JP4615260B2 - Pit fissure filling kit - Google Patents

Description

  The present invention relates to a kit for filling pits and fissures used for dental treatment. Specifically, the surface of pits and fissures (no-column enamel) and a pit and fissure filling material are acid-etched on the surfaces of pits and fissures. The present invention relates to a kit for filling pits and fissures that can be bonded without any treatment.

  The columnar enamel that constitutes the outermost layer of the tooth is different in composition and crystal structure from the enamel trabeculae that are composed of the enamel trabeculae and trabecular interstitium, etc. high. One dental treatment for such columnar enamel is prevention of dental caries using a foveal fissure filling material. This dental treatment, which does not necessarily require cutting of the tooth with a turbine or the like, generally starts with decalcifying and roughening the surface of the toothless enamel of the tooth with a phosphoric acid etchant (phosphoric acid aqueous solution). Is done.

  However, the phosphoric acid etchant decalcifies teeth more than necessary. As a result, the enamel trabecular portion having low acid resistance inside the pillarless enamel layer is exposed on the surface of the tooth, and caries bacteria may enter from the exposed portion and caries may occur.

  Also, due to excessive demineralization, the gloss of the teeth disappears, plaques, food proteins, coloring agents, etc. accumulate on the irregularities of the surface of the tooth caused by demineralization, and the tooth surface, especially The surface of the tooth around the pit and fissure filling material may be discolored.

  Furthermore, it is clinically difficult to apply the phosphoric acid etching process only to the site to be treated strictly, though the tooth damage due to excessive decalcification in the phosphoric acid etching process should be minimized. In some cases, tooth damage may extend to areas that do not require treatment.

  The above-mentioned adverse effects caused by excessive decalcification with a phosphoric acid etching agent are, for example, by applying a phosphoric acid etching treatment after applying a masking material such as enamel protective varnish in advance to a portion that does not require treatment, Can prevent to some extent. However, it is difficult to completely protect a portion that does not require treatment from demineralization with a masking material, and the bonding operation becomes complicated by the addition of the masking process. In addition, when an acid etching agent such as a phosphoric acid etching agent is used, it is necessary to completely remove it by a water washing treatment after the etching treatment, and when this water washing treatment is insufficient, the adhesiveness is significantly reduced. In addition, the bonding operation becomes complicated by the addition of the washing step and the subsequent drying step.

  As an adhesive composition for pillarless enamel that does not require acid etching treatment, an adhesive composition containing an acidic group-containing polymerizable monomer, a water-soluble solvent, and water has been proposed (Patent Document 1). reference). This adhesive composition can be used not only as an adhesive between a pillarless enamel and a dental restorative material such as a coating material, but also as a dental restorative material having adhesion to the pillarless enamel. (See Patent Document [0044]). This adhesive composition penetrates into the tooth while chemically decalcifying the surface of the columnar enamel and chemically bonds with the tooth. Therefore, when this adhesive composition is used as an adhesive, the columnar enamel and the dental restoration material can be firmly bonded. In addition, when this adhesive composition is used as a foveal fissure filling material, it becomes possible to fill the foveal fissures of human teeth without performing an acid etching treatment.

JP 2002-226314 A

  However, as a result of investigation by the present inventor, the above adhesive composition contains water. Therefore, when the composition is used as an adhesive or a foveal fissure filling material after long-term storage, a pillarless enamel is used. It has been found that the adhesion to the resin is significantly reduced. In addition, when the above adhesive composition is used as an adhesive between the pit and fissured portion and the pit and fissure filling material, if the adhesive is not applied over a wider area than the filling site, good adhesive force and side The sealing ability cannot be obtained. However, at the periphery of the hardened (adhered) pit and fissure filling material, an adhesive that adheres to the dentine at the same time as demineralization is exposed, and this is colored by food-derived proteins and coloring agents, and is aesthetically pleasing. It may reduce the sex. As an improvement measure for this, after bonding, for example, by rubbing the surface of the exposed adhesive with cotton containing an organic solvent such as ethanol, a cured body of an uncured adhesive or a low-polymerized adhesive. A method for removing the surface has been proposed, but such operations such as rubbing with cotton are clinically very complicated.

  The present invention has been made to solve the above-described problems, and has excellent adhesiveness to the surface of the pits and fissures of human teeth (columnar enamel having high acid resistance), and is stored. It is an object of the present invention to provide a kit for filling a pit and fissure with excellent stability.

To achieve the above object, a kit for filling a pit and fissure according to the first aspect of the present invention comprises a tooth surface treatment agent (A) comprising water or an aqueous solution of an inorganic substance having a pH of 5 to 9, and an acidic group-containing polymerizable monomer. mer (a), crosslinkable polymerizable monomer (b) and a polymerization initiator containing (c), and water also Hama pit and fissure containing neither have organic solvents such has a polymerizable塞材(B ).

