JP7173043B2 - Oral stain remover, oral stain formation inhibitor, and oral composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an oral stain remover, an oral stain formation inhibitor, and an oral composition containing the same, which can effectively suppress stain adhesion to teeth and is useful for tooth whitening.

Stain, which is a type of tooth stain, causes a coloring reaction in pellicles containing coloring-causing ingredients contained in saliva, food, beverages, luxury goods, etc. that adhere to the tooth surface. As a result, a strong colored stain was formed. As means for suppressing the adhesion of stains to solve this problem, a method of removing stains and a method of suppressing the formation of stains are conceivable.

Conventionally, as a means for removing colored stains, polishing removal by the physical action of an abrasive compounded in the composition has generally been used. There was a limit to what could occur. Furthermore, it is also known that condensed phosphates such as sodium polyphosphate are used in combination to impart stain removal effects, but the effect may not be exhibited unless the amount of condensed phosphates is relatively large. Moreover, the problem that oral mucous membrane irritation|stimulation became strong also generate|occur|produced as the compounding quantity was increased.

Patent Document 1 (International Publication No. 2016/194645) discloses that a condensed phosphate and a fatty acid or fatty acid ester having a specific branched chain structure are used in combination to alleviate oral mucosal irritation while reducing stain chemically. In Patent Document 2 (Japanese Patent Application Laid-Open No. 9-175966), a technique for removing stains on the tooth surface by chemical action by blending water-soluble pyrophosphate and polyphosphate is proposed. However, there is room for improvement in the removal effect.

Also, a technique for preventing the formation of stains in advance has attracted attention, and the establishment of a technique for suppressing the formation of stains is expected.
As a method for suppressing stain formation, methods using various surfactants are proposed in Patent Documents 3 to 5 (Japanese Patent Application Laid-Open Nos. 2003-81797, 2013-142061, and 2015-174830). However, unless a relatively large amount of surfactant is blended, the effect may not be exhibited, or an unpleasant taste derived from the surfactant may occur.

On the other hand, Patent Document 6 (Japanese Patent Laid-Open No. 2000-247851) proposes a technology that applies polyacrylic acid having a molecular weight of 20,000 or more as a coloring control coating agent that suppresses tooth coloring due to stain accumulation. In Document 7 (Japanese Patent Publication No. 7-29907), a polyacrylic acid polymer or polyacrylic acid copolymer having a weight average molecular weight of about 3,500 to 7,500 is used as an anticalculus agent in an amount of about 2.5% or more. is proposed to be incorporated into the oral composition in an amount of

WO2016/194645 JP-A-9-175966 Japanese Unexamined Patent Application Publication No. 2003-81797 JP 2013-142061 A JP 2015-174830 A JP-A-2000-247851 Japanese Patent Publication No. 7-29907

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a new stain adhesion inhibitor for oral cavity that suppresses stain adhesion to teeth and an oral composition containing the same.

The present inventors conducted intensive studies to achieve the above object, and found that a polyacrylate having a weight-average molecular weight within a specific range has stain-removing action and stain-formation-suppressing action in the oral cavity. It has been found that an excellent stain adhesion suppressing effect is exhibited. Furthermore, when a polyacrylate having a weight average molecular weight within a specific range is used in combination with a specific chelating agent and/or a specific alginic acid derivative, the stain removing action and/or stain formation inhibiting action in the oral cavity is enhanced, and the stain is It was found that the effect of suppressing adhesion is further improved.
In particular, by blending the above-mentioned combined system into an oral composition, it is possible to impart a high stain removing action and/or a stain formation suppressing action, to impart an excellent stain adhesion suppressing effect, and to provide a good feeling during use. The inventors have found that a satisfactory feeling of effect can be given, and have completed the present invention.

More specifically, the present inventors have found that, as the first invention, polyacrylates having a weight average molecular weight of a specific value or less have the effect of removing stains, which are colored stains firmly adhered to teeth in the oral cavity. However, it has been found that an excellent stain removing effect can be obtained, and furthermore, when a specific chelating agent is used in combination, the effect of the above polyacrylate is enhanced and the stain removing effect is remarkably improved. Thus, by blending the combination system of the polyacrylic acid salt and the specific chelating agent in the oral composition, an excellent stain removal effect is imparted, and oral irritation to the oral cavity, especially the mucous membrane is prevented. The present inventors have found that it is possible to suppress it and give a feeling of use with good aroma and taste, and have completed the first invention.

Polyacrylic acid or a salt thereof is known as a binder for oral compositions, but generally a crosslinked polyacrylic acid having a weight average molecular weight of 100,000 or more, usually about 300,000, or a salt thereof is used. ing. In addition, the stain is strongly constructed by forming a colored pellicle on the tooth surface with saliva components, food and drink, etc., and laminating and depositing the colored pellicle.
On the other hand, in the first invention, (a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less, especially a linear polyacrylate, is already attached to the tooth surface. It has been found that there is a hitherto unknown effect of removing strong stains that are present, and as a result, polyacrylates with a weight average molecular weight of more than 20,000 or a weight average molecular weight of 20,000 or less However, a particularly remarkable effect was obtained that could not be achieved with polyacrylic acid that was not in the form of a salt.

As shown in Comparative Example I in Tables 1 and 5 below, the stain removal effect of sodium polyacrylate having a weight average molecular weight of 300,000 or polyacrylic acid having a weight average molecular weight of 6,000 was x. However, as shown in Examples in Tables 1 to 5, the stain removal effect of the component (a) was all excellent, being ◯ or ⊚ or better.
In addition, the stain removal rate by the chelating agent was low, and in some cases, almost no removal effect was observed (comparative examples in Table 5 below). However, as shown in Example I in Tables 3 to 5, in the first invention, when component (a) and (b) a specific chelating agent described later are used in combination, both act synergistically to remove stains. The effect was remarkably enhanced, and the unpleasant odor caused by the component (a) and the oral irritation and offensive taste caused by the component (b) were suppressed, thereby maintaining a good feeling during use.

