JP2013155165A - Dentifrice - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dentifrice which can improve property of removing dental plaque or contamination and which allows for sufficiently feeling its presence and effect in an oral cavity.SOLUTION: A dentifrice includes the following ingredients (A) and (B): (A) granules including zeolite and a water soluble inorganic binder, and (B) granules having higher wet collapse strength than that of (A).

Description

  The present invention relates to a dentifrice containing granules.

  2. Description of the Related Art In recent years, dentifrices containing granules that can effectively remove dental plaque that causes dental caries and periodontal disease and can feel the effect in the oral cavity are known. These granules are substantially spherical agglomerated particles so as not to damage the enamel and gums on the tooth surface, and contain functional materials such as drugs, enzymes, and abrasives. Some are aimed at visual effects.

  For example, a dentifrice using granules containing a water-insoluble powder material such as calcium carbonate (see Patent Document 1) and a dentifrice using silica granules that disintegrate by applying a certain load (see Patent Document 2). Are known. Since these granules disintegrate to a certain size during the brushing process, the frictional force generated between the tooth surface and the granules can exert plaque removal effects, and the granules in the mouth You can feel the presence and effect.

  In addition, for example, a dentifrice using granules obtained by binding a water-insoluble powder material such as zeolite known to have preventive effects such as calculus formation with a water-insoluble inorganic binder such as colloidal silica (Patent Document) 3) is also known.

JP 2010-173986 A JP 2010-275260 A JP-A-1-299211

  However, when using zeolite as a dentifrice granule, in order to demonstrate good disintegration in the process of brushing teeth while maintaining an appropriate strength in a dentifrice containing a large amount of water, further investigation is required. Cost. In addition, any of the above-mentioned dentifrices can still increase the frictional force generated between the tooth surface and the granules to improve the plaque or dirt removal performance, while maintaining a good feeling in the oral cavity. There is room for improvement.

  Therefore, the subject of this invention is providing the dentifrice which can fully improve the plaque or dirt removal performance of the conventional granule containing dentifrice, and the presence feeling and effect of the granule in an oral cavity.

  Therefore, the present inventor uses a specific granule together with a granule containing a zeolite and a water-soluble inorganic binder, resulting in a dramatic increase in the contact area between the tooth surface and the granule in the process of brushing teeth. The present inventors have also found that the frictional force generated between the tooth surface and the granule is remarkably increased and exhibits an excellent effect of removing plaque or dirt, thereby completing the present invention.

That is, the present invention includes the following components (A) and (B):
(A) A dentifrice containing granules containing a zeolite and a water-soluble inorganic binder, and (B) granules having higher wet disintegration strength than the granules (A).

According to the present invention, in a dentifrice, the shape and strength of the granule are maintained well, and it exhibits good disintegration during brushing, and the friction generated between the tooth surface and the granule due to the mixing of specific granules. The force is remarkably increased, and plaque and dirt are pushed out from a narrow region between the teeth, and an excellent effect of removing plaque and dirt such as colored dirt can be exhibited.
Further, the presence and effect of the granules can be palpated well in the mouth, and an excellent usability can be brought about.

It is a figure which shows the result of the frictional force test of Examples 1-2 and Comparative Examples 1-4.

Hereinafter, the present invention will be described in detail.
The dentifrice of the present invention contains granules (A) containing zeolite and a water-soluble inorganic binder.

  As the zeolite contained in the granules (A), natural ones contain impurities and lack homogeneity, so synthetic ones, ie synthetic zeolites, are preferred, and A-type zeolites are more preferred.

  The particle size of the zeolite itself, that is, the primary particle size is preferably 0.1 to 20 μm, and more preferably 10 μm or less. In the case of the dentifrice of the present invention, even if it is a dentifrice containing granules (A) obtained by granulating particles having a low average particle size and low abrasiveness, a colored pellicle strongly adsorbed on the tooth surface can be obtained. It produces a sufficient polishing force to whiten the teeth, reduces the polishing force after the granule collapses, and can impart the characteristics of not damaging the teeth even for a long time of brushing operation (low harm) Excellent plaque removal effect and stain removal effect such as colored stains can be exhibited.

  On the other hand, if the average particle size of the zeolite is small, there is an advantage that the ion exchange ability is enhanced, and the effect of removing plaque or dirt and the effect of preventing calculus are further enhanced. In this case, the smaller the particle size, the higher the ion exchange capacity and the higher the plaque removal effect. However, in consideration of the polishing effect, the average particle size of the primary particles of the zeolite used is preferably 0.5 to 10 μm. -8 μm is more preferable, and 2-7 μm is more preferable. The average particle diameter can be measured with a laser diffraction / scattering particle size distribution measuring apparatus.

