular zeolite becomes low, and there may be a case where sufficient brushing feeling cannot be obtained. There may be a case where the sensation of origin is not sufficiently obtained.

  Further, examples of titanium oxide include two types, a rutile type and an anatase type. In the present invention, rutile type titanium oxide is particularly preferable. Commercially available products can be used as the titanium oxide, and specifically, there are TIPAQUE manufactured by Ishihara Sangyo Co., Ltd., TR-600 manufactured by Fuji Titanium Industrial Co., Ltd., and the like.

  The average particle size of titanium oxide (average particle size by the same measurement method as the above zeolite) is preferably 0.05 to 10 μm, particularly 0.1 to 5 μm from the viewpoint of polishing properties and wiping feeling. More preferred. If the average particle diameter is larger than 10 μm, the abrasiveness may exceed an appropriate range and the damage to the teeth may be increased, and if it is smaller than 0.05 μm, the brushing feeling may not be sufficiently obtained.

  The content of titanium oxide in the granular zeolite is not particularly limited, but is preferably 0 to 25%, particularly 0.5 to 20%, particularly 0.5 to 10% of the whole granular zeolite from the viewpoint of brushing feeling and cleanability. . If the content exceeds 25%, the amount of zeolite is relatively reduced, and the sensation of cleaning derived from zeolite and the cleanability may not be sufficiently obtained.

The aluminum oxide is preferably produced by the Bayer method and the sintering temperature is controlled to about 1,000 to 1,200 ° C. so that the α degree is 50 to 70%, and the α degree is 70. If it exceeds 50%, an appropriate polishing force cannot be maintained, and the polishing force may become too high.
The average particle size of aluminum oxide (average particle size by the same measurement method as that of the above zeolite) is preferably 0.1 to 10 μm, particularly preferably 0.5 to 3 μm. If the average particle size exceeds 10 μm, the abrasiveness may exceed an appropriate range and the damage to the teeth may be increased, and if it is less than 0.1 μm, sufficient brushing feeling may not be obtained.
A commercially available product can be used as the aluminum oxide, and specifically, aluminum oxide (alumina, average particle size 1 μm) manufactured by Nippon Light Metal Co., Ltd. can be used.

  The content of aluminum oxide in the granular zeolite is not particularly limited, but is preferably 0 to 25%, particularly 1 to 20% of the whole granular zeolite. When the content exceeds 25%, the amount of zeolite is relatively decreased, and the feeling of brushing derived from zeolite may be lowered.

  Further, the granular zeolite may contain titanium oxide or aluminum oxide, or may contain titanium oxide and aluminum oxide, but the total content of titanium oxide and aluminum oxide in the granular zeolite is 0 to 30%, In particular, a range of 0.5 to 25%, particularly 0.5 to 15% is preferable. When the total content exceeds 30%, the amount of zeolite is relatively decreased, and the feeling of brushing derived from zeolite may be lowered.

  In the present invention, as a raw material of the granular zeolite, in addition to the above-described zeolite and anhydrous silicic acid, and in addition to titanium oxide and / or aluminum oxide, various insoluble materials can be used as long as the performance of the granular zeolite is not hindered. Optional ingredients can be added. Specifically, dibasic calcium phosphate (dihydrate or anhydride), primary calcium phosphate, tertiary calcium phosphate, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, magnesium carbonate, tertiary magnesium phosphate, insoluble sodium metaphosphate, Examples include insoluble potassium metaphosphate and zirconium silicate. In addition, when adding the said insoluble material, the addition amount is 20% or less in a granular zeolite, and 0 to 10% is especially preferable.

  Furthermore, in addition to the above insoluble materials as raw materials, the granulated zeolite can be blended with medicinal components, colorants, fragrance ingredients, other excipients and the like that are generally blended into dentifrice compositions. In this case, as the colorant, water-insoluble ones such as gunjo, koji, bengara, titanium mica, and lake dye are preferably blended.

