JPH01299211A - Dentifrice - Google Patents

Abstract

PURPOSE:To obtain a dentifrice containing granules detectable in the mouth and giving little feeling of foreign matter in the mouth in spite of the recognition of the feeling of the cleaning effect, by granulating a water-insoluble powdery material with a water-insoluble inorganic binder and compounding the resultant granule having specific size and strength. CONSTITUTION:A water-insoluble powdery material having particle diameter of about 0.1-20mum and used as a conventional tooth polishing material (e.g., calcium hydrogen phosphate, insoluble sodium metasilicate, silica or zeolite) is granulated with a water-insoluble inorganic binder (preferably magnesium metasilicate aluminate or colloidal silica) to obtain a granule having particle size passing through a 30 mesh sieve but incapable of passing through a 200 mesh sieve and collapsing under a load of 0.1-10g per one granule. The granule is compounded to a dentifrice. The above binder is preferably a combination of a binder acting as an excipient and a binder having strong adhesivity to effect remarkable increase in the strength of granule.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a dentifrice containing granules that has an aesthetic effect and a stain-removing effect that can be recognized by the feel of the granules in the mouth. More specifically, although the granules contained in toothpaste are strong and large enough to be felt in the mouth, they gradually disintegrate during the process of brushing, which is unpleasant. This invention relates to a dentifrice containing granules that do not give a foreign body sensation.

[Conventional technology and its problems]

Dentifrices containing granules or granular substances have been known for a long time. Such granules include those containing functional materials such as drugs, enzymes, and abrasives, and those intended for aesthetic effects. In addition, conventional dentifrices include granules that are palpable immediately after brushing, but become unpalpable during tooth brushing;
There are some products that cannot be felt from the beginning and can only be seen with the naked eye. Various water-soluble and water-insoluble binders have been used as binders for these granules. As the water-soluble granule binder, various water-soluble polymer compounds such as methyl cellulose and carboxymethyl cellulose are used. However, granules prepared using such a water-soluble binder have no problems when used in a dry state such as pharmaceuticals, but they do not pose any problem when used in a dry state such as a pharmaceutical product, but when used in a high-moisture composition such as a toothpaste that contains a large amount of water. The strength of the granules decreases significantly, and the granules collapse during the mixing process during dentifrice manufacturing, and even if they retain their shape, they are softened and cannot be felt in the mouth at all, resulting in a loss of the presence and effectiveness of the granules. Unable to recognize feelings.

On the other hand, there are methods of using various organic binders as water-insoluble binders, such as methods of forming granules in which colorants and abrasives are bound with wax (JP-A-49-132249, JP-A-50-81594). ), or a method of granulating an abrasive powder such as calcium carbonate with a water-insoluble but ethanol-soluble binder, such as ethyl cellulose (Japanese Patent Application Laid-Open No. 1983-1999)
No. 126806), etc. are known. However, although granules granulated using these binders are stable in dentifrice, when they are hard and large enough to be palpable, they can be perceived as an unpleasant foreign body sensation in the mouth9 or a foreign body sensation. If the hardness was set to such a low level that it would not become visible, it would not be palpable during the day.

In addition, the method using the wax binder described above requires a hot melting process, and the method of dissolving the ethyl cellulose binder in an organic solvent involves risks such as fire, so equipment and strict regulations are required to prevent this. The disadvantage is that it requires a lot of manipulation.

Therefore, the object of the present invention is to provide granules that are visible to the naked eye, aesthetically pleasing, and have a size and strength that are palpable in the oral cavity, while providing a comfortable tactile feel and polishing effect without the sensation of a foreign body. It is an object of the present invention to provide a dentifrice containing granules that has the practical effect of increasing the abrasive power without damaging the dentifrice.

[Means to solve the problem]

As a result of extensive research into dentifrice granules from the above perspective, the present inventors found that a dentifrice containing granules of a water-insoluble powder material granulated with a water-insoluble binder that maintains a certain size and strength can be used in the mouth. Although the granules can be palpated and the effect can be recognized, there is almost no foreign body sensation, and it has been discovered that the polishing force can be increased without damaging the teeth, and in completing the invention. It's arrived.

