JP2015224233A - Composition for tooth cleaning treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for tooth treatment that is capable of tooth cleaning treatment and hyperesthesia preventive treatment.SOLUTION: The present invention provides a neutral or weak alkaline composition for tooth cleaning treatment, for forming a coating composed of an emulsion polymer on a tooth surface.

Description

  The present invention relates to a tooth cleaning treatment composition, and more particularly to a PMTC composition. More specifically, the present invention relates to a tooth cleaning treatment composition capable of forming a film made of a water-soluble and / or aqueous emulsion polymer on the tooth surface after the tooth cleaning treatment.

In dentistry, a tooth cleaning treatment called PMTC (Professional Mechanical Tooth Cleaning) is performed. This is a treatment that removes the deposited pigment by polishing the coloring or plaque that cannot be removed by ordinary toothpaste cleaning with a dedicated polishing paste and a cup-type or pencil-type brush.
In this procedure, the tooth itself is slightly polished when removing the deposits of the tooth, and in some cases, symptoms such as hypersensitivity may appear, and a gel containing fluoride is used after the treatment to prevent it. Etc. may be applied.
Hypersensitivity is a defect caused by wear of tooth enamel, etc., and is caused by exposure of dentin. There are many pores called dentinal tubules in the dentin, and pain is caused by stimulating the pulp through them. As a treatment for hypersensitivity, there is a method of sealing dentinal tubules exposed by applying a drug or the like (Patent Document 1).

Further, after the tooth cleaning treatment, in order to prevent coloring and plaque from redepositing on the tooth, a treatment for coating an antifouling material or the like may be further performed.
On the other hand, sulfonic acid compositions and the like are known as a hypersensitivity suppressing material, and there is an attempt to use this for a dentifrice or a coating agent.

JP 2008-184436 A

However, for example, a sensitization inhibitor such as a sulfonic acid type utilizes an action mechanism in which it reacts with the calcium content of teeth and is bound and fixed. Therefore, these hypersensitivity suppressing materials are used in the form of an acid in which the sulfonic acid group substantially releases hydrogen ions. In other words, the composition has been used acidic. However, toothpaste, that is, treatment involving physical polishing of teeth, when using acidic conditions, tooth decalcification is induced and the mechanical strength is reduced. Tooth quality has a problem that the risk of being greatly damaged is extremely high beyond an allowable range.
Moreover, also in the case of the treatment which coats antifouling materials, such as a sulfonic acid type, the composition is used by the acid with the same mechanism of action.

  In addition, when the composition is acidic, there is a problem that the oral mucous membrane and the taste system are too irritating to cause discomfort to the patient.

  As a result of intensive studies on the solution of the above problems, the present inventors have performed tooth cleaning treatment and / or cleaning by applying a paste and / or gel-like composition containing a water-soluble and / or aqueous emulsion polymer to the tooth surface. The present inventors have found that by protecting the later teeth, it is possible to prevent hypersensitivity as well as cleaning the teeth, thereby reaching the present invention.

  That is, the present invention is a neutral or weakly alkaline tooth cleaning treatment composition for forming a film made of an emulsion polymer on the tooth surface.

  A composition for oral cavity for forming a film comprising a water-soluble and / or aqueous emulsion polymer on the tooth surface, and particularly a paste and / or gel-like composition suitable for tooth cleaning treatment and / or tooth protection after cleaning It is possible to prevent hypersensitivity as well as tooth cleaning treatment.

  Hereinafter, the composition for tooth cleaning treatment of this invention is explained in full detail. Hereinafter, unless otherwise indicated, “%” represents “% by weight”.

The composition of the present invention is a neutral or weakly alkaline tooth cleaning treatment composition capable of forming a film made of an emulsion polymer on the tooth surface. More specifically, it is a paste and / or gel-like composition containing (A) a water-soluble and / or aqueous emulsion polymer, (a) water, and (B) an abrasive. Further, as necessary, (C) thickener, (D) binder, (E) flavor, (F) antiseptic / storage stabilizer, (G) pH adjuster, (H) surfactant, (I) Medicinal components, (J) coloring agents and the like can also be included. By adding the components (E) to (J), it is possible to further improve the stability of the composition, improve the tooth cleaning efficiency, and impart a medicinal effect.
Each of the above components is preferably 100 parts by weight of the total of the components (A) to (D), preferably 1 to 30 parts by weight of the component (A), 1 to 30 parts by weight of the component (B), (C) The component is in the range of 10 to 70 parts by weight, and the component (D) is in the range of 0.01 to 10 parts by weight. Further, when the components (E) to (G) are added, the component (E) is 0.01 to 10 parts by weight and the component (F) is in 100 parts by weight of the total of the components (A) to (G). 0.001 to 5 parts by weight, (G) component is preferably 0.001 to 5 parts by weight, and when components (H) to (I) are further added, components (A) to (I) It is preferable that the component (H) is 0.01 to 5 parts by weight and the component (I) is 0.0001 to 5 parts by weight in a total of 100 parts by weight. When the component (J) is added, The component (J) is preferably in the range of 0.001 to 5 parts by weight in a total of 100 parts by weight of the components A) to (J).
The component (A) of the present invention is a water-soluble and / or aqueous emulsion polymer.

  The water-soluble and / or aqueous emulsion polymer in the present invention refers to a water-soluble polymer, an aqueous emulsion polymer, or a mixture of both. Furthermore, a polymer whose properties change depending on changes in room temperature or the presence or absence of an electrolyte, and at least one of them has water-soluble or aqueous emulsion properties (for example, water-soluble and aqueous emulsion properties). Also included are polymers that can interchange between each other.

A polymer forming a film comprising a water-soluble and / or aqueous emulsion polymer on the tooth surface is a polymer that can be dissolved in water or an aqueous solvent or can be emulsified in a colloid and / or a water-soluble state and A cross-linked polymer formed from a polymer in a colloidal aqueous emulsion state. For example, when it is contained as a polymer in the composition of the present invention, it remains in a dissolved state or an emulsion state, but remains in the form of a water-soluble or aqueous emulsion after film formation. Alternatively, it may be insolubilized with water or made non-emulsifiable with a crosslinking agent or the like after the coating is formed. In addition, the polymer in the composition of the present invention is applied before application due to a temperature change within a normal temperature range, a substance normally present in the oral cavity or a dental material that can be used in combination with the application of the composition of the present invention. In addition, when it changes to properties other than water-soluble and / or aqueous emulsion properties, such as water insolubility or non-emulsion properties, it is difficult to recover the original homogeneous or dispersed system, which may cause inconvenience in operability. Therefore, a polymer that is unlikely to change at least before coating is preferable.
The solubility of the water-soluble polymer in water or an aqueous solvent is preferably 0.01% or more, more preferably 0.05% or more, and further preferably 0.1% or more.

  The average molecular weight of the water-soluble and / or aqueous emulsion polymer of the component (A) of the present invention is 1,000 or more, and the (P) polymer is dispersed in an aqueous solvent in a dissolved, semi-dissolved or emulsified state. It is a thing. (P) The lower limit of the average molecular weight of the polymer is preferably 1,000, more preferably 10,000, and still more preferably 50,000. In the case of a water-soluble polymer, the upper limit of the average molecular weight is preferably 5,000,000, more preferably 4,000,000, and still more preferably 3,000,000. When the value falls below the lower limit of the numerical range, the formed film immediately dissolves in saliva and the like.On the other hand, in the case of a water-soluble polymer, the solubility in an aqueous solvent is remarkably poor, and it becomes a hard gel. There may not be. On the other hand, in the case of an aqueous emulsion polymer, there is no particular upper limit on the average molecular weight as long as it has aqueous emulsion properties. However, in a normal production method such as emulsion polymerization, about 10,000,000 is on the production technology. It is a limit. In addition, all the said average molecular weights are the measured values (polystyrene conversion) by gel permeation chromatography.

  Specific examples of the (P) polymer include a homopolymer or a copolymer synthesized from the radical polymerizable monomer (p1). Examples of the radically polymerizable monomer that can be used most generally as (p1) include conjugated diene monomers such as butadiene and isoprene; aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; acrylonitrile , Vinyl cyanide monomers such as methacrylonitrile; methyl (meth) acrylate (hereinafter referred to as “(meth) acrylate” as a general term for acrylate and methacrylate), methyl (meth) acrylate, ethyl (meth) acrylate, Alkyl (meth) acrylates such as butyl (meth) acrylate; vinyl halides and vinylidenes such as vinyl chloride, vinyl bromide, vinylidene chloride and vinylidene bromide; vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylamide (Hereafter, Nyl (meth) acryloyloxyethyl-acetamide, N- (meth) acryloxypropyl-acetamide, N- (meth) acrylic is a generic name for rilamide and methacrylic amide. Examples thereof include N- (meth) acryloxyalkyl-acetamide such as roxyisopropyl-acetamide, N- (meth) acryloxybutyl-acetamide, N- (meth) acryloxypropyl-acetamide. These radically polymerizable monomers can be used alone or in combination of two or more for polymerization. Of these, alkyl (meth) acrylate radically polymerizable monomers are preferably used.