In the kit for filling the pit and fissure according to the invention described in claim 2, the inorganic substance in the kit for filling the pit and fissure according to claim 1 is sodium chloride, lithium chloride, potassium chloride, sodium bromide, chloride. Calcium, calcium bicarbonate, sodium bicarbonate, calcium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium hydrogen phosphate, disodium hydrogen phosphate, sodium borate, Selected from the group consisting of sodium dihydrogen phosphite, potassium dihydrogen phosphite, sodium fluoride, calcium fluoride, lithium fluoride, potassium fluoride, tin fluoride, sodium monofluorophosphate and potassium monofluorophosphate Limited to inorganic salts .

  In the kit for filling the pit and fissure according to the invention described in claim 3, the pit and fissure filling material (B) in the kit for filling the pit and fissure according to claim 1 or 2 is further hydrophilic. It is limited to what contains a polymerizable monomer (d).

  In the kit for pit and fissure filling according to the invention of claim 4, the pit and fissure filling material (B) in the kit for pit and fissure filling according to any one of claims 1 to 3, Furthermore, it is limited to what contains a filler (e).

  In the kit for filling the pit and fissure according to the invention described in claim 5, the pit and fissure filling material (B) in the kit for filling the pit and fissure according to any one of claims 1 to 4, Furthermore, it is limited to the thing containing a fluorine ion releasing substance (f).

  In the following, the kit for filling the pit and fissure according to any one of claims 1 to 5 may be referred to as the kit for filling a pit and fissure according to the present invention.

  According to the invention of any one of claims 1 to 5, the pit and fissure can be filled without using an acid etching agent or an adhesive, and the pit and fissure are filled with good storage stability. A kit is provided.

The tooth surface treating agent (A), which is an essential component of the kit for filling a pit and fissure according to the present invention, is composed of water or an aqueous solution of an inorganic substance having a pH of 5 to 9. The tooth surface treatment agent (A) is an agent for wetting the columnar enamel on the surface of the pit and fissured part. By adhering moisture to the surface layer of the tooth surface, the demineralization effect on columnar enamel by the acidic group-containing polymerizable monomer (a) in the pit and fissure filling material (B) to be subsequently applied is promoted. This is to improve the adhesion. Therefore, a small fissure groove coated tooth surface treating agent on the surface (A) is a dental air syringe (for example, three-way syringe) must Ru to be careful not to dry off the like.

  Since the tooth surface treatment agent (A) having a pH of 5 to 9 hardly decalcifies the surface of the pillarless enamel, the tooth is damaged by excessive decalcification, or the tooth is discolored by a coloring agent or protein in food. It is hard to let you. The pH of the tooth surface treating agent (A) is preferably in the range of 5.5 to 8.5, and most preferably in the range of 6 to 8. If the pH is less than 5, the teeth may be excessively damaged or discolored significantly. On the other hand, if the pH is greater than 9, the follicular fissure filling material (B) to be subsequently applied (B) A portion of the acidic group-containing polymerizable monomer (a) is neutralized by the tooth surface treating agent (A), resulting in insufficient decalcification, and as a result, no pit and fissure filling material (B) is present. Adhesion to column enamel may be reduced.

  Examples of water used as the tooth surface treating agent (A) include purified water, distilled water, ion exchange water, tap water, and spring water.

In order to adjust the pH and viscosity of the tooth surface treating agent (A) , the inorganic substance is added to water in the aqueous solution of the inorganic substance having a pH of 5 to 9. Specific examples of inorganic substances include sodium chloride, lithium chloride, potassium chloride, sodium bromide, calcium chloride, calcium bicarbonate, sodium bicarbonate, calcium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, sodium dihydrogen phosphate, Potassium dihydrogen phosphate, calcium hydrogen phosphate, disodium hydrogen phosphate, sodium borate, sodium dihydrogen phosphite, potassium dihydrogen phosphite, sodium fluoride, calcium fluoride, lithium fluoride, potassium fluoride Inorganic salts such as tin fluoride, sodium monofluorophosphate, potassium monofluorophosphate, and the like. The blending amount of the inorganic substance with respect to water is preferably in the range of 0.001 to 15% by weight, more preferably in the range of 0.005 to 10% by weight, and in the range of 0.01 to 5% by weight based on the total weight of the aqueous solution. Is most preferred. When the blending amount is more than 15% by weight, the adhesion to the pillarless enamel may be lowered. In order to improve the moisture retention of the surface of the columnar enamel, an inorganic fine particle filler such as silica or alumina may be added to the tooth surface treating agent (A).

The amount of the tooth surface treatment agent (A) made of water or an aqueous solution of an inorganic substance having a pH of 5 to 9 that adheres to the pit and fissure cuff is usually in the range of 0.0001 g to 0.05 g per 1 cm ² of the adhesion area. Is in the range of 0.0002 g to 0.01 g, more preferably in the range of 0.0005 g to 0.005 g.

  The pit and fissure filling material (B), which is another essential component of the pit and fissure filling kit according to the present invention, comprises an acidic group-containing polymerizable monomer (a), a crosslinkable polymerizable monomer ( b) and a polymerization initiator (c).