Examples of the water-soluble inorganic binder contained in the granules (A) include sodium silicate, polyacrylic acid, processed celluloses, polyvinyl pyrrolidone, and silicone. Among these, sodium silicate is preferable from the viewpoint of satisfactorily exerting the effects of the present invention. Such sodium silicates include sodium metasilicate (Na ₂ SiO ₃ ), sodium orthosilicate (Na ₄ SiO ₄ ), sodium disilicate (Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ Si ₄ O ₉ ), and These hydrates can be mentioned, but they are generally represented by a molecular formula of Na ₂ O.nSiO ₂ .mH ₂ O. The coefficient n (molecular ratio of SiO ₂ · Na ₂ O) is called a molar ratio and can be expressed by the following formula (I).
Molar ratio = mass ratio (SiO ₂ mass% / Na ₂ O mass%) × Na ₂ O molecular weight / SiO ₂ molecular weight (I)

  Although the physical properties of sodium silicate vary depending on the molar ratio, the molar ratio is preferably 2.0 to 4.0, more preferably 2.4 to 3, from the viewpoints of laws and regulations (outside original regulations) and the pH of the resulting granules. 0.5, more preferably 2.8 to 3.5, and even more preferably 3.0 to 3.3. In addition, m is preferably in the range of 0 to 46.

The granule (A) has moderate durability against disintegration, but its wet disintegration strength is lower than the wet disintegration strength of the granule (B) described later. Therefore, when the dentifrice of the present invention is used, the granules (A) disintegrate first in the oral cavity, and then the granules (B) having a higher wet disintegration strength than the granules (A) It will collapse in the presence, the contact area between the tooth surface and the granule will increase dramatically, the frictional force between the tooth surface and the granule generated in the process of brushing teeth will remarkably increase, The dirt removal performance can be remarkably improved. The wet disintegration strength of the granule (A) increases the contact area between the tooth surface and the granule in combination with the granule (B), and also penetrates into a narrow region between the teeth and the dental plaque and While extruding dirt, it is possible to effectively increase the frictional force generated between the tooth surface and the granule by the brushing load, to feel the granule in the mouth, to recognize the effect of removing plaque or dirt, and to suppress the feeling of foreign matter However, it is preferably 10 to 55%, more preferably 20 to 50% from the viewpoint of exerting a remarkable polishing force.
In addition, the wet disintegration strength of the granules (A) is measured by the method described in the examples.

In addition, the disintegration strength of the granules (A) is preferably 1 to 10 gf / piece (disintegrated with a load of 1 to 10 g per granule), more preferably 2 to 7 gf / piece, more preferably 3 to 4 gf / piece. It is a piece.
In addition, the disintegration intensity | strength of a granule (A) is measured by the method as described in an Example.

The average particle size of the granule (A) has sufficient polishing power, and after the granule collapses, it also enters a narrow region between the teeth and the tooth gap, and also occurs between the tooth surface and the granule in this region. From the viewpoint of effectively increasing the frictional force, it is preferably 500 μm or less, more preferably 50 to 400 μm, more preferably 75 to 350 μm, and further preferably 100 to 300 μm.
In addition, an average particle diameter can be measured by the method as described in an Example.

  The dentifrice blended with the granules (A) has the property that the pH of the 10-fold diluted solution of the dentifrice after granule disintegration is higher than the pH of the 10-fold diluted solution of the dentifrice before granule collapse, that is, the dentifrice at the time of disintegration It has an agent pH raising property. Accordingly, the pH of the 10-fold diluted solution of the dentifrice after granulation of the dentifrice granule is preferably 8.0 to 10.5, more preferably 8.5 to 10.5, and still more preferably. 9.0-10.5. Further, the difference between the pH of the 10-fold diluted solution of the dentifrice after granule disintegration of the granule for dentifrice of the present invention and the pH of the 10-fold diluted solution of the dentifrice before granule breakdown (post-collapse dentifrice pH-pre-collapse dentifrice) The agent pH) is preferably 0.1 to 1.0, more preferably 0.15 to 0.8, and still more preferably 0.2 to 0.5.

Due to the property of raising the pH, the dentifrice of the present invention is considered not only excellent in the usual dirt removing effect but also particularly excellent in the plaque removing effect. The reason is that when the granule (A) disintegrates in the gap between the teeth, the pH rises locally, so that it effectively acts on dental plaque containing proteins that are particularly present in the gap between the teeth, It is considered that the plaque removal effect is remarkably excellent due to the adhesive structure destruction action of protein-containing plaque by alkali.
The pH of the 10-fold diluted solution of the granule (A) -containing dentifrice after the disintegration of the granule (A) and the pH of the 10-fold diluted solution of the granule (A) -containing dentifrice before the disintegration are the methods described in the examples. Can be measured.

  In addition, the granule (A) has a water absorption rate of preferably 60 to 150% by mass, more preferably 80 to 130%, based on the weight of the granule (A), from the viewpoint of improving the separation stability of the dentifrice. It is mass%, More preferably, it is 100-120 mass%. The granule (A) does not disintegrate itself even if it absorbs a large amount of water in this way, and when it disintegrates in the oral cavity, a large amount of water having a high pH that has been absorbed inside is released. Highly preferred for destroying dirt. In addition, a water absorption rate can be measured by the method as described in an Example.