  The film formed by the component (A) is preferably attached or adhered to the tooth surface. Therefore, the radical polymerizable monomer constituting the component (P) is preferably a radical polymerizable monomer (p2) having at least one acidic group in the molecule in order to interact with the tooth substance. Examples of the acidic group include at least one selected from the group consisting of a carboxyl group, a group in which at least one hydroxyl group is bonded to a phosphorus atom, and a sulfonic acid group. Examples of a method for introducing such a functional group include a method of hydrolyzing a polymer containing a polymer unit derived from a carboxylic acid ester or a phosphate ester. Furthermore, as a method for producing the component (P), the radical polymerizable monomer and the radical polymerizable monomer having the functional group or a functional group that can be easily converted into the functional group in water are used. There is a method of polymerization, and this method is preferred. Examples of the radical polymerizable monomer having a functional group that interacts with the tooth substance include the following compounds.

  Examples of the radically polymerizable monomer having a carboxyl group of component (p2) or a functional group that can be easily converted into a carboxyl group in water include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid, and anhydrides thereof. Can be mentioned. Specifically, α-unsaturated carboxylic acid ((meth) acrylic acid, maleic acid, etc.), carboxylic acid (4-vinylbenzoic acid etc.) added with vinyl aromatic rings, (meth) acryloyloxy group and carboxylic acid group Carboxylic acid (11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid (MAC-10) etc.) having a linear hydrocarbon group between them, and carboxylic acid having an aromatic ring (1,4-di ( (Meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid, etc.), 4- (meth) acryloyloxyalkyl trimellitic acid and its anhydride (4- (meta ) Acryloyloxymethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxyethyl trimellitic acid and Its anhydride, 4- (meth) acryloyloxybutyl trimellitic acid and its anhydride), carboxylic acid having a hydrophilic group such as a hydroxyl group in the alkyl chain and its anhydride (4- [2-hydroxy-3- ( Meth) acryloyloxy] butyl trimellitic acid and its anhydride), compounds having carboxybenzoyloxy (such as 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate), N- And / or O-mono or di (meth) acryloyloxyamino acid (N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) Acryloyloxyphenylalanine), N- (meth) acryloylamino Benzoic acid (N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5-aminobenzoic acid, etc.), addition reaction product of hydroxyalkyl (meth) acrylate and unsaturated polycarboxylic anhydride ( 2 or 3 or 4- (meth) acryloyloxybenzoic acid, 4 or 5- (meth) acryloylaminosalicylic acid, addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride (PMDM), 2-hydroxyethyl (meth) acrylate and maleic anhydride or 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) or 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride addition reaction product), a compound having polycarboxybenzoyloxy and (meth) acryloyloxy (Such as 2- (3,4-dicarboxybenzoyloxy) -1,3-di (meth) acryloyloxypropane), N-phenylglycine or an adduct of N-tolylglycine and glycidyl (meth) acrylate, 4-[(2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 3 or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthale An acid etc. can be mentioned. Of these, 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10) and 4-methacryloyloxyethyl trimellitic acid (4-MET) or its anhydride (4-META) are preferably used.

  (P2) a group in which at least one hydroxyl group of the component is bonded to a phosphorus atom and a functional group that can be easily converted into the group in water, for example, a group having one or two hydroxyl groups with a phosphate group Can be preferably exemplified. Examples of the polymerizable monomer having such a group include phosphate esters having one or more (meth) acryloyloxyalkyl groups (2- (meth) acryloyloxyethyl acid phosphate, 2 and 3- (Meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyloxyoctyl acid phosphate Fate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate, bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2 Or 3- (meth) acryloyloxypropyl] acid phosphate A phosphate ester (2- (meth) acryloyloxyethylphenyl acid phosphate, wherein a linear hydrocarbon group exists between the (meth) acryloyloxy group and the phosphate group, and also has an aromatic group, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate, etc.). The compound which substituted the phosphate group in these compounds by the thiophosphate group can also be illustrated. Of these, 2- (meth) acryloyloxyethylphenyl acid phosphate and 10- (meth) acryloyloxydecyl acid phosphate are preferably used.

  (P2) As a polymerizable monomer having a sulfonic acid group or a functional group that can be easily converted into a sulfonic acid group in water, for example, 4-styrene sulfonic acid or a salt thereof, a substituent containing hetero (halogen or alkoxy) (Meth) acrylates having 2-sulfonic acid groups (2-sulfoethyl (meth) acrylate, 2- or 1-sulfo-1- or 2-propyl (meth) acrylate), 1 or 3 -Sulfo-2-butyl (meth) acrylate, 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate, etc.) 1,1-dimethyl-2-sulfoethyl (meth) acrylamide and the like. Among these, 2-methyl-2- (meth) acrylamide propanesulfonic acid, 4-styrenesulfonic acid or a salt thereof is preferably used.

  The content of the component (p2) constituting the component (P) is preferably 0.1 to 30 mol%, more preferably 0.5 to 25 mol%, still more preferably 1 with respect to the total amount of the constituting monomers. It is in the range of ˜20 mol%. If the amount is less than 0.1 mol%, the interaction effect with the tooth cannot be confirmed. If the amount exceeds 30 mol%, the acidity in the aqueous solution increases, and there is a concern about harm to the living body.

  As the radical polymerizable monomer constituting the component (P), an antibacterial radical polymerizable monomer (p3) can also be used. (P3) can impart antibacterial properties to the coating itself covering the tooth surface. Examples of such compounds include 12- (meth) acryloyloxidedecylpyridinium bromide, benzylbis [(meth) acryloyloxyethyl] dodecylammonium chloride, N, N, N-tris [(meth) acryloyloxyethyl] dodecylammonium chloride. be able to.

The aqueous polymer (Aw) having a preferable water solubility as the acidic group-containing (co) polymer (A) component is a (meth) acrylamidoalkanesulfonic acid (H ₂ C═C (R1)) in the polymer molecule. _{-CO-NH-R2-SO 3} H, R1: H or _CH 3, R2: 2 divalent hydrocarbon group) is a polymer having a component unit derived from a radically polymerizable monomer (p2) and the like. Further in the molecule of the polymer, of 4 to 8 carbon atoms having a hydroxyl group one or more (poly) hydroxyalkyl (meth) acrylamide _{(H 2 C = C (R3} ) -CO-NH-R4 (OH) n, Component units derived from R3: H or CH ₃ , R4: hydrocarbon group, n: integer of 1 or more) are in a hydroxyl group molar ratio (total number of hydroxyl groups of the units in the polymer / number of moles of total monomer units). ), Preferably 0.7 to 11.0 [mol / mol], more preferably 0.75 to 10.5 [mol / mol], and still more preferably 0.8 to 10.0 [mol / mol]. It is preferable to use the polymer which has.

  Copolymers other than the copolymer (hereinbelow referred to as AS-HA polymer) having the (meth) acrylamide alkanesulfonic acid unit and the (poly) hydroxyalkyl (meth) acrylamide unit (herein, the following) In the case of AS-HA equivalent polymer), the molar weight ratio [moles] is the ratio of the number of moles of acidic groups (sulfonic acid, etc.) and hydroxyl groups contained in the AS-HA equivalent polymer to the weight of the AS-HA equivalent polymer. / G] is a molar weight ratio corresponding to the numerical range of the molar ratio [mol / mol] in the case of the AS-HA polymer (provided that the AS-HA polymer is 2,3-dihydroxypropyl (meta ) Acrylic amide and 2- (meth) acrylic amide-2-methylpropanesulfonic acid, and the ratio is measured as a copolymer having methyl acrylate as required. ) Preferably in the above range.

  In the present invention, a styrene sulfonic acid unit is preferred as the (Ms) component unit forming the polymer (Ae) having a preferred aqueous emulsion form as the acidic group-containing (co) polymer as the component (A). Furthermore, in the polymer molecule, the (meth) acrylic acid alkyl ester unit having 4 to 8 carbon atoms is preferably in a molar ratio (number of moles of the unit / number of moles of total polymerized units in the polymer). It is an emulsion containing a copolymer having ˜99.9 [mol / mol], more preferably 80 to 99.9 [mol / mol], and still more preferably 85 to 99.5 [mol / mol] as emulsion particles. .

The component (A) is prepared by dissolving the component (P) in an aqueous solvent such as distilled water, purified water, or ion exchange water. The concentration of the component (P) in the component (A) is in the range of 0.001% to 30%, more preferably 0.01% to 20%, and still more preferably 0.1% to 10%. It is done.
(A) component shows acidity by the acidic group in (P) component. Therefore, you may perform a neutralization process as needed so that pH may be adjusted to neutrality as the whole composition. In neutralization, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and other alkali metal salts can be used. A calcium phosphate material having the same ionization tendency as the calcium atom of a calcium phosphate material such as apatite is preferably used. Therefore, it is preferable to use a calcium phosphate-based material as an abrasive, particularly when the pH is adjusted from neutral to weakly alkaline without adding a neutralizing agent.