The acidic group-containing polymerizable monomer (a) is partially dissolved in the tooth surface treatment agent (A) applied earlier to generate hydrogen ions, and the deionized columnar enamel is decalcified by the hydrogen ions. Penetrates and chemically binds to the tooth. The acidic group-containing polymerizable monomer (a) has a monovalent phosphate group [phosphinico group: = P (═O) OH], a divalent phosphate group [phosphono group: —P (═O) (OH ₂ ), pyrophosphate group [-P (= O) (OH) -OP (= O) (OH)-], carboxylic acid group [carboxyl group: -C (= O) OH, acid anhydride group : -C (= O) -OC (= O)-], at least one acidic group such as sulfonic acid group [sulfo group: -SO ₃ H], and acryloyl group, methacryloyl group, vinyl group, It is a hydrophobic monomer having at least one polymerizable group (polymerizable unsaturated group) such as a vinylbenzyl group. In this specification, hydrophobic means that the solubility in water at 25 ° C. is less than 10% by weight. Specific examples include the following. In the following, methacryloyl and acryloyl are collectively referred to as (meth) acryloyl.

  Examples of the phosphoric acid group-containing polymerizable monomer (a-1) include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxy. Butyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) Acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) a Liloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (Meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyl Xyldecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate 2- (meth) acryloyloxyethyl phenylphosphonate, (5-methacryloxy) pentyl-3-phosphonopropionate, (6-methacryloxy) hexyl-3-phosphonopropionate, (10-methacryloxy) decyl-3 -Phosphonopropionate, (6-methacryloxy) hexyl-3-phosphonoacetate, (10-methacryloxy) decyl-3-phosphonoacetate, 2-methacryloyloxyethyl- (4-methoxyphen Nyl) hydrogen phosphate, 2-methacryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate, their acid chlorides, alkali metal salts and amine salts.

  Examples of the pyrophosphate group-containing polymerizable monomer (a-2) include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl) pyrophosphate, bis [6 pyrophosphate] -(Meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, acid chlorides, alkali metal salts and amine salts thereof. Illustrated.

  As the carboxylic acid group-containing polymerizable monomer (a-3), maleic acid, methacrylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid; 4- (meth) acryloxyethyltrimetic acid, 4- ( (Meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and these 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (Meth) acryloyloxy-1,1-de Njikarubon acid, 11- (meth) acryloyloxy-1,1-undecane dicarboxylic acid, their acid chlorides, alkali metal salts, amine salts are exemplified.

  Examples of the sulfonic acid group-containing polymerizable monomer (a-4) include 2- (meth) acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylate, acid chlorides thereof, and alkalis. Metal salts and amine salts are exemplified.

Among the acidic group-containing polymerizable monomers (a-1) to (a-4), a polymerizable monomer having a phosphate group, a pyrophosphate group or a carboxylic acid group is superior to a columnar enamel. In particular, a polymerizable monomer having a phosphate group or a pyrophosphate group is more preferable, and a divalent phosphate group [phosphono group: —P (═O) (OH) ₂ ]. Most preferred is a polymerizable monomer having Among the phosphoric acid group-containing polymerizable monomers, a divalent phosphoric acid group-containing polymerizable monomer having an alkyl group or alkylene group having 6 to 20 carbon atoms in the main chain is particularly preferable. A divalent phosphate group-containing polymerizable monomer having an alkylene group having 8 to 12 carbon atoms in the main chain in the molecule, such as methacryloyloxydecyl dihydrogen phosphate, is most preferable. In addition, the sulfonic acid group-containing polymerizable monomer (a-4) is inferior in adhesiveness to teeth compared with other acidic group-containing polymerizable monomers, but the acidic group-containing polymerizable monomer ( Among the a-1) to (a-4), since the decalcification power for the tooth is the strongest, the combined use with the acidic group-containing polymerizable monomers (a-1) to (a-3) Excellent adhesion may be obtained.

  The acidic group-containing polymerizable monomer (a) may be used alone or in combination of two or more. Adhesive strength with respect to the columnar enamel may be reduced when the amount of the acidic group-containing polymerizable monomer (a) is too large or too small. The blending amount of the acidic group-containing polymerizable monomer (a) is preferably in the range of 1 to 50% by weight, and in the range of 1 to 40% by weight, based on the total weight of the pit and fissure filling material (B). More preferably, the range of 5 to 30% by weight is most preferable.

  The crosslinkable polymerizable monomer (b) is a hydrophobic polymerizable monomer having at least two polymerizable groups in the molecule and no acidic group. The crosslinkable polymerizable monomer (b) is strongly polymerized with the hydrophobic acidic group-containing polymerizable monomer (a) inferior in polymerization curability, and has excellent curability (particularly mechanical strength and water resistance). Property) to the cured product. In the following, acrylic ester and methacrylic ester are collectively referred to as (meth) acrylate. Specific examples of the crosslinkable polymerizable monomer (b) include bisphenol A diglycidyl (meth) acrylate (hereinafter referred to as “Bis-GMA”), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl. ] Propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (hereinafter referred to as “UDMA”) ), Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate Fine following Formula 1, Formula 2, Formula 3, Formula 4, a compound represented by Formula 5 or Formula 6 can be mentioned. Among them, in order to obtain excellent curability, a compound having a hydrocarbon group having at least 3 polymerizable groups in the molecule and having at least 6 consecutively bonded carbon atoms in a cyclic or linear form. preferable.