  As a method for forming the granular zeolite, there are a compression molding method, an extrusion molding method, a spray drying method, and the like, but it is preferable to use a sintering method because it is easy to obtain granules in the above average disintegration strength range. In this case, in the sintering method, the granulation / drying time is 15 to 50 minutes, the firing is performed at 90 ° C. to 150 ° C., particularly 90 ° C. to 120 ° C. for 15 to 30 minutes, particularly 20 to 30 minutes, It is preferable to screen after that. In addition, sieving is preferably carried out with a JIS sieve, and those that pass through a sieve having an aperture of 106 μm (140 mesh) and those that do not pass through an aperture of 850 μm (18 mesh) are excluded. By granulating and firing under such conditions, granules having the above-mentioned specific average particle diameter and average disintegration strength can be easily obtained. If the granulation / drying time is less than 15 minutes or the firing conditions are less than 90 ° C., the average particle size may be less than 150 μm, the granulation / drying time may exceed 50 minutes, or the firing conditions may be 150 If it exceeds 0 ° C., the average particle size may exceed 800 μm. If the firing time is less than 15 minutes, the average disintegration strength may be less than 15 g / piece, and if it exceeds 30 minutes, the average disintegration strength may exceed 100 g / piece.

  In the dentifrice composition of the present invention, the above-mentioned granular zeolite can be blended alone or in combination of two or more, but the blending amount is composition from the viewpoint of brushing feeling and irritation to gingiva. 3 to 20%, especially 5 to 15% of the whole product is preferable. If the blending amount is less than 3%, sufficient cleaning properties and brushing feeling derived from the granular zeolite cannot be obtained, and if it exceeds 20%, the abrasiveness exceeds an appropriate range and the harmfulness to the teeth increases, and the gingiva is increased. You may feel irritation.

  The dentifrice composition of the present invention can be prepared as a dentifrice such as a toothpaste, a liquid dentifrice, a liquid dentifrice, and a toothpaste, particularly a dentifrice. In this case, according to the dosage form, other known additives can be blended as optional components in addition to the essential components as long as the effects of the present invention are not impaired. For example, abrasives, thickeners, binders, surfactants, sweeteners, preservatives, active ingredients, fragrances, colorants and the like can be blended, and these ingredients can be mixed with water for production.

  As the abrasive, in addition to the synthetic amorphous aluminum-bonded silicate of component (A), other known abrasives, for example, silica-based abrasives such as silica gel and zirconosilicate, dicalcium phosphate dihydrate, Anhydrous dibasic calcium phosphate, phosphoric acid type abrasives such as calcium pyrophosphate, aluminum hydroxide, crystalline zirconium silicate, polymethyl methacrylate, insoluble calcium metaphosphate, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, third phosphorus It is possible to use one or more of magnesium oxide, zirconium silicate, tricalcium phosphate, hydroxyapatite, fluoroapatite, calcium deficient apatite, tertiary calcium phosphate, fourth calcium phosphate, eighth calcium phosphate, synthetic resin-based abrasive, etc. so That.

  The above-described abrasive as an optional component can be blended in an amount of 0 to 30% of the entire composition, and may not be blended. Furthermore, it is preferable to mix | blend in the range from which the total compounding quantity with the synthetic amorphous aluminum joint silicate of (A) component will be 5-45%.

  As a thickener, sugar alcohols such as glycerin, sorbit, propylene glycol, polyethylene glycol having an average molecular weight of 200 to 6000, ethylene glycol, 1,3-butylene glycol, reduced starch saccharified product, one or two kinds of polyhydric alcohols The above can be blended. The amount is usually 5 to 70% based on the total amount of the composition.

  Binders include cellulose binders such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl ethyl cellulose, methyl cellulose, xanthan gum, carrageenan, guar gum, sodium alginate, cationized cellulose, montmorillonite, gelatin And sodium polyacrylate, and the like, and one or more of them can be blended. A compounding quantity is 0.1 to 5% normally with respect to the composition whole quantity.

  Surfactants include anionic surfactants such as sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, acyl sarcosine salts such as sodium lauroyl sarcosine sodium and sodium myristoyl sarcosine, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride N-acyl glutamate such as sodium monosulfate, sodium lauryl sulfoacetate, sodium N-palmitoyl glutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate, etc. Can be mentioned. Examples of the nonionic surfactant include polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, sucrose fatty acid ester, alkylol amide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, alkyl glucoside, Decaglyceryl laurate or the like is used. Of these, polyoxyethylene alkyl ethers and alkyl glycosides are preferred from the viewpoint of foaming. Examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, and coconut oil fatty acid amidopropyl. Although betaine etc. are used, it is not restricted to the above. The compounding quantity of surfactant is 0.1 to 10% normally.