The composition of the present invention is not particularly limited as long as the pH is neutral to weakly alkaline, but is preferably 5.0 to 12.0, more preferably 6.0 to 11.0, still more preferably 7 0.0-10.0. If the lower limit of the numerical range is not reached, there is a possibility that the tooth surface will be desorbed by acid, while if it exceeds the upper limit, an adverse effect on the mucous membrane or the like may be caused by alkali, which is not preferable.
In the present invention, the acidic group-containing (co) polymer of the component (A) is preferably an aqueous emulsion (Ae) or a water-soluble polymer (Aw), and particularly when it is a water-soluble polymer, The solubility in water of the acidic group-containing (co) polymer at 25 ° C. is preferably 25% or more.

When the acidic group-containing (co) polymer is an aqueous emulsion (Ae), the particles of the components in the aqueous emulsion (Ae) are used to penetrate the aqueous emulsion to a depth sufficient to seal the dentin tubules. The diameter is preferably smaller than the diameter of the dentinal tubule. In general, the diameter of the dentinal tubule varies depending on the position or depth, and although there are individual differences, it is usually in the range of 1 to 3 μm. Therefore, the average particle size of the component particles constituting the aqueous emulsion (Ae) is preferably 3 μm or less, more preferably 1 μm or less.
The diameter of the dentinal tubule is determined by removing the enamel from the extracted tooth, brushing the exposed dentin surface with a dentifrice and a toothbrush for 1 minute or more, then performing ultrasonic cleaning in water, scanning type It can measure by observing with an electron microscope (SEM).

  Further, since there is a distribution in the particle size of the component constituting the aqueous emulsion (Ae), it is not particularly required that the particle size of all the emulsion particles is smaller than the dentinal tubule diameter. In the present invention, among the particles forming the emulsion of the aqueous emulsion (Ae) component, those having a particle size of less than 3 μm preferably account for 50% or more, and the particle size of 90% or more of the emulsion particles is less than 3 μm. More preferred. In addition to the above conditions, among the particles forming the aqueous emulsion used as the polymer (A) component having a radical polymerizable monomer as a single unit, those having a particle size of 1 μm or less occupy 65% or more. Is particularly preferable, and it is particularly preferable to occupy 75% or more. When the emulsion particles have a particle size distribution as described above, pain due to hypersensitivity is reduced.

  As a more preferred aqueous emulsion (Ae) component, for example, polymer emulsion particles are preferably dispersed in a high-speed mixer or homogenizer, for example, with a diameter of 3 μm or less, more preferably 1 μm or less, and most preferably 0. It is desirable to form emulsion particles of 5 μm or less and improve the dispersion stability by preparing the emulsion particles to be present in an amount of 0.5% or more in the acidic group-containing (co) polymer (A) component. Further, in the acidic group-containing (co) polymer (A) component, it is preferable that emulsion particles having a particle size of 1.0 μm or less occupy 50% or more, particularly 75% or more of the whole emulsion particles, and emulsion particles Most preferably.

The component for forming an aqueous emulsion (Ae) having a particle diameter smaller than the dentin tubule diameter contained in the acidic group-containing (co) polymer is highly water-soluble and usually has a solubility in water of 25 ° C. of 0.5 g. When a calcium compound, for example, calcium chloride, is added to the acidic group-containing (co) polymer (A), an aggregate having a diameter larger than the diameter of the dentinal tubule reacts with the calcium compound. Can be formed.
The diameter of the aggregate formed in this manner usually exceeds 3 μm, preferably 10 μm or more, more preferably 50 to several thousand μm.
There is no restriction | limiting in particular in the manufacturing method of an acidic group containing (co) polymer (A), It can manufacture by a conventionally well-known method.
As a specific production method, when the acidic group-containing (co) polymer (A) is an aqueous emulsion (Ae), it can be produced by employing a conventionally known emulsion polymerization method. Specifically, in the presence of a polymerization initiator, various monomers can be added all at once, divided, or continuously dropwise into an aqueous medium. The polymerization temperature at this time is generally 0 to 100 ° C., and practically 30 to 90 ° C.

  Moreover, when an acidic group containing (co) polymer is a water-soluble polymer (Aw), it can manufacture by a conventionally well-known method using water or an aqueous medium. For example, after charging various monomers and a polymerization initiator in water or an organic solvent and allowing the polymerization reaction to proceed by raising the temperature, for example, a method of obtaining an aqueous polymer by reprecipitation purification or the like can be mentioned. In this case, the reaction temperature is generally 40 to 200 ° C.

  The component (A) is 1 to 30 parts by weight per 100 parts by weight of the composition of the present invention, for example, in the composition comprising the components (A) to (D) in 100 parts by weight of the total of the components (A) to (D). More preferably, it is used in the range of 3 to 25 parts by weight, and when it is below the lower limit value, it becomes difficult to form a film on the dentin, and the effect of suppressing hypersensitivity and the effect of suppressing plaque adhesion are reduced, and the upper limit value. In the case where it exceeds 1, the operability is lowered along with the change in the physical properties of the paste, so that both are not preferable.

The component (B) of the present invention is an abrasive. As the component (B), such as abrasive silicic anhydride, aluminum hydroxide, alumina, magnesium carbonate, tertiary magnesium phosphate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, titanium oxide, synthetic resin-based abrasive, etc. Usually, the well-known abrasive | polishing material used for a dentifrice is mentioned. Preferably, calcium phosphate-based materials such as dentifrice calcium hydrogen phosphate, calcium pyrophosphate, calcium carbonate, and hydroxyapatite are preferable, and hydroxyapatite is particularly preferably used.
Component (B) is, for example, a composition comprising components (A) to (D) per 100 parts by weight of the composition of the present invention, and 5 to 50 parts by weight in a total of 100 parts by weight of components (A) to (D). More preferably, it is used in the range of 10 to 40 parts by weight, and when the value is below the lower limit and / or the value exceeds the upper limit, the operability is lowered with changes in the physical properties of the paste, which is not preferable. In particular, the phosphoric acid calcium material is used in a range of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, in a total of 100 parts by weight of the components (A) to (D). If the value falls below the lower limit of the numerical range, the paste viscosity becomes low. On the other hand, if the value exceeds the upper limit, the paste viscosity becomes high.

  The inorganic calcium salt (B) in the dental abrasive composition having a hypersensitivity suppressing property of the present invention is a calcium salt whose solubility in water at 25 ° C. is usually less than 0.5 g / 100 ml. It is. The inorganic calcium salt has a function of removing organic substances and inorganic deposition components on the tooth surface.

Specific compounds include CaHPO ₄ (hereinafter referred to as DCP), Ca ₃ (PO ₄ ) ₂ (hereinafter referred to as TCP), Ca ₅ (PO ₄ ) ₃ OH, and Ca ₄ O (PO ₄ ) _2. (Hereinafter referred to as TTCP), Ca ₈ H ₂ (PO ₄ ) ₆ , Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ (hereinafter referred to as HAP), CaP ₄ O ₁₁ , Ca (PO ₃ ) ₂ , Ca ₂ P ₂ O ₇ , Ca (H ₂ PO ₄ ) ₂ , CaO, Ca (OH) ₂ , CaCO ₃ and hydrates thereof. These can be used alone or in combination. There are no particular limitations on the crystal structure of these inorganic calcium salts, and non-stoichiometric defects may also be included. Of these, DCP, TCP, TTCP, and HAP are preferably used in the present invention. These inorganic calcium salts can be used alone or in combination.

Of these inorganic calcium salts, when DCP or TTCP is used, it is preferable to use both. By using both at the same time, after applying the dental abrasive composition having the sensitivity to hypersensitivity, these phosphates bind to the tooth surface in the presence of moisture in the oral cavity and are similar to hard tissues It can be converted into HAP and the tooth surface can be modified.
The usage-amount of an inorganic calcium salt (B) component is 0.1 to 50% normally with respect to the whole quantity of a composition, Preferably it is 1 to 40%, More preferably, it is 3 to 30%. If the upper limit of this numerical range is exceeded, the viscosity of the composition will increase and cleaning operations will not be possible, and it will be difficult for the composition to penetrate the tooth surface or interdental area, resulting in poor cleaning performance and excessive tooth surface. In addition, if it falls below the lower limit, the desired cleaning effect is hardly exhibited.

Further, in the present invention, when DCP and TTCP are used at the same time, the mixing weight ratio (TTCP / DCP) of the both is usually 0.33 to 3.5, preferably 2.3 within the range of the amount used. Is in the range of ~ 3, particularly preferably 2.6 to 2.8. Beyond this range, the conversion to hydroxyapatite may not be sufficient.
In the present invention, the shape of the inorganic calcium salt (B) component is not particularly limited, and may be spherical, spindle-shaped or irregular, but in order to polish and clean the tooth surface in a short time, it is irregular. Preferably there is. In order to further improve the cleaning performance, it is preferable to include a sintered body having high hardness.