  One kind of the crosslinkable polymerizable monomer (b) may be blended, or a plurality of kinds may be blended in combination. When the compounding amount of the crosslinkable polymerizable monomer (b) is excessive, the penetrability of the acidic group-containing polymerizable monomer (a) into the tooth is lowered, and the adhesion force to the columnar enamel is reduced. May decrease. On the other hand, when the blending amount is too small, the curability of the composition may be lowered, and a large adhesive force may not be exhibited with respect to the pillarless enamel. The blending amount of the crosslinkable polymerizable monomer (b) is preferably in the range of 5 to 60% by weight, more preferably in the range of 10 to 50% by weight, based on the total weight of the pit and fissure filling material (B). The range of 20 to 40% by weight is most preferable.

  In order to improve the affinity and adhesion of the pit and fissure filling material (B) with the tooth substance, it has no acidic group and is hydrophilic (water solubility at 25 ° C. is 10% by weight or more). A polymerizable monomer (d) may be blended.

  As the hydrophilic polymerizable monomer (d), those having a solubility in water at 25 ° C. of 30% by weight or more are preferable, and those capable of being dissolved in water at an arbitrary ratio at 25 ° C. are most preferable. Examples of the hydrophilic polymerizable monomer (d) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl ( Examples include meth) acrylate and polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups).

  As the hydrophilic polymerizable monomer (d), one kind may be blended, or a plurality of kinds may be blended in combination. When the blending amount of the hydrophilic polymerizable monomer (d) is excessive, curability and water resistance are deteriorated, and the adhesive force to the columnar enamel may be reduced. Usually, the blending amount of the hydrophilic polymerizable monomer (d) is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total weight of the pit and fissure filling material (B). Most preferred is% by weight or less.

  Furthermore, in order to improve the hydrophilic / hydrophobic balance, viscosity adjustment, mechanical strength or adhesive strength of the fovea fissure filling material (B), the acidic group-containing polymerizable monomer (a) and the crosslinkable polymerization are used. Hydrophobic polymerizable monomers other than the polymerizable monomer (b) may be blended.

  Such hydrophobic polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2, Examples include 3-dibromopropyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, and 10-hydroxydecyl (meth) acrylate.

  The said hydrophobic polymerizable monomer may mix | blend individually by 1 type, and may mix | blend multiple types in combination. When the blending amount of the hydrophobic polymerizable monomer is excessive, the penetrability of the acidic group-containing polymerizable monomer (a) into the tooth is lowered and the adhesion to the columnar enamel is lowered. Sometimes. Usually, the compounding amount of these polymerizable monomers is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight or less, based on the total weight of the fovea fissure filling material (B). Most preferred.

  A known polymerization initiator can be used as the polymerization initiator (c). Specific examples include α-diketones (c-1), ketals (c-2), thioxanthones (c-3), acylphosphine oxides (c-4), coumarins (c-5), halomethyl. And group-substituted s-triazine derivatives (c-6) and peroxides (c-7). Among them, photopolymerization polymerization initiators such as α-diketones (c-1), ketals (c-2), thioxanthones (c-3), acylphosphine oxides (c-4) (photopolymerization initiation) Agent) is preferable because it imparts excellent curability to the pit and fissure filling material (B), and in particular, the acylphosphine oxides (c-4) have extremely excellent surface curability for the pit and fissure filling material (B). More preferably, the combined use of acylphosphine oxides (c-4) and α-diketones (c-1) not only provides excellent surface curability to the pit and fissure filling material (B), Since the pit and fissure filling material (B) that has entered the deep part of the pit and fissure is also hardened, it is most preferable.

  Examples of α-diketones (c-1) include camphorquinone, benzyl, and 2,3-pentanedione.

  Examples of ketals (c-2) include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of thioxanthones (c-3) include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  Acylphosphine oxides (c-4) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) phenylphosphine oxide, tris (2,4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethyl Reuben benzoyl ethoxyphenyl phosphine oxide are exemplified.

  Examples of the coumarins (c-5) include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, and 3-chenoylcoumarin.

  Examples of the halomethyl group-substituted s-triazine derivative (c-6) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine is exemplified.

  Examples of the peroxide (c-7) include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Specific examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy Examples include 2-ethylhexanoate and t-butyl peroxyisopropyl carbonate. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Specific examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like. Specific examples of the hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, and p-diisopropylbenzene peroxide.

  A polymerization initiator (c) may mix | blend 1 type individually, and may mix | blend multiple types in combination. Usually, the blending amount of the polymerization initiator (c) is preferably in the range of 0.01 to 10% by weight, and in the range of 0.05 to 7% by weight, based on the total weight of the pit and fissure filling material (B). Is more preferable, and the range of 0.1 to 5% by weight is most preferable.