  As sweeteners, saccharin sodium, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyl dihydrochalcone, perilartine and the like, as preservatives, parabens such as butylparaben and ethylparaben, paraoxybenzoate, Examples thereof include sodium benzoate.

  Various active ingredients include fluorine compounds such as sodium fluoride, sodium monofluorophosphate, tin fluoride, water-soluble phosphate compounds such as potassium salt and sodium salt of orthophosphoric acid, tranexamic acid, epsilon-aminocaproic acid, allantoin. Chelating phosphate compounds such as chlorohydroxyaluminum, hinokitiol, sodium lauroyl sarcosine, ascorbic acid, dl-tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, glycerophosphate , Copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid and its derivatives, Sodium acid, zeolite, methoxyethylene, maleic anhydride copolymer, polyvinyl pyrrolidone, epidihydrocholesterin, cetylpyridinium chloride, benzethonium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, sweet cherry extract, buckwheat extract, Examples include chamomile, clove, rosemary, ougon, safflower extracts. In addition, an active ingredient can be mix | blended in an effective amount in the range which does not prevent the effect of this invention.

  Perfumes include peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, Lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, Iris concrete, absolute Natural fragrances such as peppermint, absolute rose, orange flower, and fragrances processed by these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and , Menthol, carvone, anethole, cineol, salicyl Methyl, cinnamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octyl Aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, propyl alcohol , Butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate Perfume, ethyl thioacetate, and other flavors such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. The well-known fragrance | flavor raw material used for a dentifrice composition can be used, It is not limited to the fragrance | flavor of an Example. In addition, it is preferable to use 0.000001-1% of the said fragrance | flavor raw material in a composition. As a fragrance | flavor for fragrance | flavor which uses the said fragrance | flavor raw material, it is preferable to mix | blend 0.1 to 2.0% in a composition.

Examples of the colorant include Blue No. 1, Yellow No. 4, Green No. 3, and the like.
In addition, the compounding quantity of these components can be made into a normal quantity in the range which does not prevent the effect of this invention.

  The material in particular of the container which accommodates the dentifrice composition of this invention is not restrict | limited, Usually, the container used for a dentifrice composition can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used.

  In the dentifrice composition of the present invention, for example, in the measurement method described later, the amount of polishing measured using a gold plate as a polishing plate is in the range of 0.4 to 1.1 mg from the point of harm to teeth. preferable. When the polishing amount is less than the lower limit, cleaning properties cannot be expected. When the polishing amount exceeds the upper limit, the polishing properties exceed an appropriate range, and the damage to the teeth may increase.

Measuring method of polishing amount;
Using a horizontal reciprocating brushing type polishing machine, a toothpaste dispersion (40 mL of water is added to 25 g of the dentifrice composition and dispersed) is placed on a smooth metal plate and polished for 20,000 times with a load of 400 g. The weight loss of the plate was measured, and this was made abrasive.

  Moreover, about the cleaning property of the dentifrice composition of this invention, the cleaning property is so good that the coloring stain removal rate of a tooth is high, for example, in the test method of the experimental example mentioned later, the coloring stain removal rate of a tooth is 70-100. % Range is preferred.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to preparation examples, experimental examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples,% is mass% unless otherwise specified.

[Preparation Example I]
Synthetic amorphous aluminum-bonded silicates (abrasives A to D) shown in Table 1 were prepared by the following production method.
Into a reaction vessel with a 20 L baffle plate equipped with a stirrer having a 150 mmφ turbine blade, 10 kg of 10% sodium silicate (Na ₂ O.3.14SiO ₂ ) aqueous solution was placed, and sodium chloride was added to Na ₂ O / SiO _2. As a result, the reaction temperature was maintained at 95 ° C. Further, a mixed solution of 8% Al ₂ O ₃ aluminum sulfate solution and 10% sulfuric acid was added at a rate of 80 ml / min so as to have the ratio shown in Table 1 (Al ₂ O ₃ / SiO ₂ ), and then 10% Sulfuric acid was added until pH 7.0. Next, the produced slurry was filtered, and the obtained wet cake was repulped. At the time of this repulping, 10% sulfuric acid was added to adjust the slurry pH to 8.0. Thereafter, filtration and drying were performed to produce synthetic amorphous aluminum-bonded silicates (polishing agents A to D) having different aluminum contents. The 5% slurry pH of the synthetic amorphous aluminum-bonded silicate was in the range of 9.1 to 9.5, and the aluminum elution amount was in the range of 20 to 35 ppm. Moreover, it had a pore diameter of 1.85 to 2.10 nm.