That is, the present invention provides granules obtained by binding a water-insoluble powder material with a water-insoluble inorganic binder, which pass through a 30 mesh sieve (JIS standard, hereinafter the same) and pass through a 200 mesh sieve (JIB standard, hereinafter the same). The particle diameter size (equivalent to 75 to 500 μ) does not pass through (the same), and each granule has 0.
The present invention provides a dentifrice containing granules that disintegrate when a load of 1 to 10 f is applied.

The water-insoluble powder material used in the production of the granules of the present invention is
Dibasic calcium phosphate, tertiary calcium phosphate, insoluble sodium metaphosphate, silica, aluminum hydroxide,
Any compound commonly used as a tooth abrasive may be used, such as magnesium phosphate, calcium carbonate, calcium birophosphate, zeolite, composite aluminosilicate, magnesium carbonate, red iron oxide, and calcium sulfate.

Particles with a size of about 0.1 to 20μ are used, but even if particles with a low abrasive property of 10μ or less are granulated, sufficient abrasive force will be generated to remove colored pellicles that are strongly adsorbed to the tooth surface. After the granules disintegrate, the abrasive force decreases and does not damage the teeth even when brushing for a long time (low toxicity).
This feature can be provided. In particular, ion-exchangeable fine powder such as fine zeolite is most preferably used, and its ion-exchangeability has the advantage of additional effects such as plaque removal and tartar prevention. In this case, the smaller the defective particle size, the higher the ion exchange ability and the higher the plaque removal effect, but in consideration of the polishing effect, α is preferably about 5 to 10 μm. In addition, particles with a particle size of 10 to 20μ, which is normally used in anticipation of a polishing effect, can also be produced by the granulation of the present invention.
The initial abrasive power is enhanced and it is highly effective in removing dirt from teeth.
As the granules disintegrate into primary particles during tooth brushing, they hardly cause any damage to the teeth.

Binders for producing the granules of the invention are water-insoluble inorganic compounds. Prior art documents describe water-insoluble organic binders, but none describe water-insoluble inorganic binders. Examples of binders used in the present invention include colloidal silica, magnesium aluminate metasilicate, bentonite, montmorillonite, kaolin, synthetic aluminum silicate, calcium silicate, aluminum hydroxide, alumina sol, magnesium carbonate, synthetic hydrotalcite, oxidized Examples include magnesium and magnesium hydroxide, with silicon-based compounds being particularly preferred. Among these, magnesium aluminate metasilicate, synthetic aluminum sulfate, and colloidal silica are preferred from the viewpoint of operability in the spray granulation method. These inorganic binders can be used alone or in combination.

Among these, there are binders that work relatively rigidly to shape the granules (e.g., magnesium aluminate metasilicate, synthetic aluminum silicate), and binders that have strong adhesive properties and significantly increase the strength of the granules (e.g., , colloidal silica, and alumina sol), various types of granules can be obtained by freely changing the type and amount of powder materials while maintaining a predetermined strength.

These inorganic binders are preferably used in an amount of 10% or more and 80% or less in the granules.

Therefore, it is preferable that the water-insoluble powder material is present in an amount of 20% or more and 90% or less, but the blending ratio is appropriately selected depending on the type of water-insoluble powder material, the type of inorganic binder, and the manufacturing method.

Unlike organic binders, granules made with these inorganic binders are palpable at first, but give a sleet-like feel (crunchy feeling), and gradually disintegrate, making it possible to perceive the effect. It has characteristics. Note that binders other than the water-insoluble inorganic binder described above may be added within a range that does not impair the effects of the present invention. .

Furthermore, the present granules can also contain a coloring agent such as titanium oxide or ultramarine blue, and the aesthetic effect of the colored granules can be added to the dentifrice. It is appropriate that the coloring agent is incorporated in the granules in an amount of 0.01 to 10% by weight.

The particle size of the granules of the present invention is such that it passes through a mesh 111kL35 sieve but not through a mesh Nn2QO@ (75μ
~500μ). Granules need to be 75μ or larger to be visible to the naked eye and palpable in the oral cavity.