  In order to further improve the polymerization ability of the polymerization initiator (c), it may be used in combination with a polymerization accelerator. Examples of the polymerization accelerator include aromatic tertiary amines, aliphatic tertiary amines, sulfinic acids and salts thereof, aldehydes, and compounds having a thiol group.

Aromatic tertiary amines include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N- Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl- 4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2 -Hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N- (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di- Isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, Examples include n-butoxyethyl 4-N, N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate, and 4-N, N-dimethylaminobenzophenone.

Aliphatic tertiary amines include trimethylamine, triethylamine, N-
Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine Examples include monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate.

  Examples of sulfinic acid and its salts include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, calcium toluenesulfinate. , Lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfine Calcium oxide, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Thorium, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-isopropylbenzenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, Examples include potassium 2,4,6-triisopropylbenzenesulfinate and calcium 2,4,6-triisopropylbenzenesulfinate.

  Examples of aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.

  Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.

  One kind of polymerization accelerator may be blended, or a plurality of kinds may be blended in combination. Usually, the blending amount of the polymerization accelerator is preferably in the range of 0.01 to 10% by weight, more preferably in the range of 0.05 to 7% by weight, based on the total weight of the pit and fissure filling material (B). The range of 0.1 to 5% by weight is most preferable.

  In order to improve applicability, fluidity, adhesiveness, and mechanical strength, a filler (e) may be added to the pit and fissure filling material (B). A filler (e) may mix | blend 1 type individually, and may mix | blend multiple types in combination. Examples of the filler (e) include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.

As the inorganic filler, silica; minerals based on silica such as kaolin, clay, mica, mica; silica based, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La Examples thereof include ceramics and glasses containing ₂ O ₃ , SrO ₂ , CaO, P ₂ O _{5 and the} like. As the glass, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used. Crystal quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride are also preferably used It is done.

  Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymer, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

  Examples of composite fillers of inorganic fillers and organic fillers include inorganic fillers dispersed in organic fillers and inorganic / organic composite fillers coated with various polymerizable monomers. Is done.

  In order to improve the fluidity, applicability and the like of the pit and fissure filling material (B), a filler surface-treated with a known surface treatment agent such as a silane coupling agent may be used as the filler (e). As the surface treatment agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Examples are mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

  The filler (e) is preferably a fine particle filler having a primary particle diameter of 0.001 to 0.1 μm in terms of operability, fluidity, permeability to a pit and fissured part, adhesion to a columnar enamel, and the like. . Specific examples include “Aerosil OX50”, “Aerosil 50”, “Aerosil 200”, “Aerosil 380”, “Aerosil R972”, “Aerosil 130” (all of which are manufactured by Nippon Aerosil Co., Ltd., trade names). .

  The blending amount of the filler (e) is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 0.5 to 20% by weight, based on the total weight of the pit and fissure filling material (B). A range of 1 to 10% by weight is most preferred.

  In order to impart acid resistance to the tooth, a fluoride ion releasing substance (f) may be blended in the pit and fissure filling material (B). Examples of the fluorine ion-releasing substance (f) include fluorine glasses such as fluoroaluminosilicate glass, metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, and methacrylic acid. Examples include fluorine ion releasing polymers such as a copolymer of methyl and methacrylic acid fluoride, and fluorine ion releasing substances such as cetylamine hydrofluoride.

  The compounding amount of the fluoride ion releasing substance (f) is preferably in the range of 0.01 to 40% by weight, and in the range of 0.05 to 30% by weight, based on the total weight of the pit and fissure filling material (B). Is more preferable, and the range of 0.1 to 20% by weight is most preferable.

  You may mix | blend a stabilizer (polymerization inhibitor), a coloring agent, a fluorescent agent, and an ultraviolet absorber with the pit and fissure filling material (B). Also, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan Good.

Pits and fissures Hama塞材(B), the water also do not contain organic solvents not having a polymerizable. Examples of the organic solvent having no polymerizability include acetone, methanol, ethanol, and ethyl acetate. Storage stability is good because it contains no water. Moreover, since it does not contain an organic solvent having no polymerizability, it has good curability, mechanical strength, and adhesion durability.

The weight ratio of the tooth surface treatment agent (A) made of water or an aqueous solution of an inorganic substance having a pH of 5 to 9 and the pit and fissure filling material (B) is usually in the range of 1: 1000 to 1:10, preferably 1: The range is from 500 to 1:20, more preferably from 1: 200 to 1:50.