Although the details of the action mechanism of stain removal in the first invention are not clear, the stain is removed by the component (a) reacting specifically with the stain and facilitating the lifting of the stain. guessed. Moreover, it is presumed that the above action is enhanced when the component (b) is used in combination.

In addition, as a second invention, the present inventors have found that a polyacrylate having a weight average molecular weight of a specific value or less has the effect of suppressing the formation of stains in the oral cavity, and exhibits an excellent stain formation suppression effect. Further, the present inventors have found that when a specific alginic acid derivative (alginate or alginic acid ester) is used in combination, the action of the polyacrylate is enhanced and the stain formation inhibitory effect is remarkably improved. Thus, by blending the combination system of the polyacrylate and the alginic acid derivative in the oral cavity composition, it is possible to impart an excellent stain formation suppressing effect and to give a satisfactory feeling of effect. The headline led to the present second invention.

In the second invention, (a) the polyacrylate having a weight-average molecular weight of 1,000 or more and 20,000 or less, particularly a linear polyacrylate, does not form stains on the tooth surface in the oral cavity. It has been found that there is a hitherto unknown effect of suppressing the A particularly remarkable effect was obtained that could not be achieved with polyacrylic acid that was not

As shown in Comparative Example II in Tables 6 and 8 below, the effect of suppressing stain formation by sodium polyacrylate having a weight average molecular weight of 300,000 or polyacrylic acid having a weight average molecular weight of 6,000 was x. However, as shown in Example II in Tables 6 and 7, the effect of suppressing stain formation by the component (a) was either ◯ or ⊚, and was excellent.
In addition, as shown in Comparative Examples in Table 8 below, almost no effect of suppressing stain formation by alginate or alginate was observed, but as shown in Examples in Tables 6 and 7, the second invention Then, when the component (a) and (c) one or more alginic acid derivatives selected from alginates and alginate esters are used in combination, the two act synergistically to remarkably enhance the effect of suppressing stain formation. Even after use, it was felt that the tooth surface became smooth, and it was also possible to impart a real feeling of effect that the formation of stains was sufficiently suppressed.

Although the details of the mechanism of action for suppressing stain formation in the second invention are not clear, due to the specific action of the component (a), saliva components and metal ions derived from food and drink bind to the tooth surface, resulting in discoloration. It is speculated that stain formation is suppressed by chemically inhibiting pellicle formation and preventing deposition. In addition, when the component (c) is used in combination, the above effects are remarkably improved, and at the same time, the adsorption and retention of the component (c) on the tooth surface are improved, and the formation of stains is continuously suppressed even after continuous use. It is presumed that the effect will be felt more strongly.

As described above, Patent Document 6 is directed to suppressing discoloration by coating, and by making the tooth surface hydrophilic after coating, the stained pellicle (colored pellicle) can be easily removed and prevented from accumulating. Patent Document 7 discloses that calculus suppression by a polyacrylic acid polymer or the like can be achieved with a usage amount of about 2.5% or more.
In contrast, the present invention is (a) stain removal and stain formation suppression by a polyacrylic acid salt of a specific molecular weight, and stain adhesion suppression by them, and such effects are inferior to polyacrylic acid that is not in the salt form. On the other hand, it is excellent even if the amount of component (a) in the oral composition is 1% by mass or less.

Accordingly, the present invention provides the following oral stain remover, oral stain formation inhibitor, and oral composition.
[1]
(a) An oral stain remover containing a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less.
[2]
(a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less; An oral stain remover containing one or more chelating agents selected from citric acid, malic acid, succinic acid, dicarboxylic acid and salts thereof.
[3]
The stain remover for oral cavity according to [2], wherein (a)/(b) is 0.01 to 50 as a mass ratio.
[4]
The stain remover for oral cavity according to any one of [1] to [3], wherein the polyacrylate of component (a) has a weight average molecular weight of 1,000 or more and 10,000 or less.
[5]
(a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less; An oral composition containing one or more chelating agents selected from citric acid, malic acid, succinic acid, dicarboxylic acid and salts thereof.
[6]
The oral cavity composition according to [5], wherein the polyacrylate of component (a) has a weight average molecular weight of 1,000 or more and 10,000 or less.
[7]
The oral composition according to [5] or [6], wherein (a)/(b) is 0.01 to 50 as a mass ratio.
[8]
The oral composition according to any one of [5] to [7], containing 0.01 to 2% by mass of component (a) and 0.03 to 3% by mass of component (b).
[9]
The oral cavity composition according to any one of [5] to [8], further comprising (c) 0.05 to 2% by mass of one or more alginic acid derivatives selected from alginates and alginic acid esters.
[10]
The oral cavity composition according to any one of [5] to [9], which is for removing stains.
[11]
The oral composition according to any one of [5] to [10], which is a dentifrice composition.
[12]
(a) A stain formation inhibitor for oral cavity containing a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less.
[13]
(a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less; and (c) one or more alginic acid derivatives selected from alginates and alginate esters.
[14]
The stain formation inhibitor for oral cavity according to [13], wherein (a)/(c) is 0.05 to 5 as a mass ratio.
[15]
The stain formation inhibitor for oral cavity according to any one of [12] to [14], wherein the polyacrylate has a weight average molecular weight of 1,000 or more and 10,000 or less.
[16]
An oral composition containing (a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less, and (c) one or more alginic acid derivatives selected from alginates and alginic acid esters.
[17]
The oral composition according to [16], wherein the polyacrylate has a weight average molecular weight of 1,000 or more and 10,000 or less.
[18]
The oral composition according to [16] or [17], wherein (a)/(c) is 0.05 to 5 as a mass ratio.
[19]
The oral cavity composition according to any one of [16] to [18], containing 0.01 to 2% by mass of component (a) and 0.05 to 2% by mass of component (c).
[20]
The oral cavity composition according to any one of [16] to [19], which is for suppressing stain formation.
[21]
The oral composition according to any one of [16] to [20], which is a dentifrice composition.