[Comparative Preparation Example I-1 (Abrasive E)]
A synthetic amorphous silicate (polishing agent E) was obtained by synthesis under the same conditions as in the preparation examples except that the aluminum sulfate solution was not added.

[Comparative Preparation Example I-2 (Abrasive F)]
In a reaction vessel similar to that of the preparation example, 10 kg of 10% sodium silicate (Na ₂ O · 3.14SiO ₂ ) aqueous solution was added and maintained at a reaction temperature of 95 ° C. Further, a mixed solution of 190 ml of 8% Al ₂ O ₃ aluminum sulfate and 2850 ml of 10% sulfuric acid was added at a rate of 80 ml / min so as to have the ratio shown in Table 1 (Al ₂ O ₃ / SiO ₂ ), 10% sulfuric acid was added until pH 7.0. Next, the produced slurry was filtered, and the obtained wet cake was repulped. At the time of this repulping, 10% sulfuric acid was added to adjust the slurry pH to 8.0. Thereafter, filtration, drying and pulverization were performed to obtain a synthetic amorphous silicate (polishing agent F).

[Comparative Preparation Example I-3 (Abrasive G)]
5 kg of 10% sodium silicate (Na ₂ O.3.14SiO ₂ ) aqueous solution was placed in the same reaction vessel as in the preparation example, and the reaction temperature was maintained at 95 ° C. Furthermore, silica is deposited at a rate of 80 ml / min in a mixed solution of 190 ml of 8% Al ₂ O ₃ aluminum sulfate and 2850 ml of 10% sulfuric acid so that the ratio shown in Table 1 (Al ₂ O ₃ / SiO ₂ ) is obtained. Was added, stopped, and aged for 10 minutes. Then, the remaining solution of the above mixed solution of 10% sulfuric acid and 8% Al ₂ O ₃ aluminum sulfate solution and 5 kg of 10% sodium silicate (Na ₂ O · 3.14SiO ₂ ) aqueous solution were 80 ml / min and 120 ml / min, respectively. And then 10% sulfuric acid was added until pH 7.0. Next, the produced slurry was filtered, and the obtained wet cake was repulped. At the time of this repulping, 10% sulfuric acid was added to adjust the slurry pH to 8.0. Thereafter, filtration, drying, and pulverization were performed to obtain a synthetic amorphous silicate (polishing agent G).

  The OH group amount of the obtained abrasives A to G was measured by the following method. In Table 1, the OH group amount is also shown.

OH group measurement method;
Using EXSTAR-6000 manufactured by Seiko Denshi Kogyo Co., Ltd., OH / SiO ₂ (mass%) was calculated from the following formula by mass change between 190 ° C. and 900 ° C., and this was defined as the OH group amount. The amount of OH groups is the same as the amount of water released between 190 ° C and 900 ° C.
OH / SiO ₂ (mass%) =
((Mass after firing at 190 ° C.−mass after firing at 900 ° C.) / Mass after firing at 190 ° C.) × 100

[Preparation Example II]
Granule zeolite (granule A to C) was prepared by the production method (sintering method) shown below using the raw materials shown in Table 2.
Each raw material was mixed in the granulation container with the components and blending ratios shown in Table 2, and then granulated and dried for 30 minutes and baked at 100 ° C. for 20 minutes. Thereafter, those passing through a sieve having an aperture of 106 μm (140 mesh) and those not passing through an aperture of 850 μm (18 mesh) were excluded by screening with a JIS sieve, and granular zeolites having different average particle sizes and average disintegration strengths (granule A To C).

[Comparative Preparation Example II-1 (Granule D)]
Using the raw material shown in Table 2, it prepared on the same conditions as granule AC except having changed the calcination time into 5 minutes, and obtained the granular zeolite (granule D).

[Comparative Preparation Example II-2 (Granule E)]
Using the raw materials shown in Table 2, granulation / drying time is 5 minutes, sieving conditions are those that pass through a sieve with an opening of 26 μm (518 mesh) and those that do not pass through an opening of 106 μm (140 mesh). A granule zeolite (granule E) was obtained under the same conditions as granule A to C except that it was changed to exclude by sieving.