In general, the abrasive power of toothpaste abrasives increases as the particle size increases (it is said that the difference does not change much above about 30 μm), so the abrasive power is sufficiently high. However, large particles exceeding 500 μm have a strong rough texture and are unpleasant to use.

Furthermore, the granules of the present invention need to be disintegrated by the brushing operation during tooth brushing, and the strength of the granules is also important.

If the strength (hardness) of the granules collapses under a load of -0.1 per piece or less, the granules cannot be recognized.

In addition, if the strength of the granules does not collapse under a load of 102 or more,
When this is added to toothpaste, it only feels like a foreign body, and it does not disintegrate at all even when brushing, potentially damaging tooth enamel.

As mentioned above, the strength of the granules of the present invention is 0 per granule.
．． It collapses under a load of 1 to 10 f, preferably under a load of 1 to 51 f. Although spherical granules are preferable for caries disintegration, angular granules may damage the teeth and have a greater impact on the gums.

The granules having the particle size and strength as described above can be changed depending on the type, combination and amount of the inorganic binder and the manufacturing conditions of the granules.

The granules of the present invention can be manufactured by a known granulation method. Among these, the spray granulation method is suitable as a method for producing the granules of the present invention because the granules are almost perfectly spherical in shape and are easy to handle. In the case of extrusion granulation, etc., angular particles are obtained, and a spheroidization operation using a marmerizer or the like is required to obtain spherical particles.

In the case of the spray granulation method, the above-mentioned shape-forming binder is preferably blended in an amount of 30% by weight or more based on the water-insoluble powder material in order to obtain a good spray condition, and the adhesive binder is used to control the viscosity of the spray slurry. 0.5 to 30% by weight based on the total amount of granules, as it causes problems such as poor spraying and nozzle clogging.
It is preferable to add it within the following range.

The granules of the present invention obtained by this process can be incorporated into various dentifrices such as toothpaste and powdered toothpaste, but it is particularly suitable to incorporate them into toothpastes since the granules can express their aesthetic properties.

The granules of the present invention are incorporated into a dentifrice in an amount of 1 to 50 fi, preferably 3 to 3 Ofi. If the granules of the present invention contain granules of 75 μm or less during production, they can be blended into dentifrices as they are, but if they contain granules of 500 μm or more, they are removed by passing them through a 30-meter sieve before blending. It is preferable. Further, the granules of the present invention can be used alone as an abrasive component, but a commonly used abrasive for toothpaste can be used in combination.

The dentifrice can be prepared according to conventional methods and may contain other ingredients commonly used in dentifrices. For example, sodium carboxymethyl cellulose as a binder? Sodium acrylate, hydroxyethyl cellulose, thickening silica, montmorillonite, carrageenan, sodium alginate, guar gum, pectin, etc. can be used. In addition, as surfactants, salts of acyl amino acids such as sodium acylglutamate and sodium acylsarcosinate, salts of alkyl phosphates such as sodium lauryl phosphate, sucrose fatty acid ester, sorbitan fatty acid ester, etc. Lioxyethylene fatty acid ester etc. can be used. In addition, the medicinal ingredients include allantoin,
Tranexamic acid, vitamin E1, vitamin C1, sodium chloride, bittern, sodium fluoride, tin fluoride, carpazochrome, prolis, glycyrrhetinic acid, chlorhexicine, cetyl-rizonium chloride, etc. can be used. In addition, humectants, sweeteners, preservatives, fragrances, etc. may be added.

〔Effect of the invention〕

When using the toothpaste containing granules of the present invention, the granules can be palpated in the mouth and the dirt-removing effect can be recognized with almost no foreign body sensation. In fact, the presence of granules increases the initial abrasive force and contributes to the dirt removal effect, and as the granules gradually disintegrate during the brushing operation, the particle size becomes smaller and the abrasive force decreases, resulting in a long-lasting It can also prevent harm such as horizontal defects that occur when brushing for a long time or when brushing pressure is too strong. Furthermore, a dentifrice prepared using an ion-exchangeable fine powder such as zeolite as a water-insoluble powder material is advantageous in that it has both a high tartar prevention effect and a tooth discoloration prevention effect.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 ω The solid content was zeolite (type 4A; 99.9 wt% of zeolite having a particle size of 10μ or less).