Furthermore, the granule (A) does not rapidly disintegrate due to the load of brushing, but changes its shape and has moderate durability against disintegration. That is, the deformation ratio of the granule (A) is preferably 3 to 40%, more preferably 5 to 35%, and still more preferably 10 to 30%. Thus, since it has moderate durability against disintegration, it is possible to effectively remove even the plaque behind the teeth. In particular, when used in combination with the granule (B), the contact area between the tooth surface and the granule is dramatically increased, the frictional force is increased, and it is possible to effectively remove even the plaque behind the teeth. is there.
The deformation rate of the granule (A) means a value represented by the formula (II) obtained from a shape displacement that collapses when the granule is compressed with a load of 3.0 gf / piece. Can be measured by the method described in Examples.
Deformation rate (%) = shape displacement of the granule at the time of disintegration (μm) / particle diameter of the granule before the disintegration (μm) × 100 (II)

  The content of the zeolite in the granule (A) is preferably 75 to 99% by mass, more preferably from the viewpoint of dryness and disintegration in water, polishing power after granule disintegration and prevention of damage to teeth. It is 85-98 mass%, More preferably, it is 89-97.5 mass%, More preferably, it is 93-97 mass%. The content of the water-insoluble powder material in the granule (A) is a value obtained by extracting the granule (A) from the dentifrice, washing it with a solvent, and removing water by heating and drying.

  The content of the water-soluble inorganic binder in the granule (A) shows the dryness of the granule, the disintegration strength in water, the stability in dentifrice, and the pH increase property in the locality of the granule (A) From a viewpoint of making it, 1-25 mass% is preferable, 2-15 mass% is more preferable, 2.5-11 mass% is further more preferable, and 3-7 mass% is still more preferable. The content of sodium silicate in the granule (A) is a value obtained by extracting the granule (A) from a dentifrice, washing it with a solvent, and removing moisture by heating and drying.

  In the granule (A), the mass ratio of the water-soluble inorganic binder to the zeolite is preferably 0.005 to 0.00 from the viewpoint of improving the dryness of the granule, the disintegration strength in water and the stability in dentifrice. 30, more preferably 0.01 to 0.28, still more preferably 0.01 to 0.15, still more preferably 0.02 to 0.13, and even more preferably 0.02 to 0.10, and 0.03-0.08 is more preferable. Usually, in order to increase the disintegration strength of granules and the stability in dentifrice, it is necessary to increase the amount of binder. However, although the reason is not clear, when a water-soluble inorganic binder, especially sodium silicate, which is a water-soluble component, is used, the amount of the water-soluble inorganic binder is different from that of the zeolite. By making it into a specific range or less, the strength of the granule in the multi-moisture composition such as a dentifrice is further improved, and the stability is further improved.

  The granule (A) can further contain other components other than zeolite and the water-soluble inorganic binder, for example, water-insoluble fibers, medicinal components, and colorants as long as they do not affect the present invention. These may be used alone or in combination of two or more.

  The content of the water-insoluble fiber, medicinal component, and colorant is preferably 3 parts by mass or less in total with respect to 100 parts by mass of the total amount of zeolite and water-soluble inorganic binder from the viewpoint of disintegration feeling. The following is more preferable, 0.1 parts by mass or less is further preferable, and it is particularly preferable not to blend.

  The granule (A) used in the present invention is prepared, for example, by mixing a zeolite, a water-soluble inorganic binder, and water by a batch method, a continuous method, a semibatch method or the like to prepare a water slurry, and then drying the obtained water slurry. It is manufactured by doing. Granule (A) is usually produced by mixing a zeolite, a water-soluble inorganic binder and water to prepare a water slurry and drying it. Such a water-soluble inorganic binder, especially sodium silicate, is distributed uniformly in the granules as the water evaporates during the water slurry drying, preferably when the water slurry is spray dried, and has a function of increasing the strength of the granules. Have.

When sodium silicate is used as the water-soluble inorganic binder, the SiO ₂ is a 28.0 to 38.0% by mass aqueous solution, the Na ₂ O is 9.0 to 19.0% by mass, A degree of 40 or more is preferred, SiO ₂ is an aqueous solution of 28.0 to 36.0% by mass, Na ₂ O is 9.0 to 15.0% by mass, and a Baume degree at 15 ° C. is 40. To 57, more preferably an aqueous solution of 28.0 to 30.0% by mass of SiO ₂ , 9.0 to 10.0% by mass of Na ₂ O, and a Baume degree of 40 to 40 at 15 ° C. 53 is more preferable. The Baume degree can be measured according to the description of JISZ8804 (established on September 1, 1960, last revised on March 1, 1994).

  When using the aqueous sodium silicate solution as described above, it may not be necessary to add water because it contains water, but it is usually preferable to add water separately. From the viewpoint of obtaining productivity and desired disintegration strength, the amount of water is adjusted so that the solid content concentration in the water slurry is 30 to 60% by mass including water of the water-soluble inorganic binder aqueous solution. Is preferable, and it is more preferable to adjust so that it may become 40-60 mass%.

  The mixing temperature of each component should just be about normal room temperature, and 5-40 degreeC is preferable. The mixing time is not particularly limited as long as the solid content concentration becomes uniform to some extent, but is usually 10 to 300 minutes, preferably 20 to 180 minutes, and preferably 30 to 120 minutes.