  The longest diameter of the inorganic calcium salt (B) component used here is usually 0.001 to 300 μm, preferably 0.05 to 250 μm, and more preferably 0.01 to 200 μm. Here, the longest diameter means the diameter of the maximum length of the particle including the case where the particle shape of the inorganic calcium salt (B) component is spherical. If the upper limit of this numerical range is exceeded, the dental hard tissue may be excessively ground, and if the lower limit is exceeded, the polishing performance will be extremely low, and polishing will take a long time. There are concerns about adverse effects. Furthermore, when DCP and TTCP are used simultaneously, the longest diameter of DCP is usually in the range of 0.001 to 30 μm, preferably 0.05 to 20 μm, more preferably 0.1 to 15 μm. The longest diameter is usually in the range of 0.5 to 30 μm, preferably 1 to 25 μm, more preferably 10 to 20 μm. If the value is below the lower limit of the numerical range, the composition tends to aggregate during the polishing operation and the operation becomes difficult. If the value exceeds the upper limit, it takes a long time to convert the tooth surface to HAP, and the tooth surface is modified. Quality effects are less likely to appear.

  Further, there is no particular limitation on the presence form of these calcium phosphate salts, and both may be particles that are mixed and molded in an amount within the above-mentioned blending range, or the entire blending The respective particles may be mixed so that the ratio is substantially within the above range, or particles having different blending ratios may be mixed so as to be within the above range.

As the component (B) of the present invention, hydroxyapatite is preferable, but the hydroxyapatite used as the abrasive is preferably highly crystalline hydroxyapatite, and the average particle size of the particles is more preferably in the range of 10 to 1000 nm. Are combined with hydroxyapatite or other abrasives having individual or different average particle diameters of 20-150 nm, more preferably 25-50 nm nanoparticles and fine particles having an average particle diameter of 1-50 μm, more preferably 1-30 μm. Therefore, a higher polishing effect can be expected.
Here, “high crystallinity” according to the highly crystalline hydroxyapatite of the present invention means that the half width at d = 2.814 is 0.7 or less, preferably 0.5 or less. .

  Below, the manufacturing method of highly crystalline hydroxyapatite is demonstrated. Highly crystalline hydroxyapatite can be obtained by sintering amorphous hydroxyapatite. The hydroxyapatite may be artificially produced by a known production method such as a wet method, a dry method, a hydrolysis method, a hydrothermal method, or a natural product obtained from bone, teeth, etc. It may be derived from. Moreover, as a lower limit of sintering temperature, 500 degreeC is preferable. If the sintering temperature is lower than 500 ° C., the sintering may not be sufficient. On the other hand, the upper limit of the sintering temperature is preferably 1800 ° C, more preferably 1250 ° C, and particularly preferably 1200 ° C. When the sintering temperature is higher than 1800 ° C., hydroxyapatite may be decomposed. Therefore, highly crystalline hydroxyapatite can be produced by setting the sintering temperature within the above range. In addition, the sintering time is not particularly limited, and may be set as appropriate. In some cases, the particles may be fused together by sintering. In such a case, the sintered particles can be used after being pulverized.

The highly crystalline hydroxyapatite is preferably produced by the following method. This production method is preferably a method including at least a sintering step, and a method for producing highly crystalline hydroxyapatite having a uniform particle size in the range of 20 to 100 nm is a method including a mixing step and a sintering step. It is preferable that there is a primary particle generation step and a removal step. These processes are performed in the order of, for example, a primary particle generation process, a mixing process, a sintering process, and a removing process.
On the other hand, the method for producing hydroxyapatite having an average particle diameter of 1 to 50 μm is preferably a method including a spray drying step and a sintering step, and may include a primary particle generation step and a removal step. These processes are performed in the order of, for example, a primary particle generation process, a spray drying process, a sintering process, and a removal process.

(Primary particle generation process)
The primary particle generation step is not particularly limited as long as it is a step capable of generating hydroxyapatite, and may be adopted after being appropriately selected depending on the raw material of the highly crystalline hydroxyapatite to be produced.

  There is no particular limitation on the method for generating primary particle groups that are fine (nanometer size) and have a uniform particle size (narrow particle size distribution), such as hydroxyapatite according to the best mode. The method described in JP-A-2002-137910 can be used. In other words, calcium phosphate (phosphoric apatite) fine particles (primary particles) are obtained by solubilizing and mixing a calcium solution and a phosphoric acid solution in a surfactant / water / oil emulsion phase and reacting at a cloud point or higher of the surfactant. It can be synthesized. At this time, the size of the calcium phosphate fine particles can be controlled by changing the functional group of the surfactant and the ratio of the hydrophilic / hydrophobic ratio.

  The principle for producing the calcium phosphate fine particles will be briefly described as follows. In the method of solubilizing and mixing calcium solution and phosphate solution in surfactant / water / oil emulsion phase and reacting them to synthesize calcium phosphate fine particles, the core of calcium phosphate grows in the micelle of surfactant Then, the particles grow. At this time, the thermodynamic stability of the micelle is controlled by changing the reaction temperature (in the case where the surfactant is a nonionic surfactant, the clouding point of the surfactant should be set). be able to. That is, raising the reaction temperature of the surfactant means lowering the ability to form surfactant micelles. Then, it is considered that the driving force for the growth of calcium phosphate particles, which has been limited in the frame of micelles, is larger than the driving force for maintaining the frame of micelles. Therefore, the shape of the particles can be controlled using the mechanism.

  When making surfactant micelles, the functional group (hydrophilic site) of the surfactant and the hydrophilic / hydrophobic ratio in the molecule are important. The stability and cloud point of the micelle also differ depending on this difference. . The cloud point of the surfactant varies depending on the type. Therefore, by appropriately changing the type of the surfactant, the functional group of the surfactant and the ratio of the hydrophilic / hydrophobic ratio can be changed, and the size of the calcium phosphate fine particles can be controlled.

  The type of surfactant used in the above method is not particularly limited, and other types of known anions, cations, amphoteric ions, and nonionic surfactants disclosed in JP-A-5-17111. It can be used by appropriately selecting from agents. Among these surfactants, in the case of a nonionic surfactant, since it has a cloud point of the surfactant, it becomes easy to control the shape of the crystal using the above-mentioned mechanism. More specifically, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkyl allyl ether Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be used. Further, as the cationic surfactant, quaternary ammonium salts such as stearylamine hydrochloride, lauryltrimethylammonium chloride, and alkylbenzenedimethylammonium chloride can be used. As the anionic surfactant, sodium lauryl alcohol sulfate is used. Higher alcohol sulfates such as sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl amino acid salts such as sodium lauryl glutamate, and alkylaryls such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate Sulfonic acid salts can be used, and amphoteric surfactants include alkylbetaine type, alkylamide betaine type, amine amine. Side type and the like are available. Said surfactant is used by 1 type or in combination of 2 or more types. Among these, it is desirable to use pentaethylene glycol dodecyl ether, sodium lauryl sulfate, and sodium lauryl glutamate, particularly from the viewpoint of cloud point and solubility.

Examples of the oil phase usable in the above method include hydrocarbons such as toluene, xylene, hexane, dodecane, and cyclohexane, halogenated hydrocarbons such as chlorobenzene and chloroform, ethers such as diethyl ether, and alcohols such as butanol. , Ketones such as methyl isobutyl ketone, cyclohexanone, etc., and these solvents have low water solubility depending on the surfactant used, and one or two of the above-mentioned surfactants are dissolved so as to dissolve any of the above surfactants. Select a species. Among these, it is particularly desirable to use dodecane from the viewpoints of water solubility and surfactant solubility. In addition to this, the reaction temperature, reaction time, addition amount of the raw material, and the like may be adopted after selecting optimal conditions according to the composition of the primary particles. However, since the upper limit of the reaction temperature is an aqueous solution reaction, it is preferably a temperature at which the solution does not boil, and preferably 90 ° C. or less.
Further, this step may include a step of washing the produced primary particles with water or the like, and a step of collecting the primary particles by centrifugation, filtration or the like.

(Mixing process)
The mixing step is a step of mixing the primary particles and the anti-fusing agent. By interposing an anti-fusing agent between the particles of the primary particle group obtained by the primary particle generation step, it is possible to prevent the fusion of primary particles in the subsequent sintering step. It is. The mixture of primary particles and anti-fusing agent obtained by the mixing step is called “mixed particles”.

  Here, the “fusion preventive agent” is not particularly limited as long as it can prevent fusion between primary particles, but may be non-volatile at a sintering temperature in a subsequent sintering step. preferable. Because it is non-volatile under the sintering temperature condition, it does not disappear from the primary particles during the sintering process, and the fusion of the primary particles can be reliably prevented. However, it is not necessary to have 100% non-volatility at the sintering temperature, as long as it is non-volatile so that 10% or more remains between the primary particles after the sintering process is completed. The anti-fusing agent may be chemically decomposed by heat after completion of the sintering process. That is, if it remains after the end of the sintering process, it is not necessary to be the same substance (compound) before and after the start of the sintering process.

  The anti-fusing agent is preferably a substance that dissolves in a solvent, particularly an aqueous solvent. As described above, by using an anti-fusing agent that dissolves in a solvent as an anti-fusing agent, it is possible to prevent adhesion by simply suspending calcium phosphate fine particles mixed with the anti-fusing agent in an aqueous solvent such as pure water. Agents (such as calcium carbonate) can be removed. In particular, if the anti-fusing agent is soluble in an aqueous solvent, it is not necessary to use an organic solvent to remove the anti-fusing agent. It becomes. Therefore, it can be said that the anti-fusing agent can be removed from the calcium phosphate fine particles more easily. Although it does not specifically limit as said solvent, For example, water, ethanol, methanol etc. are mentioned as an aqueous solvent, Acetone, toluene etc. are mentioned as an organic solvent.