An aqueous slurry containing 60 parts by weight of particles with an average particle size of 2μ, 10 parts by weight of silicic anhydride (colloidal silica), 2 parts by weight of titanium oxide, and 28 parts by weight of magnesium aluminate metasilicate (the water content is approx. 60% by weight) using a spray granulator. During the manufacturing process, the spray condition was extremely stable. This product was a spherical body with a smooth or spherical surface, and 92% by weight of the product passed through a 30-mesh sieve but did not pass through a 200-mesh sieve.

The remaining 8% passed through a 200 mesh sieve.

The granule strength was measured by separating the obtained granules with a sieve and dividing them into a certain number (100 to 2 granules) of the same size (about 200μ).
00 pieces), the granules are placed in a single layer in an acrylic cell as shown in Figure 1, an acrylic plate is placed on top, a load is applied from above with a dish delguso, and the load when the granules disintegrate is measured. did. Divide this load by the number of granules used in the test,
The load per granule was determined, and this was taken as the granule strength.

(1) Next, the stability of this granule (approximately 200μ) in an aqueous system (
In order to examine the strength), Part 3. Of was placed in a 30d sample bottle, 25ml of distilled water was added, the bottle was stoppered, and the bottle was left for one day. Thereafter, an iron ball (one piece with a diameter of 7 mm and a mass of 3.6 f) was placed in the sample bottle, and the sample bottle was shaken for 5 minutes using a shaker with the stopper closed (this operation is referred to as "pulverization abuse"). Thereafter, the contents of the sample bottle were transferred to a 200-mesh sieve to remove iron balls, and then granules of 75 μm or less were removed under running water. Then, the granules remaining on the sieve were dried at 110° C. for 2 hours, and then their weight was measured. The results are shown in Section 3 below.

(-) In order to evaluate the feel of the granules, the manufactured granules were directly blended into a dentifrice having the formulation shown in Table 1. The dentifrice was left for one week after production to stabilize the fragrance. Thereafter, 20 Q-naires were asked to use this toothpaste and immediately thereafter evaluated the feel of the granules. A regular round-cut toothpaste was used. The visibility of the granules in the oral cavity is
■...I felt it in 1 after I started brushing my teeth and when I finished brushing.

■... Granules were palpable at the beginning of tooth brushing, but became palpable during tooth brushing; ■... Granules could not be palpated. classified into.

The feel of the granules was evaluated on a five-point scale: ■...Good;
(?)... Fairly good, ■... Neutral, ■・
It was rated as ...somewhat poor, ■...poor. The results are also shown in Section 3 below.

Table 1 Example 2 Solid contents include 60 parts by weight of calcium hydrogen phosphate (85% by weight and t% average particle size of 6 μm having a particle size of 10 μ or less), 10 parts by weight of silicic anhydride (colloidal silica), and titanium oxide. Granules were produced using a spray granulator from an aqueous slurry containing 2 parts by weight of magnesium aluminate metasilicate and 28 parts by weight of magnesium aluminate metasilicate. During the manufacturing process, the spray condition was extremely stable. This object is a spherical body with a smooth spherical surface, and 90% of the object passes through a 30-mesh sieve but does not pass through a 200-mesh sieve, and the remaining 10%.
passed through a 200 mesh sieve.

This granule was also evaluated in the same manner as in Example 1 regarding the strength of the granule, the stability (strength) in an aqueous system, and the feel when added to toothpaste.

Example 3 Contains 60 parts by weight of zeolite (AA type; 85% by weight having a particle size of 10 μ or less, average particle size 8 μ), 38 parts by weight of magnesium aluminate metasilicate, and 2 parts by weight of hihititanium acid as solid content. Granules were produced using a spray granulator from a water streak of 10 (water content is approximately 60% by weight). During the manufacturing process, the spray condition was extremely stable. This material is a spherical body with a smooth spherical surface that rarely passes through 30 mesh vBt, and 87% by weight does not pass through a 200 mesh sieve, and the remaining 13% by weight passes through a 200 mesh sieve. did.