According to the present invention, an oral stain remover, an oral stain formation inhibitor, and an oral stain remover having a stain removing action and/or a stain formation inhibiting action in the oral cavity, thereby exhibiting an excellent stain adhesion inhibiting effect, and containing these It is possible to provide an oral composition that
That is, according to the present invention, it is possible to provide, as a first invention, an oral stain remover having an excellent effect of removing stains in the oral cavity and an oral composition containing the same. Since this oral composition has a high stain removing effect and a good feel when used, it can effectively suppress stains, and is therefore suitable for whitening the oral cavity and preventing or suppressing oral diseases.
In addition, as a second invention, it is possible to provide an oral stain formation inhibitor having excellent effect of suppressing stain formation in the oral cavity and an oral cavity composition containing the same. Since this oral composition has a high stain formation inhibitory effect and gives a satisfactory feeling of effect, it can effectively suppress stain formation, and is therefore effective for whitening of the oral cavity and prevention or inhibition of oral diseases.

The present invention will be described in further detail below.
The oral stain remover and oral stain formation inhibitor of the present invention comprise (a) a polyacrylate having a weight average molecular weight of 1,000 or more and 20,000 or less, preferably component (a) and (b) 1 mass. 1 or 2 or more chelating agents selected from condensed phosphoric acid, phytic acid, edetic acid, citric acid, malic acid, succinic acid, dicarboxylic acid, and salts thereof, having a pH of 1 to 11 in % aqueous solution at 25°C and/or (c) one or more alginic acid derivatives selected from alginates and alginate esters.
That is, the oral stain remover of the first invention contains component (a), preferably components (a) and (b), and component (a), preferably component (a) and component (b) , is an active ingredient for stain removal. The oral stain formation inhibitor of the second invention contains component (a), preferably components (a) and (c), and component (a), preferably components (a) and (c), It is an active ingredient that suppresses stain formation. Therefore, in the present invention, by using the component (a), the components (a) and (b), or the components (a), (b) and (c), the stain removing action and/or the stain formation suppressing action are obtained. With these actions, excellent action and effect of suppressing adhesion of stains are exhibited.
In the present invention, "stain adhesion" means a state in which stain is adhered, and "stain adhesion suppression" means a state in which stain is not adhered. "Removal of stain" means removal of adherent stain that has formed, and "inhibition of stain formation" means prevention of adherence of stain.

The polyacrylate of component (a) has a weight average molecular weight (Mw) of 1,000 or more and 20,000 or less. In this case, the weight average molecular weight is 1,000 or more, preferably 2,000 or more, and 20,000 or less, preferably 10,000 or less, from the viewpoint of stain removal effect and stain formation suppression effect. , more preferably 8,000 or less. If the weight average molecular weight is less than 1,000, the stain removal effect and the stain formation suppression effect are inferior. If it exceeds 20,000, the stain removing effect and the stain formation suppressing effect are lowered, and sufficient effects cannot be obtained.

The weight average molecular weight was measured by GPC (gel permeation chromatography) under the method and measurement conditions described in Japanese Patent No. 5740859. Specifically, it is shown below (same below).
Method for measuring weight average molecular weight;
The weight average molecular weight is a value measured using a gel permeation chromatograph/multi-angle laser light scattering detector (GPC-MALLS) under the following conditions.
Mobile phase: 0.3M _NaClO4
NaN ₃ aqueous solution column: TSKgelα-M 2 pre-column: TSKguardcolumn α
Standard substance: Polyethylene glycol

The polyacrylate of the component (a) is preferably a linear polyacrylate from the standpoint of stain removal effect and stain formation suppression effect.
The salt is preferably a monovalent salt, more preferably an alkali metal salt or an ammonium salt, more preferably an alkali metal salt such as a sodium salt or a potassium salt, and particularly preferably a sodium salt.
As such polyacrylic acid salts, commercial products sold by Polyscience Co., Ltd. or Toagosei Co., Ltd. can be used.
Specific commercial products include sodium polyacrylate (Mw: 1,000); linear, manufactured by Polyscience, sodium polyacrylate (Mw: 6,000); linear, manufactured by Toagosei Co., Ltd. , AC-10NP, AC-10NPD, Aron T-50, sodium polyacrylate (Mw: 8,000); linear, manufactured by Polyscience, sodium polyacrylate (Mw: 20,000); linear , Toagosei Co., Ltd., Aron A-20UN, etc. can be used.

In addition, the polyacrylate of the component (a) has a lower weight average molecular weight than the polyacrylate of the binder usually used in dentifrices, and is different from the known polyacrylate as a binder. It is.
When a polyacrylic acid salt other than the component (a) is used instead of the component (a), or when polyacrylic acid that is not in the form of a salt is used, the stain removing effect and the stain formation inhibiting effect are inferior, and further Even if the component (b) is used in combination, the effect is inferior, and even if the component (c) is used in combination, the above effect is inferior and the effect is not actually felt, and the object of the present invention is not achieved.

In the present invention, in the oral stain remover of the first invention, it is preferable to use (b) a specific chelating agent in combination with (a) component as an active ingredient. When the (a) and (b) components are used together, the stain removal effect is further improved.

Component (b) is a chelating agent selected from the following (b1) to (b5). These may be blended singly or in combination of two or more. It is also possible to use two or more of the components (b1) to (b5) in combination.
(b1): condensed phosphorus having a pH of 1 to 11 at 25° C. in a 1% by mass aqueous solution
One or more selected from acids and salts thereof (b2): One or more selected from phytic acid and salts thereof (b3): One or more selected from edetic acid and salts thereof (b4): Citric acid and salts thereof One or more selected (b5): selected from malic acid, succinic acid, dicarboxylic acid and salts thereof
One or More Types In each of the above (b1) to (b5), the type of salt is not particularly limited, but metal salts such as sodium salts and potassium salts are exemplified, and sodium salts are particularly preferred.