  The method of drying the water slurry is preferably a method using a spray dryer or a fluidized bed dryer from the viewpoint of productivity. From the viewpoint of the disintegration strength of the granules, the sphericity of the granules, and the thermal efficiency, a countercurrent spray is used. A spray drying method such as a drying tower is more preferable.

  The content of the granule (A) in the dentifrice of the present invention is a friction that increases the contact area between the tooth surface and the granule sufficiently by the load of brushing in combination with the granule (B) described later after disintegrating in the oral cavity. From the viewpoint of enhancing the force, improving the plaque and dirt removal effect, and from the viewpoint of giving a palpable feel (sharpness) in the mouth, it is preferably 1 to 25% by mass. Preferably it is 3-15 mass%, More preferably, it is 5-11 mass%. The content of the granule (A) in the dentifrice is a value obtained by extracting the granule (A) from the dentifrice, washing it with a solvent, and removing moisture by heating and drying.

  The dentifrice of the present invention contains the granule (A) and a granule (B) having a higher wet disintegration strength than the granule (A). Thereby, when the dentifrice of this invention is used, the granule (A) which has moderately low wet disintegration strength in an oral cavity, and moderate durability with respect to disintegration disintegrates first, and then from a granule (A) Tooth that occurs in the process of brushing teeth because the granule (B) with high wet disintegration strength disintegrates in the presence of the disintegrant of granule (A), and the contact area between the tooth surface and the granule increases dramatically. The frictional force between the surface and the granule is remarkably increased, and the plaque or dirt removing performance can be remarkably improved. As the granule of such component (B), a granule (b-1) containing a water-insoluble powder material and containing no binder, and / or a granule containing a water-insoluble powder material and a water-insoluble binder (b- 2) is preferred.

  The granule (b-1) that can be used as the granule (B) is a granule containing a water-insoluble powder material and no binder. Examples of the water-insoluble powder material include silica, magnesium carbonate, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium phosphate, calcium pyrophosphate, calcium sulfate, and the like. As the water-insoluble powder material used in -1), silica is more preferable from the viewpoint that it can be easily granulated without containing a binder. Such a binder is not limited to an organic binder and an inorganic binder, and means not only a water-soluble binder but also a water-insoluble binder.

  Thus, by manufacturing the granule (b-1) without using a binder, not only can the cost be reduced, but the wet disintegration strength is moderately low by mixing with the granule (A). And the granule (A) which has moderate durability with respect to disintegration disintegrates first, and then the granule (B) having higher wet disintegration strength than the granule (A) disintegrates in the presence of the disintegrant of the granule (A). Therefore, it is possible to contribute to an increase in the contact area between the tooth surface and the granules, and it is also possible to easily adjust the hardness and size of the granules that can be palpated in the mouth.

  Among these, the granule (b-1) does not rapidly disintegrate due to the load of brushing, but disintegrates after gradually changing its shape, so that the wet disintegration strength is moderately low and moderate durability against disintegration. Since the granule (A) having the property disintegrates first, and then the granule (B) having a wet disintegration strength higher than that of the granule (A) is gradually deformed, it disintegrates in the presence of the disintegrant of the granule (A). It is considered that the contact area between the tooth surface and the granule can be increased, and the frictional force generated between the tooth surface and the granule can be dramatically increased and maintained. From this viewpoint, the deformation rate of the granule (b-1) is preferably 20 to 70%, more preferably 30 to 60%, and further preferably 40 to 55. The deformation rate of the granule (b-1) means a value calculated by the same method as the deformation rate of the granule (A).

  In the granule (b-1), 70 to 100% of the granule (b-1) is preferably spherical, and more preferably 80 to 100% is spherical. The spherical shape has a generally smooth surface having no depressions or protrusions whose overall shape cannot be determined as a spherical shape, and the diameters in the vertical direction and the width direction are substantially equal visually. In addition, when it is recognized that the granule is missing due to mixing or the like, the overall shape is determined by a virtual surface supplemented with the missing portion, and the spherical shape is determined when the overall shape is determined to be spherical. And the quantity ratio of the granule judged to be spherical among a plurality of visually observed granules (50 to 100) is shown. Specifically, when a plurality of granules are sampled at random and visually observed 200 to 300 times with a microscope (for example, KEYENCE, digital high-definition microscope), it is determined that the surface is a smooth sphere or missing. When the missing part is covered with a virtual surface, the number ratio of the number of granules determined to be spherical to the total number of granules is shown. Whether or not the chip is missing is determined because the surface state of the chipped portion is not smooth.

  The wet disintegration strength of the granule (b-1) is that when used in a dentifrice, the granule can be palpated in the mouth and the effect can be recognized, but also plaque or dirt without damaging the teeth. From the viewpoint of having the removal power of, it is preferably 51 to 90%, more preferably 56 to 85%, and further preferably 60 to 80%, on condition that the value is higher than the disintegration strength of the granule (A). It is. In addition, the wet disintegration strength of the granule (b-1) is measured by the same method as the wet disintegration strength of the granule (A).