This granule was also evaluated in the same manner as in Example 1 regarding the strength of the granule, the stability (strength) in an aqueous system, and the feel when added to toothpaste.

Example 4 As solid contents, 40 parts by weight of silica (67% particles with a particle size of 20 μm or less, average particle size of 16 μm), 10 parts by weight of alumina vine,
Granules were produced from a water slurry containing 49 parts by weight of synthetic aluminum silicate and 1 part by weight of Prussian blue (water content approximately 50% by weight) using a spray granulator. During the manufacturing process, the spray condition was extremely stable. This material passed through a 30-mesh sieve, and 70% by weight of the material did not pass through a 20-mesh sieve. The remaining 30% passed through 200 meshes. The strength of the granules and the amount of remaining granules after being subjected to powdering treatment in the same manner as in Example 1 [Initial 3.
0] was measured. In addition, in order to fully evaluate the feel of the granules, the above granules were blended into a dentifrice having the formulation shown in Table 2. The dentifrice was left for one week after production to stabilize the fragrance. The appearance was favorable, as blue granules appeared to be floating on the surface of the white paste.

Table 2 Comparative Example 1 Dibasic calcium phosphate as solid content (85 weight'!jk% with particle size of 10 μ or less, average particle size 6 μ) 6
Granules were produced using a spray granulator from a water slurry containing 0 parts by weight of magnesium aluminate metasilicate, 35 parts by weight of magnesium aluminate metasilicate, and 5 parts by weight of carboxymethylcellulose salt.

During the manufacturing process, the spray condition was extremely stable. This product is a spherical body with a smooth spherical surface, and 87% by weight of the product passes through a 3o mesh sieve but does not pass through a 200 mesh sieve, and the remaining 13% by weight passes through a 200 mesh sieve. did. The comparative examples were also evaluated in the same way as the examples.

Comparative Example 2 Zeolite (type 4A; 99.9% by weight having a particle size of 10 μ or less, average particle size 2 μ) was used as a solid content of 30
Granules were produced using a spray granulator from a water slurry containing 30 parts by weight of magnesium aluminate metasilicate, 20 parts by weight of alumina sol, and 20 parts by weight of silicic anhydride (colloidal silica).

During the manufacturing process, the spray condition gradually deteriorated, and the spray nozzle became clogged, resulting in a spray problem. Nzo's motor has broken down, so production has to be discontinued. The granules obtained before production discontinuation were spherical bodies with smooth spherical surfaces, passed through a 30-mesh sieve, and passed through a 20-mesh sieve.
Those that did not pass through the 0 mesh sieve accounted for 87% by weight of the total, and the remaining 13% by weight passed through the ¥1,200 mesh.

Comparative Example 3 60 parts by weight of dibasic calcium phosphate (855 parts by weight having a particle size of 10 μ or less, average particle size 6 μ), 3 parts by weight of ethyl cellulose, and an appropriate amount of a7ton were added to this, and the mixture was mixed. Then, a prototype of granules was produced using the push-out granulator. These particles were approximately cylindrical and angular, and passed through a 30-mesh sieve, with 844 parts by weight of the total not passing through a 200-mesh sieve, and the remaining 166 parts by weight passing through a 200-mesh sieve. .

Margin Experiment Example 1 The abrasiveness of the toothpaste containing granules of the present invention was compared with that of a powdered product. That is, an acrylic plate like the one shown in Figure 2 was set in a brushing machine. The dentifrice was diluted with distilled water to make a 50% solution, and then 150 d of this solution was poured into a brushing machine and brushing was performed with a load of 640 t. After a certain period of time, the amount of wear and tear on the acrylic plate after brushing was measured using a microbalance. Table 4 shows the toothpaste used in the experiment.
Kl, that's right. The results are shown in FIG.

Table 4: Raw material powder This is a powder product with the same composition as the granules in Example 30. In other words, it is simply a mixture of the raw material powders for the granules.

As is clear from the results in Figure 3, in the case of the product of the present invention (granule product), the initial abrasive force is stronger than that of the powder product, and as the granules are disintegrated by brushing, the abrasive force decreases to the same level as the powder product. You can see that it is.