[Comparative Preparation Example II-3 (Granule F)]
Using the raw materials shown in Table 2, granulation / drying time is 60 minutes, firing time is 40 minutes, and the sieving conditions are those that pass through a sieve having an opening of 500 μm (30 mesh), and the opening is 1180 μm (14 mesh) A granule zeolite (granule F) was obtained under the same conditions as granules A to C, except that the sample that did not pass through JIS sieve was excluded.

The average disintegration strength and average particle size of the granules were measured by the following methods.
Measurement of average disintegration strength of granules:
Using a rheometer (San Rheometer CR-200D) manufactured by Sun Science Co., Ltd., find the average value when measuring the load when the granule disintegrates 30 times repeatedly when one granule is compressed at a speed of 10 mm / min. The average disintegration strength of the granules.

Average particle size measurement:
<Granules A to D> After 100 g of powder was screened with JIS sieves (22, 26, 30, 36, 42, 50, 60, 70, 74, 83, 93, 100, 119 mesh), The mass of the remaining granular zeolite was measured. The 50% particle size was calculated from the mass distribution, and this was used as the average particle size.
<Granule E> After sieving 100 g of the powder with a JIS sieve (149, 166, 200, 235, 281, 330, 390, 440 mesh), the mass of the granular zeolite remaining on each sieve was measured. The 50% particle size was calculated from the mass distribution, and this was used as the average particle size.
<Granule F> After 100 g of powder was screened with a JIS sieve (16, 18, 22, 26 mesh), the mass of the granular zeolite remaining on each sieve was measured. The 50% particle size was calculated from the mass distribution, and this was used as the average particle size.

* 1: Zeolite (4A-type zeolite, Sagus, manufactured by Degussa, average particle size 25 μm)
* 2: Silicic anhydride (precipitated silica, TIXOSIL 43, Rhodia, average particle size 25 μm)
* 3: Aluminum oxide (Alumina manufactured by Nippon Light Metal Co., Ltd., average particle size 1 μm)
* 4: Titanium oxide (rutile type, TIPAQUE manufactured by Ishihara Sangyo Co., Ltd., average particle size of 0.25 μm)

[Experimental example]
Using the abrasives A to G and granules A to F obtained above, dentifrice compositions having the compositions shown in Tables 3 to 6 were prepared by the following production method.
(Production method)
(1) A phase was prepared by mixing and dissolving water-soluble components (excluding binder and propylene glycol) in purified water at room temperature.
(2) A phase B in which a binder was dispersed at room temperature in propylene glycol was prepared.
(3) B phase was added and mixed in A phase under stirring, and C phase was prepared.
(4) In phase C, ingredients other than water-soluble ingredients such as fragrances and abrasives are mixed at room temperature using a 1.5 L kneader (manufactured by Ishiyama Kogyo), defoamed under reduced pressure (4 kPa), and dentifrice 1.2 kg of composition was obtained.

The dentifrice composition thus obtained was made into a laminated tube (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30, thickness 257 μm (Dainippon), whose innermost layer is made of linear low density polyethylene. (Printed) was filled with 50 g.
The abbreviations and names in the layer structure of the laminated tube used are as follows, and the numbers following the abbreviations indicate the thickness (μm) of each layer.
LDPE: Low density polyethylene white LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Ethylene / methacrylic acid copolymer resin

  The obtained dentifrice composition was evaluated by the following methods for polishing properties, cleanability, brushing sensation, and non-irritating gingiva. The results are shown in Tables 3-6.

(1) Abrasiveness Using a horizontal reciprocating brushing type grinder, place the toothpaste dispersion (40 g of water in 25 g of the dentifrice composition and disperse) on a smooth metal plate, and apply 20,000 times with a load of 400 g. After polishing, the weight loss of the metal plate was measured, and this was made abrasive. The abrasiveness is preferably in the range of 0.4 to 1.1 mg, and this range is regarded as appropriate abrasiveness.