The condensed phosphoric acid (b1) and its salt preferably have a pH of 11 or less, particularly 10 or less at 25° C. in a 1% by weight aqueous solution, and the lower limit is not particularly limited as long as the pH is 1 or more, but the pH may be 7 or more.
Sodium salt and potassium salt are preferable as the condensed phosphate.
Specifically, linear or cyclic polyphosphates such as sodium or potassium pyrophosphate, sodium or potassium tripolyphosphate, sodium or potassium tetrapolyphosphate, sodium or potassium metaphosphate, sodium or potassium ultraphosphate can be used. .
Among these are sodium tripolyphosphate (1% by weight aqueous solution, pH 7-10 at 25°C), sodium pyrophosphate (1% by weight aqueous solution, pH 7-11 at 25°C), sodium metaphosphate (1% by weight aqueous solution, 25°C pH 1 to 8), sodium ultraphosphate (1% by mass aqueous solution, pH 1 to 7 at 25° C.), more preferably sodium tripolyphosphate.

(b2) is particularly preferably phytic acid and (b3) is particularly preferably edetate, especially disodium edetate. (b4) is preferably citric acid, sodium citrate, especially citric acid.

(b5) is one or more selected from malic acid, succinic acid, dicarboxylic acid and salts thereof.
Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid.
(b5) is preferably selected from malic acid, succinic acid and salts thereof. In this case, those containing these can also be preferably used.

Furthermore, (a) / (b), which indicates the quantitative ratio of component (a) and component (b), is preferably 0.01 to 50, more preferably 0.01 to 10, and particularly preferably 0 as a mass ratio. .01 to 8. Within this range, the stain-removing effect and feeling of use (oral irritation, odor, taste) are more excellent.

The stain remover for oral cavity of the first invention can be obtained by using component (a) alone as an active ingredient, preferably further using component (b) in combination, and blending the above components. Furthermore, if necessary, other ingredients known for oral use may be included, and in this case, the known ingredients can be blended within a range that does not impair the effects of the present invention.

In the present invention, in the stain formation inhibitor for oral cavity of the second invention, it is preferable to use (c) one or more alginic acid derivatives selected from alginates and alginate esters in addition to (a) as an active ingredient in combination. . When the components (a) and (c) are used together, the effect of suppressing stain formation is further improved.

Component (c) is a salt or ester of alginic acid, which is a polysaccharide.
Any alginate commonly used in oral compositions can be used, but sodium alginate can be used. Sodium alginate preferably has a viscosity of 1 mass % aqueous solution (BL type viscometer, rotor No. 3, 12 rpm, 20° C., measurement time 3 minutes) of 1,000 to 4,000 mPa·s. For example, a commercially available product such as Kimika Algin from Kimika Co., Ltd. can be used.
As the alginate, any one usually used in oral compositions may be used, but propylene glycol alginate is particularly preferred. Among them, those having a viscosity of 1% by mass aqueous solution (BL type viscometer, rotor No. 2, 60 rpm, 20° C., measurement time of 3 minutes) of 10 to 200 mPa·s are preferable. For example, commercially available products such as Kimiroid BF available from Kimika Co., Ltd. can be used.

Furthermore, (a)/(c), which indicates the ratio by weight of component (a) and component (c), may be 0.005 to 20 as a mass ratio, but preferably 0.005 to 20 in terms of the effect of suppressing stain formation. 05-5, more preferably 0.1-2. Within this range, the stain formation suppressing effect and the feeling of the effect are more excellent.

The stain formation inhibitor for oral cavity of the second invention can be obtained by using component (a) alone as an active ingredient, preferably further using component (c) in combination, and blending the above components. Furthermore, if necessary, other ingredients known for oral use may be included, and in this case, the known ingredients can be blended within a range that does not impair the effects of the present invention.

In the present invention, when the components (a), (b) and (c) are used as active ingredients in combination, the stain removal effect and the stain formation suppression effect are enhanced, the stain adhesion suppression effect is further improved, and further excellent effects are imparted. It is also suitable as an oral stain adhesion inhibitor.

The oral composition of the present invention contains component (a) and components (b) and/or (c).
In the present invention, the oral composition of the first invention contains components (a) and (b), and the oral composition of the second invention contains components (a) and (c). . It is more preferable that the composition for cavities of the present invention contains components (a), (b) and (c) from the standpoint of stain removal effect and stain formation suppression effect.
Specific examples of oral compositions include paste-like, gel-like, or liquid dentifrices (toothpaste, gel-like dentifrice, liquid dentifrice, liquid dentifrice, etc.), mouthwashes, mouth sprays, coating agents, and patches. etc. can be suitably blended. Among them, it is suitable as a dentifrice composition, especially a toothpaste composition. In addition, in the first invention, since it has an excellent stain-removing effect, it is suitable as an oral cavity composition for stain removal, and in the second invention, it has an excellent stain formation-inhibiting effect, so it is an oral composition for suppressing stain formation. It is suitable as a composition for The composition for oral cavity of the present invention has an excellent effect of removing stains and suppressing stain formation, and is therefore suitable for suppressing adhesion of stains.

Here, when the components (a) and (b) are used in combination, it is preferable to define (a)/(b) as the specific ratio described above, because the stain removal effect is excellent. The blending amounts of component (a) and further component (b) are preferably in the ranges described below, respectively, from the standpoint of the stain removal effect and the feeling of use, and the above components are preferably used at concentrations that satisfy these.
When the components (a) and (c) are used in combination, it is preferable to define (a)/(c) as the above-mentioned specific ratio because the effect of suppressing stain formation is excellent. The amounts of component (a) and further component (c) are preferably in the ranges described below from the standpoint of the effect of suppressing stain formation and the realization of the effect, and the above components are preferably used at concentrations that satisfy these.
When the components (a), (b) and (c) are used in combination, the stain removal effect and the stain formation suppression effect are excellent. It is more preferable to define by the ratio of The blending amounts of components (a), (b) and (c) are preferably in the ranges described below from the standpoints of the stain removal effect and stain formation suppression effect, as well as the feeling of use and the realization of the effect. concentration can be used.