Experimental Example 2 A toothpaste having the composition of Table 4 KL female was prepared and its cleaning effect was investigated. The effect is determined by brushing a glass plate coated with black marker ink with a tooth brush using 1 ton of the test composition, and measuring the number of brushings until the black marker ink on the glass plate is completely removed when seen with the naked eye. I judged it. The results are shown in Table 5.

This experimental result shows that the granules of the present invention have a high abrasive power that zeolite, which is a powder raw material, does not have, and have excellent cleaning effects.

Experimental Example 3 Using commercially available dentifrice A (containing calcium hydrogen phosphate as an abrasive) and the dentifrice of Example 1 as a test product, using the same brush, 4 test subjects were tested before and after using the dentifrice. Plaque removal rate was determined by measuring the amount of plaque.

The amount of plaque is measured using the precious wood method (Journal of Oral Hygiene, 20, 9).
．． (1970). That is, six teeth in the upper and lower jaws were used as test teeth, and after staining the plaque with a plaque revealer, what was the height of the plaque from the gingival margin (moI)? Measurements are taken with a ketzo rope, and the measurement sites are 1 in total: 5 labial areas and 5 lingual lid areas per tooth.
The amount of dental plaque was determined as 0, and the total amount of each site was determined as the amount of plaque. The plaque removal rate was determined using the formula below.

As shown in FIG. 4, the dentifrice of the present invention showed a significantly higher plaque removal rate (p<α05) than the commercially available dentifrice. This is because the granules have a specific particle size, so they easily enter the interdental area where dental plaque tends to adhere, and when you brush your teeth, they break down and become primary particles of zeolite in the granule component, which penetrates into the dental plaque. It is thought that the Ca content in dental plaque is reduced, making it easier to remove dental plaque during brushing.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the apparatus used to measure granule strength. FIG. 2 is a perspective view of the brushing machine used in Experimental Example 1. FIG. 3 is a diagram showing the relationship between the amount of wear and tear on the acrylic plate and the number of times of brushing. FIG. 4 is a drawing showing a comparison of the plaque removal rate between a commercially available dentifrice and the dentifrice of Example 1 of the present invention. that's all

Claims (1)

[Scope of Claims] 1. Granules obtained by binding water-insoluble powder materials with a water-insoluble inorganic binder, which have a particle size that passes through a 30 mesh sieve but does not pass through a 200 mesh sieve. , A dentifrice containing granules that disintegrate when a load of 0.1 to 10 g is applied to each granule. 2. Water-insoluble powder materials include dibasic calcium phosphate, tribasic calcium phosphate, insoluble sodium metaphosphate, silica, aluminum hydroxide, magnesium phosphate, calcium carbonate, calcium pyrophosphate, zeolite, composite aluminosilicate, magnesium carbonate, red iron sulfate, calcium sulfate The dentifrice according to claim 1, which is selected from the group consisting of: and mixtures thereof. 3. The dentifrice according to claim 1, wherein the water-insoluble powder material has a particle size of 0.1 to 20μ. 4. The dentifrice according to claim 1, wherein the water-insoluble powder material is zeolite. 5. The water-insoluble inorganic binder is colloidal silica, magnesium aluminate metasilicate, bentonite, montmorillonite, kaolin, synthetic aluminum silicate, calcium silicate, aluminum hydroxide gel, alumina sol, magnesium carbonate, synthetic hydrotalcite, magnesium oxide, The dentifrice according to claim 1, which is selected from the group consisting of magnesium hydroxide and mixtures thereof. 6. The dentifrice according to claim 1, wherein the water-insoluble inorganic binder is a silicon-based compound. 7. The dentifrice according to claim 1, wherein the water-insoluble inorganic binder is a combination system of magnesium aluminate metasilicate or synthetic aluminum silicate and colloidal silica. 8. The dentifrice according to claim 1, wherein the granules further contain a coloring agent. 9. The dentifrice according to claim 1, wherein the granules have a substantially spherical shape. 10. The dentifrice according to claim 1, wherein the granules are obtained by a spray granulation method. 11, granule amount is 1-5
The dentifrice according to claim 1, which contains 0% by weight.