  Next, an example of a method for using the kit for filling a pit and fissure according to the present invention will be described. First, using a sponge, brush, brush, or three-way syringe, the tooth surface treatment agent (A) is applied to or sprayed on the surface of the pits and fissures of a human tooth, and the tooth surface treatment agent (A) is applied to the columnar enamel. Adhere to the surface. If necessary, air may be blown with a dental air syringe (three-way syringe; air) to such an extent that the water adhering to the surface of the columnar enamel is not completely dried. Next, the pit and fissure filling material (B) is applied to the surface on which the tooth surface treating agent (A) is applied or sprayed. Then, a part of the applied pit and fissure filling material (B) is cured in a mixed state with the tooth surface treatment agent previously applied or sprayed. When the polymerization initiator (c) blended in the pit and fissure filling material (B) is a polymerization initiator (photopolymerization initiator) that generates radicals by light, the pit and fissure filling material (B) It is preferable that a dental visible light irradiator is used to irradiate light and cure in terms of obtaining excellent adhesiveness.

  The invention is explained in more detail by means of examples. The present invention is not limited to the following examples. The materials used in Examples and Comparative Examples are as follows.

[Tooth surface treatment agent]
-Purified water: Wako Pure Chemical Industries, Ltd. (tooth surface treatment agent (A))
NaHCO ₃ aqueous solution: An aqueous solution (tooth treatment agent (A)) in which 0.2 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 99.8 g of purified water.
NaF aqueous solution: An aqueous solution (tooth treatment agent (A)) in which 0.1 g of sodium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 99.9 g of purified water
-10% phosphoric acid aqueous solution: An aqueous solution in which 10 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 85%) is dissolved in 85 g of purified water-Sodium hypochlorite aqueous solution: manufactured by Wako Pure Chemical Industries, Ltd.

[Acid group-containing polymerizable monomer (a)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate PDM: bis (10-methacryloyloxydecyl) pyrophosphate
・ 4-MDT: 4-methacryloyloxydecyloxycarbonylphthalic acid ・ AMPS: 2-acrylamido-2-methylpropanesulfonic acid

[Crosslinkable polymerizable monomer (b)]
UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate 3G: triethylene glycol dimethacrylate U4TH: crosslinkable polymerizable monomer represented by the following chemical formula (b) )

DPE6A: crosslinkable polymerizable monomer (b) represented by the following chemical formula 8

D26E: crosslinkable polymerizable monomer (b) represented by the following chemical formula 9

[Hydrophilic polymerizable monomer (d)]
・ HEMA: 2-hydroxyethyl methacrylate 9G: Nonaethylene glycol dimethacrylate

[Polymerization initiator (c)]
CQ: camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

(Polymerization accelerator)
DMBE: ethyl 4-N, N-dimethylaminobenzoate MBO: 2-mercaptobenzoxazole

[Filler (e)]
Ar380: Aerosil fine particle silica TIO: JP titanium dioxide

[Fluorine ion releasing substance (f)]
・ 40PMF: Fluorine ion-releasing substance represented by the following chemical formula (b)

-NaF: sodium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.)

[Polymerization inhibitor (stabilizer)]
BHT: 2,6-di-t-butyl-4-methylphenol

Example 1
Purified water was prepared as a tooth surface treating agent (A). Also, MDP (20 parts by weight), 3G (40 parts by weight), U4TH (40 parts by weight), TMDPO (2 parts by weight), CQ (0.5 parts by weight), and DMBE (1 part by weight) And BHT (0.1 part by weight) were mixed to prepare a foveal fissure filling material (B). A test piece was prepared using a kit for filling a pit and fissure with the tooth surface treatment agent (A) and the pit and fissure filling material (B), and the test piece was subjected to the following gloss test and coloring property. Tests and adhesion tests were performed. Table 1 shows the presence / absence of use of a phosphoric acid etching agent, the tooth surface treatment agent, the composition (parts by weight) of the pit and fissure filling material, and the test results. The numerical values of the tensile adhesive strength (unit: MPa) in Table 1 are all average values of the measured values for the eight test pieces. In addition, pH was measured using the ion meter (The product made by Orion, model number "920A").

(Examples 2-3 and Comparative Examples 1-4)
NaHCO ₃ aqueous solution (Example 2) and NaF aqueous solution (Example 3) as a tooth surface treating agent (A), a 10% phosphoric acid aqueous solution (Comparative Example 3) having a pH of 0.7, and hypochlorous having a pH of 10.1. A sodium chlorate aqueous solution (Comparative Example 4) was prepared. Moreover, 1 type (Examples 2 and 3 and Comparative Examples 3 and 4) of the pit and fissure filling material (B) and 2 types of comparative pit and fissure filling materials (Comparative Examples 1 and 2) were prepared. . Test pieces were prepared using a kit for filling pits and fissures composed of these tooth surface treatment agents and pit and fissure filling material, and for each of the test pieces, the following glossiness test, coloring test and adhesion test were performed. Went. Table 1 shows the presence or absence of the phosphoric acid etching agent used, the tooth surface treatment agent used, the composition (parts by weight) of the pit and fissure filling material, and the test results.