  In addition, the disintegration strength of the granules (b-1) is preferably 0.1 to 100 gf / piece from the viewpoint that the granules can be palpated in the mouth and disintegrate by brushing without damaging the teeth. From the viewpoint of obtaining, it is preferably 5 gf / piece or more, more preferably 10 gf / piece or more, and from the viewpoint of preventing a sense of incongruity or foreign matter, it is preferably 50 gf / piece or less, and further 35 gf / piece or less. It is preferable that In addition, the disintegration strength of the granule (b-1) is measured by the same method as the disintegration strength of the granule (A).

  The average particle diameter of the granule (b-1) is preferably 100 to 300 μm, more preferably 150 to 250 μm. In addition, the average particle diameter of a granule (b-1) means the value computed by the method similar to the average particle diameter of a granule (A).

  In addition to the above water-insoluble powder material, the granule (b-1) may further contain water-insoluble fibers, medicinal components, and colorants.

  The granule (b-1) is preferably produced by a wet method, specifically, preferably produced by a precipitation method or a gel method, more preferably produced by a gel method. For example, in the case of producing by a wet gel method using silica as an insoluble powder material, a method of synthesis by a neutralization reaction between a water alkali metal silicate and a mineral acid may be used. Sodium acid and sulfuric acid are used, either of which may be used. More specifically, it is performed by first mixing an alkali metal, a silicate and a mineral acid to form a silica sol, gelling the silica sol to obtain a silica hydrogel, and drying the obtained silica hydrogel. It is. In order to spheroidize the silica hydrogel, for example, the silica hydrogel whose pH has been adjusted in advance is suspended in a non-affinity oil-like medium, and solidified in the suspension to remove impurities by washing. Thereafter, a drying method or a method in which silica hydrosol is sprayed into the air to form a gel and impurities are washed away and then dried can be used.

  The granule (b-2) that can be used as the granule (B) is a granule containing a water-insoluble powder material and a water-insoluble binder. Thus, by mixing the granule (b-2) with the granule (A), the granule (A) having moderately low wet disintegration strength and moderate durability against disintegration first collapses, Since the granule (B) having a wet disintegration strength higher than that of the granule (A) disintegrates in the presence of the granule (A) disintegration product, it can contribute to an increase in the contact area between the tooth surface and the granule, and further in the mouth It is also possible to easily adjust the hardness and size of the granule to the extent that it can be touched.

Examples of such water-insoluble powder materials include calcium carbonate, magnesium carbonate, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium phosphate, calcium pyrophosphate, calcium sulfate, etc. The water-insoluble powder material used in (b-2) is preferably calcium carbonate from the viewpoint of weak alkalinity and excellent plaque removal effect. When calcium carbonate is used as the water-insoluble powder material, the average particle size thereof is preferably 0.1 to 20 μm, more preferably 0. It is 5-10 micrometers, More preferably, it is 1-5 micrometers. This average particle diameter can be measured with a laser diffraction / scattering particle size distribution analyzer. The specific surface area of the calcium carbonate, from the viewpoint of stain removal force is preferably ^{1~10m 2 / g, 2~8m 2 /} g is more preferable. This specific surface area can be determined by the BET method using N ₂ gas adsorption.

  Examples of the water-insoluble binder contained in the granule (b-2) include a water-insoluble inorganic binder and a water-insoluble organic binder. Among these, from the viewpoint of operability during granulation, a water-insoluble inorganic binder is preferable, specifically, colloidal silica, magnesium aluminate metasilicate, synthetic aluminum silicate, calcium silicate, alumina sol, and the like. A silicon-based compound having a hydroxyl group such as colloidal silica is more preferable.

  Since the granules (b-2) are unevenly distributed and form an outer shell of the granules, the granules (b-2) can exhibit good disintegration while having an appropriate strength, and have an appropriate wet disintegration strength. The granule (A) having a low and moderate durability against disintegration is first disintegrated, and then in the presence of the disintegrant of the granule (A), the granule (B) having a higher wet disintegration strength than the granule (A) Since the outer shell collapses at once, the frictional force generated between the tooth surface and the granules can be increased at once, and an excellent granular feeling can be exhibited.

  The wet disintegration strength of the granule (b-2) is that when used in a dentifrice, the granule can be palpated in the mouth and the effect can be recognized, but also plaque or dirt without damaging the teeth. From the viewpoint of having the removal power of, it is preferably 40 to 90%, more preferably 44 to 85%, and further preferably 50 to 80%, on condition that the value is higher than the disintegration strength of the granule (A). It is. In addition, the wet disintegration strength of the granule (b-1) is measured by the same method as the wet disintegration strength of the granule (A).

  Further, the disintegration strength of the granule (b-2) is preferably 0.1 to 10 gf / piece from the viewpoint of allowing the granule to be palpated in the mouth and disintegrating by brushing without damaging the teeth. From the viewpoint of obtaining a granular feeling, it is preferably 7 gf / piece or more, and from the viewpoint of preventing a feeling of discomfort or a foreign object feeling, it is preferably 9 gf / piece or less. The disintegration strength of the granule (b-2) is measured by the same method as the disintegration strength of the granule (A).