(2) Cleanability The color of the surface of the untreated hydroxyapatite pellet was measured with a color difference meter as the reference color, and the value was defined as L0. The pellet was immersed in saliva at 37 ° C. for 30 minutes, and then washed with ion-exchanged water to remove surface moisture. The following three types of immersion liquids are prepared with the recalcification liquid prepared by mixing 0.74 mM calcium ion, 2.59 mM phosphate ion, and 50 mM NaCl, and 0.5% albumin remineralization is performed on the previous pellet. Solution → 3% Japanese tea + 1% coffee + 1% black tea remineralization solution → 0.6% Ammonium iron citrate remineralization solution repeated immersion for 1 hour each time 50 times, after air drying at room temperature for 1 day, The color of the colored pellet surface, which was washed with running water and air-dried again, was measured, and the value was defined as L1.
After brushing 1,000 times with a toothbrush with 1 g of the preparation (dentifrice composition) prepared on the surface of this colored pellet, lightly wash and dry with running water, measure the color again, set the value to L2, The coloring stain removal rate of the teeth was calculated from the formula, and the cleaning property was judged according to the following evaluation criteria for the average value of 10 times.
Tooth coloring removal rate (%) = [(L1-L2) / (L1-L0)] × 100
(Evaluation criteria)
◎: Average value 80% or more and 100% or less ○: Average value 70% or more and less than 80% △: Average value 60% or more and less than 70% ×: Average value 0% or more and less than 60%

(3) Brushing sensation Using about 10 subjects, about 1 g of the dentifrice composition of each composition was taken on a toothbrush, and the brushing sensation when brushing for 3 minutes was not felt <1> 1 point, <2> 2 points that feel almost no brushing, <3> 3 points that feel slightly brushed, and <4> 4 points that feel strong, 4 points From the following criteria, the degree of brushing feeling was evaluated.
(Evaluation criteria)
◎: Average point 3.5 points or more and 4.0 points or less ○: Average point 3.0 points or more and less than 3.5 points △: Average point 2.0 points or more and less than 3.0 points ×: Average point 1.0 points More than 2.0 points

(4) No stimulation to gingiva About 10 subjects, about 1 g of dentifrice composition of each composition was taken on a toothbrush, and the degree of non-irritation to gingiva when brushing for 3 minutes, <1> 1 point to feel strong stimulation of gingiva, <2> 2 points to feel slight stimulation of gingiva, <3> 3 points to hardly feel stimulation to gingiva, <4> No stimulation to gingiva Was evaluated based on the following criteria from the average score of 10 people. The evaluation results of 10 people were averaged, and the brushing feeling was judged according to the following evaluation criteria.
(Evaluation criteria)
◎: Average point 3.5 points or more and 4.0 points or less ○: Average point 3.0 points or more and less than 3.5 points △: Average point 2.0 points or more and less than 3.0 points ×: Average point 1.0 points More than 2.0 points

  From the results of Tables 3 to 6, the dentifrice composition containing (A) the synthetic amorphous aluminum-bonded silicate of the present invention and (B) the granular zeolite has an appropriate abrasiveness and high cleaning properties, and During use, it was confirmed that both excellent wiping feeling (brushing sensation) derived from granular zeolite and lack of irritation to gingiva were compatible.

Claims (5)

(A) Synthesis amorphous aluminum in the range of 0.5 to 7.5 wt% with respect to SiO ₂ as Al ₂ O _3, and OH group content is 2.0 to 3.5 wt% with respect to SiO ₂ A dentifrice composition comprising an aluminum-bonded silicate and (B) granular zeolite having an average particle size of 150 to 800 μm and an average disintegration strength of 15 to 100 g / piece.   (A) Component Amorphous Aluminum Bonded Silicate reacts with water-soluble alkali metal silicate, water-soluble aluminum salt and mineral acid as essential raw materials in the presence of water-soluble alkali metal mineral salt electrolyte The dentifrice composition according to claim 1, wherein the dentifrice composition is obtained. The amount of the mineral electrolyte of the water-soluble alkali metal is 5 to 30% by mass with respect to SiO ₂ of the water-soluble alkali metal silicate as M ₂ O (where M represents an alkali metal). 2. The dentifrice composition according to 2.   4. The granular zeolite as component (B) is a granular zeolite containing a zeolite, silicic acid anhydride, titanium oxide and / or aluminum oxide as raw material components and prepared in the form of granules. The dentifrice composition according to Item.   The content of the synthetic amorphous aluminum-bonded silicate as the component (A) is 5 to 35% by mass, and the content of the granular zeolite as the component (B) is 3 to 20% by mass. The dentifrice composition according to Item.