(Glossiness test and coloring test)
After removing the extracted human crown, especially the pit and fissure (no-column enamel) using a tooth surface cleaning brush (trade name “Brush Cone” manufactured by Nippon Dental Industry Co., Ltd.), the tooth surface The sponge was impregnated with the treatment agent, and pressed against the crown surface (columnar enamel) to attach moisture to the crown surface. Next, the pit and fissure filling material was applied to the surface of the pit and fissured part in wet state (columnar enamel surface) using a small brush, left still for 5 seconds, and then a dental light irradiator (Morita) The product was irradiated with light for 20 seconds under the trade name “JETLITE 3000”) to cure the pit and fissure filling material to obtain a test piece. This test piece was immersed in a 0.5% aqueous suspension of a colorant (manufactured by Gavan Asaoka Co., Ltd., trade name “turmeric powder”), and stored in a thermostat set at 37 ° C. for 24 hours. Thereafter, the presence or absence of gloss on the surface of the crown portion around the pit and fissure filling material and the colorability were examined visually.

(Adhesion test)
After removing the surface of the extracted anterior labial side (columnar enamel) using a tooth surface cleaning brush (above-mentioned “brush cone”), a 3 mm diameter round hole is formed in the center of the anterior lip side. An adhesive tape having a thickness of 150 μm was attached. A sponge piece was impregnated with a tooth surface treatment agent, and this was pressed against the surface of the columnar enamel in the round hole, and moisture was adhered to the surface. Next, the pit and fissure filling material was applied to the surface of the columnar enamel in a wet state using a small brush, left standing for 5 seconds, and then released from a release film (trade name “EVAL” manufactured by Kuraray Co., Ltd.). Then, the slide glass was placed and pressed, and in this state, light was irradiated for 20 seconds with a dental light irradiator (the above-mentioned “JETLITE 3000”) to cure the fovea fissure filling material. . Adhering one end face (circular cross section) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm to this hardened surface using a dental resin cement (Kuraray Medical, trade name “Panavia Fluorocement”) Thus, a test piece was obtained. Eight test pieces were prepared. All test pieces were immersed in water after bonding and stored in a thermostat at 37 ° C for 1 day, and then the autograph (Shimadzu Corporation, model number “MODELAG” was set with a tensile bond strength of 2 mm / min. -1 "). Tensile bond strength is obtained by pulling a stainless steel cylindrical rod in a direction that does not deviate more than 5 ° with respect to the axial direction with several metal plates with a thickness of 0.5 mm attached and teeth fixed. Measured.

  As shown in Table 1, the tooth surface treatment agent (A) having a pH of 7.0, 8.3 or 6.5, an acidic group-containing polymerizable monomer (a), and a crosslinkable polymerizable monomer (b) And a pit and fissure plugging material (B) containing a polymerization initiator (c), the tensile bond strength to the columnar enamel is 10 MPa or more. (Examples 1-3). In addition, the gloss and coloring of the columnar enamel surface around the pit and fissure filling material were hardly changed compared to those before the treatment. From these facts, the kit for filling the pits and fissures of Examples 1 to 3 exhibits an excellent adhesive force with respect to the columnar enamel and does not damage the teeth so much that the luster disappears. It can be seen that the tooth surface is not colored to an unsatisfactory degree.

  On the other hand, when the pit and fissure filling material containing no acidic group-containing polymerizable monomer (a) was used, the gloss and coloring did not decrease so much after the treatment, but the tensile adhesive strength was 0.0 MPa (Comparative Example 1). From this, it can be seen that the acidic group-containing polymerizable monomer (a) greatly contributes to the excellent adhesive force exhibited by the kit for filling a pit and fissure according to the present invention. In addition, even when a fovea fissure filling material containing no crosslinkable polymerizable monomer (b) was used, the gloss and coloration after the treatment were not significantly changed from those before the treatment. The adhesive strength was 1.9 MPa (Comparative Example 2). From this, it can be seen that the crosslinkable polymerizable monomer (b) greatly contributes to the excellent adhesive force exhibited by the kit for filling the pit and fissure according to the present invention. Further, when a 10% phosphoric acid aqueous solution having a pH of 0.7 was used as a tooth surface treating agent, the gloss of the tooth surface disappeared due to excessive decalcification, and the color was changed to light yellow (Comparative Example 3). When the phosphoric acid aqueous solution is used as the tooth surface treating agent as in Comparative Example 3, the adhesiveness is low because the acid having no polymerizable group such as phosphoric acid is a polymerizable monomer in the pit and fissure filling material. This is because the polymerization of the above is inhibited. Moreover, when the sodium hypochlorite aqueous solution of pH 10.1 was used as a tooth surface treating agent, adhesiveness fell remarkably (Comparative Example 4). This is because decalcification was insufficient.

(Examples 4 to 10)
Purified water as a tooth surface treating agent (A) was prepared. A plurality of types of pit and fissure filling materials (B) were prepared. Test pieces were prepared using a kit for filling the pit and fissures composed of the tooth surface treatment agent (A) and the pit and fissure filling material (B), and each of the test pieces was subjected to the above gloss test and coloring. Property test and adhesion test were performed. Table 2 shows the presence / absence of the use of a phosphoric acid etching agent, the composition (parts by weight) of the pit and fissure filling material, and the test results.