  In addition to the water-insoluble powder material and the water-insoluble binder, the granule (b-2) may further contain a water-insoluble fiber, a medicinal component, and a colorant.

  The granule (b-2) is produced by, for example, mixing a water-insoluble powder material and a water-insoluble binder by a batch method, a continuous method, a semi-batch method, etc., preparing an aqueous slurry, and then drying. The From the viewpoint of productivity, it is preferable to use a spray dryer or a fluidized bed dryer for drying, and more preferably a spray dryer. Next, from the viewpoint of increasing the disintegration strength of the granule (b-2), it is preferable to further subject to aging treatment.

  As a granule (B) used in the dentifrice of this invention, either one of a granule (b-1) and a granule (b-2) may be used, and both may be used together. Among them, from the viewpoint of effectively increasing the contact area between the granule and the tooth surface while maintaining disintegration in the oral cavity in combination with the granule (A), the granule (b-1) is used as the granule (B-1). ) Is preferably used.

  The content of the granule (B) in the dentifrice of the present invention, in combination with the granule (A) that disintegrates in the oral cavity, from the viewpoint of sufficiently increasing the contact area between the tooth surface and the granule by the load of brushing, The total of b-1) and granule (b-2) is preferably 0.2 to 20% by mass, more preferably 0.5 to 15% by mass, and further preferably 1 to 10% by mass. . The content of the granule (B) in the dentifrice is a value obtained by extracting the granule (B) from the dentifrice, washing it with a solvent, and removing moisture by heating and drying.

  The mass ratio (A: B) of the content of granules (A) and the total content of granules (B) in the dentifrice of the present invention is such that each granule disintegrates in the mouth while From the viewpoint of effectively increasing the frictional force, it is preferably 1.7: 1 to 10: 1, more preferably 1.5: 1 to 8: 1, and still more preferably 1.3: 1 to 6 :. 1.

  The dentifrice of the present invention can be prepared by a conventional method. At this time, as components other than the granule (A) and the granule (B), components usually used in dentifrices, such as binders, wetting agents, sweeteners, surfactants, preservatives, perfumes, medicinal products Ingredients, colorants, excipients, water and the like can be included.

  Examples of the binder include sodium carboxymethyl cellulose, sodium polyacrylate, hydroxyethyl cellulose, thickening silica, montmorillonite, xanthan gum, carrageenan, sodium alginate, guar gum, pectin and the like. The content of the binder in the dentifrice of the present invention is preferably 0 from the viewpoint of sufficiently increasing the contact area between the tooth surface and the granules by the brushing load in combination with the granules (A) that disintegrate in the oral cavity. 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 3% by mass.

Examples of the wetting agent include sorbitol, propylene glycol, 1,3-butylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, xylitol, maltitol, lactitol, erythritol, and the like. Thaumatin) and aspartylphenylalanine methyl ester. The content of the wetting agent in the dentifrice of the present invention is preferably 1 to 2, in combination with the granules (A) that disintegrate in the oral cavity, from the viewpoint of sufficiently increasing the contact area between the tooth surface and the granules by the load of brushing. It is 60 mass%, More preferably, it is 5-55 mass%, More preferably, it is 10-50 mass%.
The said component can be used individually by 1 type or in combination of 2 or more types.

  The content of water in the dentifrice of the present invention is such that, while maintaining the shape and strength of the granules in the dentifrice, it exhibits good disintegration during brushing, and when specific granules are mixed, The contact area between the tooth surface and the granule is dramatically increased and the frictional force is increased, so that plaque and dirt are pushed out from a narrow area between the teeth and the tooth gap. In the dentifrice of this invention from the point which can exhibit a dirt removal effect, Preferably it is 10-65 mass%, More preferably, it is 20-55 mass%.

Hereinafter, the present invention will be specifically described based on examples. In addition, unless otherwise indicated in a table | surface, content of each component shows the mass%.
Each physical property value was measured by the following method.

(1) Solid content of water-insoluble powder and sodium silicate aqueous solution It was calculated by removing volatilization free water measured under the conditions of 105 ° C. and Auto using an infrared moisture meter (manufactured by Kett Scientific Laboratory, FD240).

(2) 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 under-sieving weight distribution by the sieving method, and this is used as the average particle diameter.

(3) Disintegration strength of granules Ten granules near the average particle diameter were measured using a micro-compression tester (manufactured by Shimadzu Corporation, trade name: MCTM-500) and expressed as an average value.