The amount of component (a) to be blended is preferably 0.01 to 2% (% by mass, hereinafter the same) of the entire composition. When it is 0.01% or more, sufficient stain removal effect and stain formation suppression effect can be obtained. When it is 2% or less, the odor derived from the component (a) is sufficiently suppressed.
Furthermore, when components (a) and (b) are used in combination, the amount of component (a) is preferably 0.01 to 2%, more preferably 0.03 to 1%, and still more preferably 0.03 to 1% of the total composition. 0.03 to 0.8%. Sufficient stain removal effect is obtained as it is 0.01% or more. When it is 2% or less, the odor derived from the component (a) is sufficiently suppressed.
When components (a) and (c) are used in combination, the content of component (a) is preferably 0.01 to 2%, more preferably 0.05 to 1%, still more preferably 0.05 to 1% of the total composition. 1 to 0.8%. When it is 0.01% or more, a sufficient stain formation suppressing effect can be obtained. When it is 2% or less, a sufficient stain formation suppressing effect is obtained, and the bad taste derived from the component (a) is sufficiently suppressed.

The content of component (b) is preferably 0.03 to 3%, more preferably 0.1 to 3% of the total composition. Sufficient stain removal effect is obtained as it is 0.03% or more. When the content is 3% or less, stimulation of the oral cavity can be suppressed, and a feeling of use with good odor and taste can be imparted.
When component (b1) is blended as component (b) within the range of the blending amount of component (b), the preferable blending amount is 0.03 to 1%, particularly 0.03 to 1% of the total composition. 0.5%. When components (b2) to (b5) are blended as component (b), the preferred blending amount of each is 0.03 to 3%, particularly 0.1 to 3%, of the total composition. Each of the components (b1) to (b5) can be used singly within the above range, or two or more of them can be used in combination so long as the total amount is within the range of the component (b).

The content of component (c) is preferably 0.05 to 2%, more preferably 0.1 to 1% of the total composition. When it is 0.05% or more, a sufficient stain formation suppressing effect can be obtained. When it is 2% or less, a sufficient feeling of effect can be obtained, and the feeling of use is also good. In addition, when the component (c) exceeds 2%, the stringiness may be enhanced and the feeling of effect may be lowered.

In addition to the components (a), (b) and (c), the oral cavity composition of the present invention may contain, as optional components, other known components according to the dosage form, etc., to achieve the effect of the present invention. can be added as necessary within a range that does not interfere with Specifically, dentifrices contain abrasives, binders, thickeners, surfactants, sweeteners, preservatives, coloring agents, fragrances, and active ingredients, and these ingredients are mixed with water. , can be manufactured.

Examples of abrasives include silica-based abrasives such as silicic anhydride, crystalline silica, amorphous silica, silica gel and aluminosilicate; tribasic calcium phosphate; quaternary calcium phosphate; calcium hydrogen phosphate anhydrate; and calcium hydrogen phosphate. Calcium phosphate abrasive such as dihydrate, zeolite, calcium pyrophosphate, calcium carbonate, sodium hydrogen carbonate, aluminum hydroxide, alumina, magnesium carbonate, magnesium tertiary phosphate, zirconium silicate, hydroxyapatite, synthetic resin abrasive is mentioned. These may be used alone or in combination of two or more. Among them, from the viewpoint of oral mucosa irritation and usability, silica-based abrasives such as inorganic abrasives such as silicic anhydride, calcium phosphate-based abrasives, Silicic anhydride is particularly preferred.
The compounding amount of the abrasive is preferably 0 to 60% of the total composition, and when compounded, 3 to 60%, particularly preferably 5 to 55%. Also, the upper limit is preferably 20% or less, or 15% or less. The amount of the abrasive in the toothpaste is preferably 10 to 55% of the total composition, and the amount of the abrasive in the mouthwash is preferably 0 to 10%, especially 0 to 5% of the total composition.
The oral cavity composition of the present invention has an excellent stain-removing effect even if it does not contain an abrasive.

Binders include, for example, gums such as xanthan gum, tragacanth gum, gellan gum, karaya gum, gum arabic, crosslinked polyacrylates having a weight average molecular weight of more than 20,000, carrageenan, and sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, Cellulose derivatives such as sodium methylhydroxyethylcellulose, organic binders such as polyvinyl alcohol, carboxyvinyl polymer, and polyvinylpyrrolidone, and inorganic binders such as silica gel, aluminum silica gel, Veegum, and laponite can be blended (the blending amount is usually from 0.3 to 10%).

Viscosity agents include sugar alcohols such as sorbitol, maltitol, lactitol, erythritol and xylitol, and polyhydric alcohols such as propylene glycol. ).

As surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants can be blended. These can use 1 type(s) or 2 or more types.
Examples of anionic surfactants include alkyl sulfates, acyl amino acid salts, acyl taurine salts, etc. having an alkyl group having 12 to 14 carbon atoms, particularly 12 carbon atoms. The acyl group of the acylamino acid salt and acyl taurine salt preferably has 12 to 14 carbon atoms, preferably 12 carbon atoms.
Specific examples of alkyl sulfates include lauryl sulfate and myristyl sulfate, and examples of acyl amino acid salts include acyl glutamates such as lauroyl glutamate and myristoyl glutamate, acyl sarcosinates such as lauroyl sarcosinate, and acyl taurine. Salts include lauroyl methyl taurine salts. Salts are preferably alkali metal salts such as sodium salts and potassium salts. Alkyl sulfates, acyl sarcosine salts, and acyl taurine salts are particularly preferred. Among them, anionic surfactants having a hydrocarbon group of 12 carbon atoms (lauryl group) are preferred, and alkyl sulfates (sodium salts) are particularly preferred because they are superior in taste to other surfactants. .
Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene hydrogenated castor oil, polyoxyethylene ethers of glycerin esters, sucrose fatty acid esters, alkylolamides , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerin fatty acid ester. Among these, polyoxyethylene alkyl ethers, polyoxyethylene hydrogenated castor oils, alkylolamides, and sorbitan fatty acid esters are preferred in terms of versatility. The polyoxyethylene alkyl ether preferably has an alkyl chain of 14 to 30 carbon atoms, and an average added mole number of ethylene oxide (average added EO) of 3 to 30. Polyoxyethylene hydrogenated castor oil preferably has an average added EO of 10-100. The alkylolamide preferably has 12 to 14 carbon atoms in the alkyl chain. The sorbitan fatty acid ester preferably has a fatty acid having 12 to 18 carbon atoms, and the polyoxyethylene sorbitan fatty acid ester preferably has a fatty acid having 16 to 18 carbon atoms and an average added EO of 10 to 40.
Examples of amphoteric surfactants include acylaminoacetic acid betaine and fatty acid amidopropyl betaine having an acyl group of 12 to 14 carbon atoms. Acylaminoacetic acid betaine includes lauroyldimethylaminoacetic acid betaine and the like, and fatty acid amidopropyl betaine includes coconut oil fatty acid amidopropyl betaine and the like.

The content of the surfactant is preferably 0-15%, more preferably 0.01-10%. When blending an anionic surfactant, its blending amount is preferably 0.1 to 3%, particularly 0.5 to 2%. When blending a nonionic surfactant, its blending amount is 0.01%. ~10% is good.

In the present invention, if a nonionic surfactant, especially polyoxyethylene hydrogenated castor oil, is used in combination with component (a), the smell and taste may deteriorate depending on the amount added, and the feeling of use may decrease. When the nonionic surfactant is added together with an anionic surfactant such as the above, the deterioration of the odor and taste is prevented, and the stain removing effect and the stain formation suppressing effect are further improved without deteriorating the usability.

Sweetening agents include saccharin sodium, stevioside, dipotassium glycyrrhizinate, perillartine, thaumatin, neohesperidyl dihydrochalcone, aspartylphenylalanine methyl ester. Preservatives include paraoxybenzoic acid esters and sodium benzoate.
Colorants include Blue No. 1, Yellow No. 4, titanium dioxide, and the like.

Peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen 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, Chamomile Oil, Caraway Oil, Marjoram Oil, Bay Oil, Lemongrass Oil, Origanum Oil, Pine Needle Oil, Neroli Oil, Rose Oil, Jasmine Oil, Iris Concrete, Absolute Peppermint , natural fragrances such as absolute rose, orange flower, and fragrances obtained by processing these natural fragrances (pre-reservoir cut, rear-reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder perfume, etc.), and menthol, carvone, anethole, methyl salicylate, cinnamic aldehyde, 3-l-menthoxypropane-1,2-diol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramenthane-3-carboxamide, Pinene, Octylaldehyde, Citral, Pulegone, Carbyl Acetate, Anisaldehyde, Ethyl Acetate, Ethyl Butyrate, Allylcyclohexane Propionate, Methyl Anthranilate, Ethyl Methyl Phenyl Glycidate, Vanillin, Undecalactone, Hexanal, Isoamyl Alcohol , hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethyl thioacetate, etc., strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, Known flavoring materials used in oral compositions, such as blended flavorings such as mixed fruit flavors and tropical fruit flavors, can be used, and are not limited to the flavorings in the examples.
Moreover, it is preferable to use 0.000001 to 1% of the entire composition of the perfume material. It is preferable to use 0.001 to 2.0% in the composition as a perfume for perfuming using the above perfume material.

Optional active ingredients include nonionic fungicides such as isopropylmethylphenol; cationic fungicides such as cetylpyridinium chloride; Enzymes; alkali metal monofluorophosphates such as sodium monofluorophosphate and potassium monofluorophosphate; fluorides such as sodium fluoride and stannous fluoride; anti-inflammatory agents such as dihydrocholesterol, glycyrrhizic acid and glycyrrhetinic acid; hypersensitivity improving agents such as potassium nitrate and aluminum lactate; zinc compounds such as glycerophosphate, chlorophyll, sodium chloride, zinc chloride, zinc oxide and zinc citrate; copper compounds such as copper acid and copper sulfate; vitamins such as vitamin A, vitamin B group, vitamin C and vitamin E; These active ingredients can be used singly or in combination of two or more, and can be blended in an effective amount within a range that does not interfere with the effects of the present invention.

The pH (25° C.) of the oral composition may be within a normal range, preferably pH 5-9, particularly pH 6-8. A known pH adjuster may be added to adjust the pH, for example, hydrochloric acid or an alkali metal hydroxide such as sodium hydroxide can be used.
Preferred embodiments of the first and second inventions are shown below.

EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, % indicates % by mass unless otherwise specified.
Also, the weight average molecular weight (Mw) was measured using a gel permeation chromatograph/multi-angle laser light scattering detector (GPC-MALLS) under the same method and measurement conditions as above.

[Example I, Comparative Example I]
The types and amounts of polyacrylates shown in Tables 1 to 3 and component (b) were added to prepare oral formulations, and the stain removal effect was evaluated by the following method. The results are also shown in Tables 1-3.
Further, dentifrice compositions (toothpaste) having compositions shown in Tables 4 and 5 were prepared by a conventional method and filled in an aluminum tube container. The stain removal effect and the feeling of use were evaluated by the following methods. The results are shown in Tables 4 and 5 together.