The aqueous solvent may contain a chelate compound such as oxalate, ethylenediamine, bipyridine, and ethylenediaminetetraacetate in order to increase the solubility of the anti-fusing agent in water. Further, the aqueous solvent may contain electrolyte ions such as sodium chloride, ammonium nitrate and potassium carbonate in order to increase the solubility of the anti-fusing agent in water.
Here, it can be said that the higher the solubility of the anti-fusing agent in the solvent is, the higher the removal efficiency becomes. The preferable solubility is preferably 0.01 g or more, more preferably 1 g or more, and most preferably 10 g or more, when the amount of solute (g) with respect to 100 g of solvent is the solubility.
Specific examples of the anti-fusing agent include calcium chloride, calcium oxide, calcium sulfate, calcium nitrate, calcium carbonate, calcium hydroxide, calcium acetate, calcium citrate, and other calcium salts (or complexes), potassium chloride, and potassium oxide. Potassium salts such as potassium sulfate, potassium nitrate, potassium carbonate, potassium hydroxide, potassium phosphate, sodium salts such as sodium chloride, sodium oxide, sodium sulfate, sodium nitrate, sodium carbonate, sodium hydroxide, sodium phosphate, etc. It is done.

  The method of mixing the primary particles and the anti-fusing agent in the mixing step is not particularly limited, and after mixing the solid anti-fusing agent with the solid primary particles, the mixture is mixed using a blender. Or a method of dispersing primary particles in a solution of an anti-fusing agent. However, since it is difficult to uniformly mix the solid and the solid, it can be said that the latter is a preferable method for interposing the anti-fusing agent uniformly and reliably between the primary particles. When the latter method is adopted, it is preferable to dry the anti-fusing agent solution in which primary particles are dispersed. This is because the state in which the primary particles and the anti-fusing agent are uniformly mixed can be kept for a long time. Also in the Example mentioned later, the hydroxyapatite (HAp) primary particle 0.5g is disperse | distributed to calcium carbonate saturated aqueous solution, It is made to dry at 80 degreeC, and the mixed particle is acquired.

  Further, the mixing step includes a solution containing a polymer compound having any of a carboxyl group, a sulfuric acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an amino group, or a salt thereof in the side chain, and the primary particles described above. May be added, and a metal salt (alkali metal salt and / or alkaline earth metal salt and / or transition metal salt) may be further added. By adopting the above steps, the polymer compound is adsorbed on the surface of calcium phosphate {hydroxyapatite (HAp)} to reliably prevent calcium phosphate {hydroxyapatite (HAp)} from contacting each other in the anti-fusing agent mixing process. Then, by adding a calcium salt, it becomes possible to reliably deposit the anti-fusing agent on the surface of the calcium phosphate {hydroxyapatite (HAp)}. In the following description, a polymer compound having a carboxyl group, a sulfate group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an amino group or a salt thereof in the side chain is simply referred to as “polymer”. Referred to as "compound".

  The polymer compound is not particularly limited as long as it is a compound having any of a carboxyl group, a sulfate group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an amino group or a salt thereof in the side chain. Examples of the polymer compound having a carboxyl group in the side chain include polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, carboxymethylcellulose, styrene-maleic anhydride copolymer, and the like. Examples of the polymer compound having a sulfate group in the chain include polyacrylic acid alkyl sulfate ester, polymethacrylic acid alkyl sulfate ester, polystyrene sulfate, etc., and the polymer compound having a sulfonic acid group in the side chain includes polyacrylic acid. Examples thereof include alkyl sulfonic acid esters, polymethacrylic acid alkyl sulfonic acid esters, polystyrene sulfonic acid, etc., and polymer compounds having a phosphate group in the side chain include polyacrylic acid alkyl phosphoric acid esters and polymethacrylic acid alkyl phosphoric acid esters. , Police Examples of the polymer compound having a phosphonic acid group in the side chain include polyacrylic acid alkylphosphonic acid ester, polymethacrylic acid alkylphosphonic acid ester, polystyrene phosphonic acid, polyacryloylamino. Examples thereof include methylphosphonic acid and polyvinylalkylphosphonic acid. Examples of the polymer compound having an amino group in the side chain include polyacrylamide, polyvinylamine, polymethacrylic acid aminoalkyl ester, polyaminostyrene, polypeptide, protein and the like. In the mixing step, any one of the above polymer compounds may be used, but a plurality of types of polymer compounds may be mixed and used.

  The molecular weight of the polymer compound is not particularly limited, but is preferably 100 g / mol or more and 1,000,000 g / mol or less, more preferably 500 g / mol or more and 500,000 g / mol or less, and 1,000 g / Mol to 300,000 g / mol is most preferred. When the ratio is less than the lower limit of the above preferable range, the ratio of entering between the primary particles decreases, and the ratio of preventing contact between the primary particles decreases. If the upper limit of the above preferred range is exceeded, the solubility of the polymer compound will be low, and the operability such as the viscosity of the solution containing the polymer compound will be poor, such being undesirable.

  The solution containing the polymer compound is preferably an aqueous solution. This is because hydroxyapatite (HAp) dissolves under strong acidic conditions. The pH of the aqueous solution containing the polymer compound is not particularly limited as long as the pH is 5 or more and 14 or less and the HAp particles are insoluble. The aqueous solution containing the polymer compound may be prepared by dissolving the polymer compound in distilled water, ion-exchanged water or the like, and adjusting the pH with an aqueous solution of ammonia aqueous solution, sodium hydroxide, potassium hydroxide or the like.

  The concentration of the polymer compound contained in the aqueous solution is preferably 0.001% w / v or more and 50% w / v or less, more preferably 0.005% w / v or more and 30% w / v or less. Most preferred is 01% w / v or more and 10% w / v or less. If the amount is less than the lower limit of the above preferable range, the amount of entering between the primary particles is small, and the ratio of preventing contact between the primary particles is low. Moreover, when the upper limit of the above preferable range is exceeded, it is not preferable because dissolution of the polymer compound becomes difficult and operability such as increase in the viscosity of the solution containing the polymer compound becomes worse.

  In this mixing step, the solution containing the polymer compound and the primary particles are mixed. Such mixing may be performed by, for example, adding primary particles into the solution and dispersing the primary particles by a stirring operation or the like. By such an operation, in the method for producing highly crystalline calcium phosphate according to the present invention, the polymer compound is adsorbed on the surface of the primary particles, and the carboxyl group, sulfate group, sulfonate group, phosphate group, phosphonate group, amino group is adsorbed. Either groups or their salts can be added to the surface of the primary particles. At this time, the carboxyl group, sulfuric acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group or amino group is present in an ionic state in the solution.

Next, if a metal salt (an alkali metal salt and / or an alkaline earth metal salt and / or a transition metal salt) is further added to a solution obtained by mixing a solution containing a polymer compound and primary particles, the surface of the primary particles Carboxylic acid ion, sulfate ion, sulfonate ion, phosphate ion, phosphonate ion, amino ion and metal ion (alkali metal ion and / or alkaline earth metal ion and / or transition metal ion) present in Then, carboxylate, sulfate, sulfonate, phosphate, phosphonate, and amino acid salt are formed on the surface of the primary particles. Carboxylic acid salts, sulfates, sulfonates, phosphates, phosphonates, and amino acid salts of such metals (alkali metals and / or alkaline earth metals and / or transition metals) function as the anti-fusing agent. . Therefore, primary particles with metal (alkali metal and / or alkaline earth metal and / or transition metal) carboxylate, sulfate, sulfonate, phosphate, phosphonate, amino acid salt formed on the surface are These are so-called “mixed particles”. In addition, since the carboxylate, sulfate, sulfonate, phosphate, phosphonate, and amino acid salt of such metal (alkali metal and / or alkaline earth metal and / or transition metal) are precipitated, the precipitate After being recovered, it may be dried and subjected to a sintering step described later. The drying is performed under reduced pressure conditions (for example, preferably 1 × 10 ⁵ Pa or more and 1 × 10 ⁻⁵ Pa or less, more preferably 1 × 10 ³ Pa or more and 1 × 10 ⁻³ Pa or less, and more preferably 1 × 10 ² Pa or more and 1 × 10 ⁻² Pa or less is most preferable) and heating (0 ° C. or more and 200 ° C. or less is preferable, 20 ° C. or more and 150 ° C. or less is more preferable, and 40 ° C. or more and 120 ° C. or less is most preferable). It is done. The drying is preferably performed under reduced pressure because the drying temperature can be lowered, but may be performed under atmospheric pressure.

  The alkali metal salt is not particularly limited. For example, sodium chloride, sodium hypochlorite, sodium chlorite, sodium bromide, sodium iodide, sodium iodide, sodium oxide, sodium peroxide, Sodium sulfate, sodium thiosulfate, sodium selenate, sodium nitrite, sodium nitrate, sodium phosphide, sodium carbonate, sodium hydroxide, potassium chloride, potassium hypochlorite, potassium chlorite, potassium bromide, potassium iodide Potassium iodide, potassium oxide, potassium peroxide, potassium sulfate, potassium thiosulfate, potassium selenate, potassium nitrite, potassium nitrate, potassium phosphide, potassium carbonate, potassium hydroxide and the like can be used.