(4) Wet disintegration strength of granules First, the granules having a particle size of 150 to 180 µm are vibrated for 5 minutes using a sieve of 500, 355, 250, 180, 150, 125, 90, 63, 45 µm according to JISZ8801-1. Was weighed as a sample (granules before disintegration). Next, 15 g of a stainless steel sphere (diameter 4 mm), 3 g of a granule sample, and 30 mL of ion-exchanged water were put into a screw tube (manufactured by Maruemu Co., No. 6) and inverted once. 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 (granulated granule) is filtered through a 150 μm sieve, dried at 105 ° C. for 30 minutes, then cooled to room temperature with a desiccator, and the 150 μm sieve is made into a micro-type electromagnetic vibrator (made by Tsutsui Riken Kikai Co., Ltd.). , Shaken with a micro type electromagnetic vibration sieve, M-2) for 5.5 minutes, and then weighed. The value calculated by the following formula was defined as the wet disintegration strength.
Wet disintegration strength (%) = granule mass after disintegration remaining on the 150 μm sieve ÷ granule mass before disintegration × 100

(5) Change in pH before and after disintegration of granules Take 2 g of granules (A), add 20 mL of ion-exchanged water, measure the resulting liquid with a pH meter, and obtain a stable (about 1 minute) value. It was set as the value of pH (10% diluted solution) before granule disintegration. Then, after adding a stirrer piece and stirring for 30 minutes, the value measured on the same conditions as the above was made into the value of pH (10% diluted solution) after granule disintegration.

(6) Water absorption amount of granules 8 g of granules were measured in a 50 mL beaker, ion-exchanged water was dropped little by little, and the mass of water when water separation occurred on the surface of the granules was weighed. The value calculated by the following formula was defined as the water absorption rate.
Water absorption rate (%) = (mass of water at the time of water separation on the granule surface (g) ÷ 8 (g) × 100

(7) Deformation rate of granules Disintegration obtained when granules near the average particle diameter were compressed with a load of 3.0 gf / piece using a micro compression tester (manufactured by Shimadzu Corporation, trade name: MCTM-500). The shape displacement value up to this was taken as the shape displacement of the granule at the time of collapse, and the value calculated by the following calculation formula (II) was taken as the deformation rate.
Deformation rate (%) = shape displacement of the granule at the time of disintegration (μm) ÷ particle diameter of the granule before disintegration (μm) × 100 (II)
In addition, the granule composition of the granule (A) blended in the dentifrice of the present invention, the average particle size of the granule, the disintegration strength of the granule, the wet disintegration strength of the granule, the water absorption amount of the granule, and the deformation rate are extracted from the dentifrice. Then, it was measured by washing with a solvent and removing moisture by heating and drying.

[Production Example 1]
In the mixing ratio shown in Table 1, zeolite (Zeobuilder Co., Ltd., trade name: zeolite (powder), solid content 91.9%, average particle size of about 3 μm) and sodium silicate aqueous solution (Fuji Chemical Co., Ltd., trade name) : No. 3 sodium silicate (molar ratio represented by the above formula (I): 3.0 to 3.3, Baume degree: 40 to 53), solid content: 54.3%) and water, Disper blade (Ashizawa Niro atomizer Co., Ltd., model: HS-P3) was mixed to obtain a water slurry having a solid content of 47.8%. The water slurry was prepared by first introducing water into a mixing tank, then adding an aqueous sodium silicate solution, and then adding and mixing zeolite.
The obtained water slurry was spray-dried at a blowing temperature of 190 ° C. and then placed under room temperature conditions to obtain granules (A) having the granule characteristics shown in Table 2 and containing 4% by mass of sodium silicate.

[Production Example 2]
Granules (b-1) were prepared by a wet method (gel method). Specifically, first, sodium silicate and sulfuric acid were mixed to produce a silica sol, which was sprayed into the air to be gelled and spheroidized. Subsequently, the spherical silica hydrogel obtained was washed with water to remove impurities, hydrothermally treated in an aqueous solution of pH 9.0 at 90 ° C. for 8 hours, filtered, air-dried at a temperature of 110 ° C. for 90 seconds, and classified ( 150 to 500 μm) to obtain granules (b-1) having the granule characteristics shown in Table 2.

[Production Example 3]
Calcium carbonate (Toyo Denka Kogyo Co., Ltd., trade name: Toyo White, solid content 99.7%, average particle size of about 2 μm, specific surface area of about 4 m 2 / g) and colloidal silica (Nissan Chemical Co., Ltd., trade name: Snowtex S, solid content: 30.5%), cellulose (manufactured by Nippon Paper Chemical Co., Ltd .: KC Flock, solid content: 95.0%), and water at a slurry composition ratio shown in Table 1 To obtain an aqueous slurry. In addition, water slurry preparation was performed by throwing water into a mixing tank first, then throwing colloidal silica, adding calcium carbonate, adding cellulose further, and mixing.
The obtained water slurry is spray-dried at a blowing temperature of 190 ° C., placed in a polyethylene zippered bag (trade name: Unipack), stored for 7 days under a temperature of 30 ° C., and has the granule characteristics shown in Table 2. Granules (b-2) were obtained.

[Examples 1-2, Comparative Examples 1-4]
Using the granules obtained in Production Examples 1 to 3, a dentifrice having the composition shown in Table 3 was produced, and according to the following method, measurement of frictional force between granules and tooth surfaces, granule feeling, plaque removal effect and The change in pH of the dentifrice with and without granule blending was evaluated. The results are shown in Table 4.