(1) Evaluation method of stain removal effect A hydroxyapatite plate (manufactured by HOYA Corporation, diameter φ7.0 mm × thickness 3.5 mm, hereinafter abbreviated as HAP plate) whose surface was previously polished by sandblasting was subjected to (i). 0.5% albumin aqueous solution, (ii) tannin solution (50 g of Japanese tea (brand: Oimatsu), 5 black tea bags (Brisk tea bags manufactured by Lipton) were extracted with hot water, and after cooling, 12 g of powdered coffee (Nescafe (manufactured by Co., Ltd.), a solution prepared to 1,200 mL with purified water, and (iii) a 0.56% aqueous solution of iron (III) ammonium citrate in order for 30 minutes each at room temperature for 1 cycle. The operation including one cycle of immersion followed by a drying step was repeated 8 to 9 times a day, and continued for about 30 days until the stain was sufficiently adhered to the HAP plate to form a strong stain.
The degree of stain adhesion was determined by measuring the L ^* value using a spectral color difference meter (manufactured by Nippon Denshoku Co., Ltd., SE-2000). The L ₀ ^* value of the HAP plate before treatment was taken as the initial value, and the L ₁ ^* value after treatment was taken as the blank value. Next, the stained HAP plate was dipped in a dentifrice solution diluted 3-fold with artificial saliva (50 mM KCl, 1 mM CaCl ₂ , 0.1 mM MgCl ₂ , 1 mM KH ₂ PO ₄ , pH 7.0) at 37° C. for 2 hours. After immersion for 5 minutes, brushing was performed in the same test solution using a plate grinder. The brushing process was performed 200 times. After brushing, the hair was washed with water and the L ₂ ^* value was measured. The stain removal rate was calculated by the following formula, and the stain removal effect was evaluated.
Stain removal rate (%) =
{((L1 ^* _-L0 ^* )-(L2 _{* -L0} ^* ))/(L1 ^* _-L0 ^* ) _} ^× ₁₀₀
Evaluation criteria for stain removal effect ◎◎◎◎: Stain removal rate is 50% or more ◎◎◎: Stain removal rate is 40% or more and less than 50% ◎◎: Stain removal rate is 30% or more and less than 40% ◎: Stain removal rate is 25% or more and less than 30% ○: Stain removal rate is 20% or more and less than 25% △: Stain removal rate is 10% or more and less than 20% ×: Stain removal rate is less than 10%

(2) Evaluation method of feeling in use (irritation of oral cavity, odor, taste) Ten subject monitors placed the dentifrice composition on a toothbrush and brushed for 3 minutes to clean the oral cavity. The feeling of use (irritation to the mouth, odor, taste) at that time was sensory evaluated according to the following rating criteria. The average value of the 10 evaluation points was calculated, and oral stimulation, odor, and taste were determined according to the following evaluation criteria.

Scoring criteria for oral stimulation 4 points: no stimulation in the oral cavity 3 points: almost no stimulation in the oral cavity 2 points: some stimulation in the oral cavity 1 point: stimulation in the oral cavity Evaluation criteria for oral stimulation ◎: Average score of 3.0 or more and 4.0 or less ○: Average score of 2.5 or more and less than 3.0 △: Average score of 1.5 or more and less than 2.5 ×: Average score of 1.5 Less than

Odor rating criteria 4 points: No unpleasant odor in the oral cavity 3 points: Almost no unpleasant odor in the oral cavity 2 points: Some unpleasant odor in the oral cavity 1 point: Unpleasant odor in the oral cavity Odor evaluation criteria ◎: Average score 3.5 to 4.0 points ○: Average score 3.0 to 3.5 points △: Average score 2.0 to 3.0 points ×: Average score less than 2.0 points

Taste evaluation criteria 4 points: no strange taste in the oral cavity 3 points: almost no strange taste in the oral cavity 2 points: slightly strange taste in the oral cavity 1 point: strange taste in the oral cavity Evaluation criteria for taste ◎: Average score 3.5 points or more and 4.0 points or less ○: Average score 3.0 points or more and less than 3.5 points △: Average score 2.0 points or more and less than 3.0 points ×: Average score less than 2.0 points

Details of raw materials used are shown below.
(a) sodium polyacrylate (Mw: 1,000)
Linear, manufactured by Polyscience (a) sodium polyacrylate (Mw: 6,000)
Linear, manufactured by Toagosei Co., Ltd., AC-10NP
(a) sodium polyacrylate (Mw: 8,000)
Linear, manufactured by Polyscience (a) sodium polyacrylate (Mw: 20,000)
Linear, manufactured by Toagosei Co., Ltd., Aron A-20UN
Sodium polyacrylate (Mw: 300,000, comparative component)
Crosslinked type, Polyscience polyacrylic acid (Mw: 6,000, comparative component)
Linear, manufactured by Toagosei Co., Ltd., Aron A-10SL
(b) Citric acid Fuso Chemical Industry Co., Ltd., product name: purified citric acid (crystal)
(b) malic acid (DL-malic acid)
Manufactured by Fuso Chemical Industry Co., Ltd., product name: Fuso malic acid (b) phytic acid (50% liquid product)
Fuso Chemical Industry Co., Ltd., product name: phytic acid (b) disodium edetate Junsei Chemical Co., Ltd. (b) sodium tripolyphosphate Taihei Chemical Industry Co., Ltd. (b) sodium metaphosphate Taihei Chemical Industry Co., Ltd. ) made

＊；フィチン酸の配合量の数値は、純分量である（以下同様）。

*; The numerical value of the compounding amount of phytic acid is the pure amount (the same shall apply hereinafter).

[Example II, Comparative Example II]
Oral preparations containing the types and amounts of polyacrylates or alginates shown in Table 6 were prepared by a conventional method, and the effect of suppressing stain formation was evaluated by the following method. The results are also shown in Table 6.
Further, dentifrice compositions (toothpaste) having compositions shown in Tables 7 and 8 were prepared by a conventional method and filled in aluminum tube containers. The stain formation inhibitory effect and actual effect were evaluated by the following methods. The results are shown in Tables 7 and 8 together.