  Examples of the alkaline earth metal salt include magnesium chloride, magnesium hypochlorite, magnesium chlorite, magnesium bromide, magnesium iodide, magnesium iodide, magnesium oxide, magnesium peroxide, magnesium sulfate, and magnesium thiosulfate. , Magnesium selenate, magnesium nitrite, magnesium nitrate, magnesium phosphide, magnesium carbonate, magnesium hydroxide, calcium chloride, calcium hypochlorite, calcium chlorite, calcium bromide, calcium iodide, calcium iodate, oxidation Calcium, calcium peroxide, calcium sulfate, calcium thiosulfate, calcium selenate, calcium nitrite, calcium nitrate, calcium phosphide, calcium carbonate, calcium hydroxide and the like can be used.

  Examples of the transition metal salt include zinc chloride, zinc hypochlorite, zinc chlorite, zinc bromide, zinc iodide, zinc iodide, zinc oxide, zinc peroxide, zinc sulfate, zinc thiosulfate, and selenium. Zinc oxide, zinc nitrite, zinc nitrate, zinc phosphide, zinc carbonate, zinc hydroxide, iron chloride, iron hypochlorite, iron chlorite, iron bromide, iron iodide, iron iodide, iron oxide, Iron peroxide, iron sulfate, iron thiosulfate, iron selenate, iron nitrite, iron nitrate, iron phosphide, iron carbonate, iron hydroxide and the like can be used. Moreover, a nickel compound may be sufficient.

  In addition, even if there is only one kind of metal salt (alkali metal salt, alkaline earth metal salt, transition metal salt) added to the solution in which the solution containing the polymer compound and the primary particles are mixed, a mixture of two or more kinds It may be. In addition, the metal salt (alkali metal salt, alkaline earth metal salt, transition metal) may be in a solid state, but can be added uniformly and the concentration can be controlled. It is preferable to add as an aqueous solution. Further, the amount (concentration) of the metal salt (alkali metal salt and / or alkaline earth metal salt and / or transition metal salt) to be added depends on the carboxylate ion, sulfate ion, sulfonate ion, phosphoric acid present on the primary particle surface. Bonded with ions, phosphonate ions, amino ions, carboxylate, sulfate, sulfonate, phosphate, phosphonate of metal (alkali metal and / or alkaline earth metal and / or transition metal), The conditions are not particularly limited as long as the amino acid salt is generated, and may be determined after appropriate examination.

  In addition, carboxylate, sulfate, sulfonate, phosphate, phosphonate, amino acid of metal (alkali metal and / or alkaline earth metal and / or transition metal) generated on the surface of primary particles by the above process The salt undergoes thermal decomposition in a sintering process described later, and becomes an oxide of a metal (an alkali metal and / or an alkaline earth metal and / or a transition metal). For example, when calcium polyacrylate is generated on the surface of the primary particles, it becomes calcium oxide by the sintering process. In addition, since the metal oxide (alkali metal oxide and / or alkaline earth metal oxide (for example, calcium oxide) and / or transition metal oxide) is water-soluble, it can be easily removed by a removal step described later. Is possible.

  Since sodium polyacrylate is soluble in water, it can be used as an anti-fusing agent in this mixing step. However, since calcium polyacrylate is insoluble in water, only polyacrylic acid is temporarily removed from the primary particle surface. It is preferable that calcium acrylate is precipitated on the primary particle surface by adding a calcium salt or the like after adsorbing to the primary particle surface. In addition, since the polymer compound decomposes when the primary particles are calcined at a high temperature (about 300 ° C. or higher), the metal salt of the polymer compound is added to the primary particles so that it functions as an anti-fusing agent even after calcining. It can be said that it is preferable to deposit on the surface. However, when the primary particles are calcined (heat treatment) at a temperature at which the polymer compound is not decomposed (not softened), it is not particularly necessary to deposit the metal salt of the polymer compound on the surface of the primary particles.

  Although the manufacturing method of the calcium phosphate fine particles according to the best mode has been described above, the anti-fusing agent used in the mixing step is preferably an anti-fusing agent containing calcium ions. That is, as the anti-fusing agent, it is preferable to use the aforementioned calcium salt or the aforementioned polymer compound and calcium salt. Thereby, since the outflow of calcium atoms from the calcium phosphate fine particles in the sintering process or the like can be suppressed, the component ratio (Ca / P value) with respect to phosphorus atoms on the surface of the obtained calcium phosphate fine particles becomes high. Thereby, the calcium phosphate fine particles are more easily adsorbed to the tooth surface. Although the mechanism is not clear, the tooth surface has a negative charge. On the other hand, a large amount of positively charged calcium is present on the surface of the fine particle, so that the adsorptive power of the fine particle on the tooth surface is increased. it is conceivable that. The abundance ratio (Ca / P) of calcium atoms to phosphorus atoms on the surface of the calcium phosphate fine particles according to the best mode is preferably 1.60 or more. The abundance ratio of the atoms is measured by XPS.

(Spray drying process)
The spray drying step is a step of aggregating and drying the hydroxyapatite obtained by the primary particle generation step to a target particle size using a spray dryer.
Hydroxyapatite obtained by the primary particle generation step is dispersed in a medium, the dispersion is sprayed into a heated fluid in a spray dryer, and the medium is vaporized and removed to agglomerate in accordance with the target particle size. Can be produced.
The medium used for obtaining the dispersion may be appropriately selected according to the temperature of the heating fluid, but water is more preferable. In addition, it is desirable to use air as the heating fluid, and it is desirable to set the heating temperature to be equal to or higher than the boiling point of the medium used for the dispersion.

(Sintering process)
The sintering step is a step of exposing the particles obtained by the mixing step or spray drying step to a sintering temperature to make the particles highly crystalline hydroxyapatite.
What is necessary is just to set suitably the sintering temperature in the said sintering process so that the hardness of highly crystalline hydroxyapatite may become desired hardness, for example, the inside of the range of 100 to 1800 degreeC is more preferable, and 150 to 1500 degreeC Is more preferable, and 200 ° C to 1200 ° C is most preferable. The sintering time may be appropriately set based on the desired hardness of the highly crystalline calcium phosphate fine particles. In the examples described later, sintering is performed at 800 ° C. for 1 hour.
In addition, the apparatus etc. which are used for the said sintering process are not specifically limited, What is necessary is just to employ | adopt after selecting a commercially available baking furnace suitably according to a manufacturing scale, manufacturing conditions, etc.

(Removal process)
The said removal process is a process of removing the anti-fusing agent mixed between the particles of the highly crystalline calcium phosphate fine particles obtained by the sintering process.

About the removal means and method, what is necessary is just to employ | adopt suitably according to the anti-fusing agent employ | adopted in the said mixing process. For example, when an anti-fusing agent having solvent solubility is used, by using a solvent that does not dissolve the highly crystalline calcium phosphate fine particles (non-soluble) and a solvent that dissolves the anti-fusing agent (soluble), Only the anti-fusing agent can be dissolved and removed. The solvent to be used is not particularly limited as long as it satisfies the above requirements, and may be an aqueous solvent or an organic solvent. For example, water, ethanol, methanol, etc. are mentioned as an aqueous solvent, and acetone, toluene, etc. are mentioned as an organic solvent.
The aqueous solvent may contain a chelate compound such as oxalate, ethylenediamine, bipyridine, and ethylenediaminetetraacetate in order to increase the solubility of the anti-fusing agent in water. Further, the aqueous solvent may contain electrolyte ions such as sodium chloride, ammonium nitrate and potassium carbonate in order to increase the solubility of the anti-fusing agent in water.

However, for the reasons such as that the equipment corresponding to the use of the organic solvent in the removal step becomes unnecessary, the organic solvent waste liquid treatment becomes unnecessary, the safety of the manufacturing work is high, and the risk to the environment is low. The solvent used is preferably an aqueous solvent.
The highly crystalline hydroxyapatite is preferably removed at pH 4.0 to pH 12.0 because the highly crystalline hydroxyapatite dissolves under conditions of pH less than 4.0.

  By the way, when removing the anti-fusing agent using a solvent, after suspending the highly crystalline calcium phosphate containing the anti-fusing agent obtained by the sintering process in the solvent, the high crystallinity is obtained by filtration or centrifugation. Only the calcium phosphate particles need be recovered. In the method for producing highly crystalline calcium phosphate according to the best mode, the above operation is not limited to once, and may be performed twice or more. By performing the above operation a plurality of times, it can be said that the removal rate of the anti-fusing agent for highly crystalline calcium phosphate is further improved. However, it is not preferable to perform the above operation more than necessary because the manufacturing process becomes complicated, the manufacturing cost increases, and the recovery rate of highly crystalline calcium phosphate decreases. Therefore, the number of operations may be appropriately determined based on the target anti-fusing agent removal rate.

  Note that this step may further include a step of classification to make the particle diameter uniform.