(1) Measuring method of frictional force between granule and tooth surface When brushed machine is cleaned with brush, the brushing machine's toothbrush holder's vertical displacement and toothbrush retention The frictional force generated between the granule and the tooth surface was determined by measuring the amount of displacement (strain amount centered on the fulcrum in FIG. 1) in the moving direction of the test table. As for the cleaning conditions, the object to be cleaned was an acrylic plate with a flat surface, the toothbrush was a check standard (manufactured by Kao Corporation), the load on the toothbrush was 100 g, and the test table was moved at a speed of 60 rpm. The stroke width was 30 mm.
Specifically, it was carried out without applying each dentifrice to the object to be cleaned, based on the frictional force tested by applying 1 g of each dentifrice to the object to be cleaned on the test bench of the brushing machine without dilution. The value obtained by subtracting the frictional force was the frictional force generated between the granules and the tooth surface.
In addition, about the measurement result of the frictional force between a granule and a tooth surface, it represents with the index | exponent which set the value in the dentifrice of the comparative example 1 to 100, and the result graphed is shown in FIG.

(2) Evaluation method of granule feeling Paneler: 10 people pass one by one to evaluate monadic evaluation items.
Usage: Change to the usual dentifrice and take a certain amount of evaluation sample and brush.
Evaluation item:
1. Overall evaluation 2. Feel of grain Feel of grain hardness 4. Teeth feel smooth. Dirty feeling (good evaluation-bad evaluation: 5 points, 4 points, 3 points, 2 points, 1 point)
The total score of the evaluation of the above 10 people is written.

(3) Evaluation method of plaque or dirt removal effect Red lipstick (Orb: RD305, manufactured by Kao Corporation) is applied to the groove of the interdental model (5 Pasteur pipettes of φ4 are aligned and fixed). Thereafter, the excess lipstick was brushed (until red color disappeared) with a toothbrush (the tip of the hair is a ball (registered trademark): normal) and dishwashing. A certain amount of each toothpaste sample was taken on the model and cleaned until the lipstick did not fall off. The lipstick remaining in the model was ultrasonically washed with 90 mL of ethanol for 10 minutes, and the poured solution was subjected to absorbance measurement (Abs) at 540 nm.
In addition, as a control (initial value), an extraction liquid which was ultrasonically washed with 90 mL of ethanol for 10 minutes after the above brushing washing was used. The plaque or dirt removal rate (%) in Evaluation Model 1 is based on the rate of decrease in absorbance (X) after evaluation with each dentifrice ((X0−X) / X0) × 100) relative to the absorbance (X0) of the control. Calculated.

(4) Change in pH of dentifrice before and after disintegration of granules 2 g of each dentifrice was taken, 20 mL of ion-exchanged water was added and stirred for 30 minutes, and the resulting liquid was measured with a pH meter and stabilized (about The value at the time of about 1 minute) was defined as the pH (10-fold dilution) of the dentifrice after granule disintegration.
Further, after each dentifrice was filtered using a 45 μm sieve defined in JISZ8801-1, 2 g of the obtained dentifrice was taken, and the value measured under the same conditions as above was the pH of the dentifrice before granule disintegration (10 times) The value of dilution).

  According to the result of FIG. 1 and Table 4, Examples 1-2 which used granule (A) and granule (b-1) or granule (b-2) together are comparative examples which used each granule independently. 1-3, and the comparative example 4 which used a granule (b-1) or a granule (b-2) together, the frictional force of a granule and a tooth surface increases notably, and the outstanding plaque removal effect is exhibited. Moreover, it turns out that it has a favorable granule feeling. Moreover, it turns out that granule (A) has the effect | action which increases the pH of a dentifrice at the time of disintegration.

Claims (9)

The following components (A) and (B):
(A) A dentifrice containing granules containing zeolite and a water-soluble inorganic binder, and (B) granules having a higher wet disintegration strength than the granules (A).   The component (B) is a granule (b-1) containing a water-insoluble powder material and no binder, and / or a granule (b-2) containing a water-insoluble powder material and a water-insoluble binder. The dentifrice according to 1.   The dentifrice of Claim 1 or 2 whose mass ratio (A: B) of a component (A) and a component (B) is 1.7: 1-10: 1. In the granule of component (b-1), the deformation rate of the particle represented by the formula (II) obtained from the shape displacement at the time of collapse when the granule is compressed with a load of 3.0 gf / piece is 20 to 70. The dentifrice of Claim 2 or 3 which is%.
Deformation rate (%) = shape displacement of the granule at the time of disintegration (μm) / particle diameter of the granule before the disintegration (μm) × 100 (II)   The dentifrice according to any one of claims 2 to 4, wherein the water-insoluble powder material in the component (b-1) is silica.   The dentifrice according to any one of claims 2 to 5, wherein the water-insoluble binder in the component (b-2) is a water-insoluble inorganic binder.   The dentifrice according to any one of claims 2 to 6, wherein the water-insoluble powder material in the component (b-2) is calcium carbonate.   The dentifrice according to any one of claims 1 to 7, wherein a mass ratio of the water-soluble inorganic binder to the zeolite (water-soluble inorganic binder / zeolite) in the component (A) is 0.005 to 0.30. Agent.   The dentifrice according to any one of claims 1 to 8, wherein the water-soluble inorganic binder in component (A) is sodium silicate.