(3) Evaluation method of stain formation suppression effect A hydroxyapatite plate (manufactured by HOYA Corporation, diameter φ7.0 mm × thickness 3.5 mm, hereinafter abbreviated as HA plate) whose surface was previously polished by sandblasting was subjected to spectral color difference. (SE-2000, manufactured by Nippon Denshoku Co., Ltd.) to determine the ΔE value (ΔE ₀ ) of the HA plate before stain formation. (i) The above HA plate was immersed in a test solution (centrifuged supernatant of a 3-fold dilution of artificial saliva of an oral preparation) and allowed to stand for 10 minutes in a 50°C constant temperature bath. Remove the HA plate, remove the moisture on the surface of the HA plate, (ii) 0.5% albumin aqueous solution, (iii) tannin solution (Japanese tea (brand: Oimatsu) 50 g, black tea tea bag (Lipton, Brisk tea bag) ) were extracted with hot water, after cooling, 12 g of powdered coffee (manufactured by Nescafé) was added, and a solution prepared to 1,200 mL with purified water, (iv) a 0.56% iron (III) ammonium citrate aqueous solution. Each solution was immersed in order for 10 minutes at room temperature in a constant temperature bath at 50° C. The immersion operations (i) to (iv) were repeated 7 times, the HA plate surface was dried, and the ΔE value (ΔE ₁ ) was measured.
Instead of the test solution, _{purified water} was used for the same treatment. The suppression rate was calculated to evaluate the effect of suppressing stain formation.
Stain formation suppression rate (%) =
[(ΔE _1b −ΔE _0b )−(ΔE ₁ −ΔE ₀ )]/(ΔE _1b −ΔE _0b )×100
Evaluation criteria for stain formation inhibition effect ◎◎: Stain formation inhibition rate is 70% or more ◎: Stain formation inhibition rate is 60% or more and less than 70% ○: Stain formation inhibition rate is 50% or more and less than 60% △: Stain formation inhibition rate is 40% or more and less than 50% ×: Stain formation suppression rate is less than 40%

(4) Evaluation method for actual effect Ten subject monitors took about 1 g of the dentifrice composition on the toothbrush and continued to use the toothpaste for 3 minutes at least twice a day for 30 days. After that, the surface of the teeth became smooth. Feeling was evaluated in four stages according to the following evaluation criteria. The average score of 10 subjects was calculated, and the feeling of effect (feeling of effect that the tooth surface became smoother) was judged according to the following criteria. In the case of ◯ or ⊚, it was judged that the feeling of smoothness of the tooth surface continued to be felt, and the effects were felt well.
Evaluation criteria for feeling effect 4 points: very much felt 3 points: somewhat felt 2 points: not felt much 1 point: not felt Criteria for feeling that smooth feeling continued ◎: Average score of 3.5 points or more ○: Average score of 3 .0 points or more and less than 3.5 points △: average score of 2.0 points or more and less than 3.0 points ×: average score of less than 2.0 points

Details of raw materials used are shown below.
The component (a), sodium polyacrylate (comparative product) and polyacrylic acid (comparative product) used are the same as above.
(c) Sodium alginate Kimika Co., Ltd. Kimika algin (c) Propylene glycol alginate Kimika Co., Ltd. Kimiroid BF

The dentifrices 12 to 19 of Example II in Table 7 were excellent in the effect of suppressing stain formation, and the effect was highly felt. In addition, there was no offensive taste derived from the component (a), and there was no stringiness, and the feeling of use was good.

In addition, the dentifrice compositions (2-1) to (2-13) of Example I in Table 4 were evaluated for the stain formation inhibitory effect in the same manner as in (3) above. It was "◎◎".

Claims (15)

(a) a polyacrylate having a weight average molecular weight of 2,000 or more and 8,000 or less; Oral stain remover containing one or more chelating agents selected from citric acid, malic acid, succinic acid , sodium salts and potassium salts thereof (excluding agents containing hypochlorite) ) . The oral stain remover according to claim 1 , wherein (a)/(b) is 0.01 to 50 as a mass ratio. (a) a polyacrylate having a weight average molecular weight of 2,000 or more and 8,000 or less; An oral composition containing one or more chelating agents selected from citric acid, malic acid, succinic acid , sodium salts and potassium salts thereof (however, oral compositions containing hypochlorite except for). The oral cavity composition according to claim 3 , wherein (a)/(b) is 0.01 to 50 as a mass ratio. 5. The oral composition according to claim 3 , which contains 0.01 to 2% by mass of component (a) and 0.03 to 3% by mass of component (b). 6. The oral composition according to any one of claims 3 to 5 , further comprising (c) 0.05 to 2% by mass of one or more alginic acid derivatives selected from alginates and alginic acid esters. The composition for oral cavity according to any one of claims 3 to 6 , which is for removing stains. The oral composition according to any one of claims 3 to 7 , which is a dentifrice composition. (a) a polyacrylate having a weight average molecular weight of 2,000 or more and 8,000 or less; and (c) one or more alginic acid derivatives selected from alginates and alginate esters. The stain formation inhibitor for oral cavity according to claim 9 , wherein (a)/(c) is 0.05 to 5 as a mass ratio. An oral composition containing (a) a polyacrylate having a weight average molecular weight of 2,000 or more and 8,000 or less, and (c) one or more alginic acid derivatives selected from alginates and alginic acid esters. 12. The oral cavity composition according to claim 11 , wherein (a)/(c) is 0.05 to 5 as a mass ratio. The oral composition according to claim 11 or 12 , containing 0.01 to 2% by mass of component (a) and 0.05 to 2% by mass of component (c). The oral cavity composition according to any one of claims 11 to 13 , which is for suppressing stain formation. The oral composition according to any one of claims 11 to 14 , which is a dentifrice composition.