(C) component of this invention is a thickener. As component (C), sugar alcohols such as sorbit, xylit, malt, lactit, erythritol, reduced starch sugar compounds, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, and ethylene glycol are usually used for dentifrices. And known thickeners. In particular, sorbit and glycerin are preferably used.
The component (C) is used in a range of 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, in a total of 100 parts by weight of the components (A) to (D). If the stability of the paste decreases due to the above, and exceeds the upper limit value, it is not preferable because the operability decreases with changes in the physical properties of the paste.

Component (D) of the present invention is a binder. Examples of the component (D) include cellulose derivatives such as sodium carboxymethylcellulose, gums such as xanthan gum, tragacanth gum, karaya gum, and arabic gum, carboxyvinyl polymers such as polyvinyl alcohol, cross-linked sodium polyacrylate, and non-cross-linked sodium polyacrylate. And known binders usually used in dentifrices, such as organic binders such as carrageenan, sodium alginate and polyvinylpyrrolidone, and inorganic binders such as silica gel, aluminum silica gel, bee gum and laponite. In particular, carboxymethylcellulose, carboxyethylcellulose, xanthan gum and carrageenan are preferably used.
The component (D) is used in a range of 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, in a total of 100 parts by weight of the components (A) to (D), and the lower limit is exceeded. If the value exceeds the upper limit, the operability is lowered due to a change in the physical properties of the paste, which is not preferable.

  (E) component of this composition is a flavoring agent. As component (E), saccharin sodium, stevioside, stevia extract, neohesperidyl dihydrochalcone, glycyrrhizin, perilartine, p-methoxycinnamic aldehyde, aspartame, xylitol, etc. as sweeteners, peppermint oil, spearmint oil, Anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, lime oil, lavender oil, rosemary oil, Laurel oil, camomile oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, Iris concrete, absolute peppermint, ab Natural fragrances such as lute rose and orange flower, and fragrances processed with these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and menthol, Carvone, anethole, cineol, methyl salicylate, synamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted paramentan 3-carboxamide, pinene, octylaldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, Nilin, undecalactone, hexanal, propyl alcohol, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate, ethyl thioacetate and other single flavors, strawberry flavor, apple flavor, Known flavoring agents that are usually used in dentifrices, such as blended fragrances such as banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, and tropical fruit flavor.

In particular, saccharin sodium, aspartame, xylitol, and mint flavor are preferably used.
When components (E) to (G) are added in addition to components (A) to (D), component (E) is 0.01 in a total of 100 parts by weight of components (A) to (G). It is used in the range of 10 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and if it exceeds the upper limit value, the taste and fragrance are excessively imparted, so the feeling of use is lowered, which is not preferable.

(F) component of this composition is a preservative and a storage stabilizer. As component (F), as preservatives, parabens such as butyl paraben, propyl paraben, ethyl paraben, methyl paraben, paraoxybenzoic acid ester, sodium benzoate, cetylpyridinium chloride, potassium sorbate, etc., as storage stabilizers, Well-known preservatives and storage stabilizers usually used for dentifrice such as vitamin C, sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, butylhydroxytoluene, propyl gallate, butylhydroxyaryl and the like can be mentioned. In particular, methyl paraben, paraoxybenzoic acid ester, sodium benzoate and vitamin C are preferably used.
When the components (E) to (G) are further added in addition to the components (A) to (D), the component (F) is 0.001 in the total 100 parts by weight of the components (A) to (G). It is used in a range of ˜5 parts by weight, more preferably 0.01 to 3 parts by weight, and if it exceeds the upper limit, there is a risk of causing an abnormality to the living body such as allergy, which is not preferable.

(G) component of this composition is a pH adjuster. As component (G), citric acid, malic acid, lactic acid, tartaric acid, acetic acid, phosphoric acid, glycerophosphoric acid and / or various salts thereof, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate And the like, and known pH adjusters usually used for dentifrices. In particular, citric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate are preferably used.
When components (E) to (G) are added in addition to components (A) to (D), component (G) is 0.001 in a total of 100 parts by weight of components (A) to (G). It is used in the range of ˜5 parts by weight, more preferably in the range of 0.01 to 3 parts by weight.

The (H) component of this composition is a surfactant. As the component (H), a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be blended. Anionic surfactants include sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, sodium N-acyl sarcosinate such as sodium N-lauroyl sarcosinate, sodium N-lauroyl-L-glutamate, sodium N-myristoyl sarcosinate Sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, N-acyl glutamate such as sodium N-palmitoyl glutamate, N-methyl-N-acyl taurate sodium, N-methyl-N- Sodium acylalanine, sodium α-olefin sulfonate, etc. are nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan Sugar alcohol fatty acid esters such as fatty acid esters and sucrose fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyhydric alcohol fatty acid esters such as polyethylene glycol fatty acid esters, polyoxyethylene polyoxypropylene Copolymers, ether type surfactants such as polyoxyethylene alkylphenyl ether, fatty acid alkanolamides such as lauric acid diethanolamide, and cationic surfactants such as alkylammonium and alkylbenzylammonium salts are amphoteric interfaces. Examples of the active agent include known surfactants usually used in dentifrices such as betaine acetate, imidazolinium betaine, and lecithin. In particular, sodium lauryl sulfate is preferably used.

  In addition to the components (A) to (G), when the components (H) to (I) are further added, the component (H) is 0.01 to 100 parts by weight of the total of the components (A) to (I). It is used in the range of 5 parts by weight, more preferably 0.1 to 3 parts by weight, and when it exceeds the upper limit, it is not preferable because foaming or the like becomes excessive and the feeling of use decreases.

  The component (I) of this composition is a medicinal component. As component (I), water-soluble phosphoric acid such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, etc., potassium salt of normal phosphoric acid, sodium salt, etc. Compound, allantoin, allantoin chlorohydroxyaluminum, hinokitiol, ascorbic acid, sodium chloride, coenzyme Q10, dihydrocholesterol, α-bisabolol, chlorhexidine salts, triclosan, epsilon aminocaproic acid, hinokitiol, isopropylmethylphenol, sanguinarine extract, azulene, glycyrrhetin Chelating properties of glycyrrhetinic acid, dipotassium glycyrrhetinate, ammonium glycyrrhetinate, copper chlorophyllin sodium, chlorophyll, glycerophosphate, etc. Acid compounds, copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, aluminum lactate, berberine, hydroxamic acid and its derivatives, zeolite, methoxyethylene, maleic anhydride copolymer, polyethylene glycol, polyvinyl pyrrolidone, epi Enzymes such as dihydrocholesterine, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, sodium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, dextranase, mutanase, protease, soft sugar extract, buckwheat extract, chamomile Well-known medicinal ingredients that are usually used in dentifrices, such as extracts from plants such as clove, rosemary, hornon, safflower and the like. Especially sodium fluoride, sodium monofluorophosphate, hinokitiol, isopropylmethylphenol, triclosan, chlorohexidine, glycyrrhetin, glycyrrhetinic acid, dipotassium glycyrrhetinate, ammonium glycyrrhetinate, epsilon aminocaproic acid, aluminum lactate, potassium nitrate, strontium chloride, polyethylene glycol Preferably used.

  In addition to the components (A) to (G), when the components (H) to (I) are further added, the component (I) is 0.0001 to 100 parts by weight in total of the components (A) to (I). 5 parts by weight, more preferably in the range of 0.001 to 3 parts by weight. When the upper limit is exceeded, there is a possibility that a decrease in operability, an increase in harmful effects on the living body, etc. may occur. Absent.

  The component (J) of the composition is a colorant. As the component (J), Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 4, Blue No. 201 , Blue No. 204, Green No. 3, mica titanium, titanium oxide and the like, and known colorants usually used for dentifrices. In particular, Blue No. 1, Blue No. 2, Yellow No. 4, Yellow No. 5, and titanium oxide are preferably used.

  When (J) component is further added in addition to (A)-(I) component, (J) component is 0.001-5 weight part in a total of 100 weight part of (A)-(J) component, More preferably, it is used in the range of 0.01 to 3 parts by weight, and if it exceeds the upper limit, the color tone of the paste is impaired, which is not preferable.

  EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention should not be construed as limited to these examples.

(Polymer synthesis: Emulsion)
A reactor equipped with a stirrer, condenser, thermometer, nitrogen inlet, and dropping funnel was charged with 180 g of distilled water and methyl methacrylate (90 mmol and 2.1 g (10 mmol) of sodium styrenesulfonate, bubbling with nitrogen for 15 minutes, and stirred vigorously. While the internal temperature was raised to 65 ° C., an aqueous solution consisting of 99 mg of potassium persulfate, 50 mg of sodium hydrogen nitrite and 10 g of distilled water was added dropwise over 45 minutes from the dropping funnel while maintaining the temperature and stirring. After further aging for 3 hours, the mixture was cooled, 2 g of 6N hydrochloric acid was added to the reaction mass, and the mixture was stirred for 30 minutes.The reaction mass was an ultrafiltration cassette set with an ultrafiltration membrane (Millipore, excluded molecular weight 10,000). Transfer to Advantech Ultra Holder) and add a total of 400 g of distilled water. Condensation was performed. Prepared polymer after ultrafiltration concentrated in distilled water to a solids content of 5% to obtain an aqueous polymer emulsion (MS emulsion).

Production Example 1 (Production of highly crystalline hydroxyapatite (average particle size 20 to 100 nm))
(Primary particle generation process)
Dodecane [CH ₃ (CH ₂ ) ₁₀ CH ₃ ] as a continuous oil phase and pentaethylene glycol dodecyl ether [CH ₃ (CH ₂ ) ₁₀ CH ₂ O (CH ₂ CH ₂ ) having a cloud point of 31 ° C. as a nonionic surfactant O) ₄ CH ₂ CH ₂ OH]. At room temperature, 40 ml of a continuous oil phase containing 0.5 g of the nonionic surfactant was prepared. Next, 10 ml of a 2.5 mol / l calcium hydroxide [Ca (OH) ₂ ] dispersed aqueous solution was added to the continuous oil phase prepared above to prepare a water-in-oil solution (W / O solution). While stirring the W / O solution, 10 ml of a 1.5 mol / l potassium dihydrogen phosphate [(KH ₂ PO ₄ )] solution was added thereto. And it was made to react, stirring for 24 hours at room temperature. Next, hydroxyapatite (HAp) primary particle groups were obtained by separating and washing the obtained reaction product by centrifugation.

(Mixing process)
By dispersing 1.0 g of hydroxyapatite (HAp) primary particle group in 100 ml of an aqueous solution having a pH of 12.0 containing 1.0 g of sodium polyacrylate (manufactured by ALDRICH, weight average molecular weight: 15,000 g / mol), Sodium polyacrylate was adsorbed on the surface of the particles. The pH of this aqueous solution was measured using a pH meter D-24SE manufactured by Horiba, Ltd.
Next, 100 ml of a 0.12 mol / l calcium nitrate [Ca (NO ₃ ) ₂ ] aqueous solution was added to the dispersion prepared above to precipitate calcium polyacrylate on the surface of the primary particles. Such calcium polyacrylate is an anti-fusing agent. The resulting precipitate was collected and dried at 80 ° C. under reduced pressure (about 0.1 Pa) to obtain mixed particles.

(Sintering process)
The mixed particles were put in a crucible and sintered at a sintering temperature of 800 ° C. for 1 hour. At this time, calcium polyacrylate was thermally decomposed to calcium oxide [CaO]. The residual ratio of calcium oxide [CaO] after the sintering process was 25% or more.

(Removal process)
In order to increase the solubility of the anti-fusing agent in water, a 50 mmol / l ammonium nitrate [NH ₄ NO ₃ ] aqueous solution was prepared. Next, the sintered body obtained in the above step is suspended in 500 ml of the aqueous solution prepared above, separated and washed by centrifugation, suspended in distilled water, and similarly separated and washed by centrifugation. The anti-fusing agent and ammonium nitrate were removed, and highly crystalline hydroxyapatite (HAp) fine particles were recovered. Detailed information on the hydroxyapatite fine particles obtained by these steps is summarized below.
XRD half width: 0.2 (d = 2.814)
Shape: Spherical average particle diameter (from electron microscope): 42 nm

Production Example 2 (Production of highly crystalline hydroxyapatite (average particle size 1 to 10 μm))
The same operation as in Production Example 1 (primary repair production step) was performed to obtain hydroxyapatite primary particles.

(Spray drying process)
An HAp dispersion was prepared by dispersing 1.0 g of hydroxyapatite (HAp) primary particles in 100 ml of distilled water. The prepared HAp dispersion is injected into a spray dryer (Mini Spray Dryer ADL310 manufactured by Yamato Scientific Co., Ltd.), sprayed into a heated fluid (normal air) temperature of 120 ° C., dried, and the target hydroxyapatite aggregate is formed. Obtained.

(Sintering process)
The agglomerates were put in a crucible and sintered at a sintering temperature of 800 ° C. for 1 hour.

(Removal process)
In order to increase the solubility of by-products such as calcium oxide in water, an aqueous solution of 50 mmol / l ammonium nitrate [NH ₄ NO ₃ ] was prepared. Next, the sintered body obtained in the above step is suspended in 500 ml of the aqueous solution prepared above, separated and washed by centrifugation, suspended in distilled water, and similarly separated and washed by centrifugation. The anti-fusing agent and ammonium nitrate were removed, and highly crystalline hydroxyapatite (HAp) fine particles were recovered.
Hereinafter, detailed information on the hydroxyapatite fine particles will be described.
XRD half width: 0.2 (d = 2.814)
Shape: Spherical average particle diameter (from electron microscope): 3 μm

(Preparation of composition)
The polymer emulsion synthesized above and other components were mixed and defoamed with a stirring deaerator (Murastar KK-L300, a planetary stirring deaerator manufactured by Kurabo Industries), and the example compositions shown in Table 1 below were prepared. Prepared. The prepared composition had a pH of 7.5. In addition, as a comparative example, a tooth polishing material Ad Nest Fine (manufactured by Neo Pharmaceutical Industries) for finish polishing was used.

(Evaluation of surface smoothness)
A dental filling composite resin fantasista (manufactured by Sun Medical Co., Ltd.) is filled in a Teflon mold with a hole of 100 x 100 x 5 mm, and both sides are sandwiched between glass plates. Polymerization and curing were carried out by irradiating with light for 5 minutes to prepare a cured product. After polishing the prepared cured body with water-resistant abrasive paper # 600, using each paste of Examples and Comparative Examples and a handpiece Mersage Pro for dental PMTC (manufactured by Matsukaze Co., Ltd.) at a rotational speed of 8000 min-1. Polishing treatment was performed for 1 minute. After water washing and air blow drying, the surface smoothness was measured with a gloss meter Gloss checker IG-331 (manufactured by HORIBA).

(Evaluation of ivory capillarity)
Polish the bovine teeth with water-resistant abrasive paper # 600 to expose the dentin, immerse it in the root canal wall smear layer remover smear clean (manufactured by Nippon Dental Co., Ltd.), perform ultrasonic cleaning for 1 minute, and remove the dentinal tubule Opened. The surface of the bovine tooth sample was polished for 1 minute at a rotational speed of 8000 min-1 using each paste of Examples and Comparative Examples, and a dental PMTC handpiece Mersage Pro (manufactured by Matsukaze). It was immersed in ultrapure water and subjected to ultrasonic cleaning for 1 minute, and the opening degree of the surface dentinal tubule was observed with SEM.

(Evaluation of plaque adhesion)
After polishing the surface of the hydroxyapatite block with water-resistant abrasive paper # 600, the surface was rotated at 8000 min-1 using each paste of Examples and Comparative Examples, and Handpiece Mersage Pro for Dental PMTC (manufactured by Matsukaze Co., Ltd.). Polishing treatment was performed for 1 minute. Each sample after the polishing treatment was treated with L.P. casei and S. et al. It was immersed in a culture solution (49.25% MRS Broth, 49.25% Tryptic Soy Broth, 1.5% sucrose) added with mutans, and cultured at 37 ° C. for 3 days. After culturing, each sample was immersed in ultrapure water to remove non-adhered components on the surface, and then gram-stained to visually confirm the amount of plaque adhering to the surface.

As a result of the evaluation of the surface smoothness, it was confirmed that the same level of surface smoothness was imparted in both Examples and Comparative Examples. In addition, in the evaluation of dentinal tubule sealing properties, an image in which the dentinal tubules were opened was observed in the sample after the treatment according to the comparative example, whereas an image in which the dentinal tubules were sealed in the sample after the treatment according to the example was confirmed. . In addition, in the evaluation of plaque adhesion, it was confirmed that the plaque adhesion was confirmed in the sample after the treatment according to the example while the plaque adhesion was confirmed in the sample after the treatment according to the example.

Claims (12)

  A neutral or weakly alkaline tooth cleaning treatment composition for forming a film made of an emulsion polymer on a tooth surface.   The composition according to claim 1, comprising (A) a water-soluble and / or aqueous emulsion polymer.   The composition according to any one of claims 1 to 2, wherein an average molecular weight of the emulsion polymer of the component (A) is 1,000 or more.   The composition according to any one of claims 1 to 3, wherein the component (A) is a copolymer containing a polymer unit derived from an alkyl (meth) acrylate monomer and a styrene sulfonic acid monomer.   pH is 6.0-10.0, The composition in any one of Claims 1-4.   (B) The composition in any one of Claims 1-5 which further contains an abrasive | polishing agent.   The composition according to any one of claims 1 to 6, further comprising (a) water.   The composition according to any one of claims 2 to 7, wherein the component (A) is contained in an amount of 1 to 30 parts by weight per 100 parts by weight of the composition.   The composition according to any one of claims 6 to 8, wherein the component (B) is contained in an amount of 5 to 50 parts by weight per 100 parts by weight of the composition.   The composition according to any one of claims 7 to 9, wherein the component (a) is contained in the range of 0.1 to 60 parts by weight per 100 parts by weight of the composition.   (B) A component is a calcium-phosphate type compound, The composition in any one of Claims 6-9. The composition according to any one of claims 6 to 11, wherein the ratio (B / A) of the component (B) to the component (A) is 0.5 or more.