  As shown in Table 2, a pit containing a tooth surface treating agent (A), an acidic group-containing polymerizable monomer (a), a crosslinkable polymerizable monomer (b), and a polymerization initiator (c) In the case of using the pit and crevice groove filling kits of Examples 4 to 10 made of the fissure filling material (B), the tensile adhesive strength to the columnar enamel was 10 MPa or more. In addition, the gloss and coloring of the columnar enamel surface around the pit and fissure filling material were hardly changed compared to those before the treatment. From these facts, the kits for filling pits and fissures of Examples 4 to 10 exhibit excellent adhesion to pillarless enamel, and do not damage the teeth so much that they lose their luster. It can be seen that the tooth surface is not colored to an unsatisfactory degree.

  Further, as the acidic group-containing polymerizable monomer (a), a phosphoric acid group-containing polymerizable monomer (MDP), a pyrophosphate group-containing polymerizable monomer (PDM) or a carboxylic acid group-containing polymerizable monomer ( When comparing three kits for embedding fissures using 4-MDT (Examples 4 to 6), kits for filling fissures and fissures containing a phosphate group-containing polymerizable monomer (MDP) ( Example 4) showed the most excellent adhesive force, and then the kit for filling the pits and fissures (Example 5) containing the pyrophosphate group-containing polymerizable monomer (PDM) showed high adhesive force. Further, the kit for embolizing the pits and fissures (Example 10) in which the phosphate group-containing polymerizable monomer (MDP) and the sulfonic acid group-containing polymerizable monomer (AMPS) are used in combination exhibits particularly high adhesive strength. It was. Further, a kit for filling a fovea and fissure (Examples 7 to 9) further blended with HEMA (hydrophilic polymerizable monomer (d)) is HEMA (hydrophilic polymerizable monomer (d)). As compared with the kit for embolizing the pit and fissures (Examples 4 to 6) in which no was added, the adhesive strength was higher.

(Examples 11 to 17)
Purified water as a tooth surface treating agent (A) was prepared. In addition, a plurality of types of pit and fissure filling materials (B) containing filler were prepared. A test piece was prepared using a kit for foveal fissure plugging (Examples 11 to 17) composed of these tooth surface treatment agent (A) and a foveal fissure plugging material (B), and for each test piece, The previous gloss test, color test and adhesion test were conducted. Table 3 shows the presence / absence of the use of a phosphoric acid etching agent, the composition (parts by weight) of the fovea fissure filling material, and the test results.

  As shown in Table 3, the tooth surface treating agent (A), the acidic group-containing polymerizable monomer (a), (crosslinkable polymerizable monomer (b), polymerization initiator (c), hydrophilic The pit and fissure block filling kits of Examples 11 to 17 comprising a polymerizable monomer (d) and a filler (e) containing the pit and fissure plug material (B) are tensile bonded to a pillarless enamel. The strength was 10 MPa or more, and the luster and coloring of the columnar enamel surface around the pit and fissure filling material were hardly changed compared to those before the treatment. From the above, the kit for filling pits and fissures of Examples 11 to 16 exhibits an excellent adhesive force with respect to the columnar enamel, and does not damage the teeth so much that the luster is lost. It can be seen that the surface is not colored to an aesthetically unsatisfactory level.

  In addition, by blending fine particle silica (filler (e)) such as Ar380, fluidity can be suppressed without deteriorating the physical properties (adhesiveness and strength) of the pit and fissure filling material (B). It was found that the property and the filling property were improved. By improving the operability and filling properties, for example, dental treatment can be performed without attaching a fovea and fissure filling material to sites other than teeth (for example, gingiva and oral mucosa). Furthermore, when using a pit and fissure filling material blended with a white filler such as TIO, it shows a white or pale yellowish white color tone, and after curing, there is no sense of incongruity with the surrounding teeth. It was found that color compatibility was obtained.

(Examples 18 to 24)
Purified water as a tooth surface treating agent (A) was prepared. A plurality of types of pit and fissure filling materials (B) were prepared. Using these tooth surface treatment agents (A) and the pit and fissure filling material (B), a test piece was prepared using the pit and fissure plug kit (Examples 18 to 24). The gloss test, the color test, the adhesion test and the acid-resistant layer formation test described below were performed. Table 4 shows the presence / absence of use of a phosphoric acid etching agent, the composition (parts by weight) of the fovea / fissure filling material, and the test results.

(Acid resistant layer formation test)
After removing the crown of the extracted human molar, especially the pit and fissure (columnar enamel), using a tooth surface cleaning brush (above-mentioned “brush cone”), impregnated with a tooth surface treatment agent. The sponge piece was pressed against the surface of the crown (columnar enamel) to allow moisture to adhere to the surface of the crown. Next, a pit and fissure filling material was applied to the surface of the pit and fissured part (columnar enamel surface) in a wet state using a small brush, and allowed to stand for 5 seconds. (JETLITE 3000)) was irradiated with light for 20 seconds to cure the pit and fissure filling material to obtain a test piece. This test piece was immersed in a phosphate buffer having a pH of 7.0, and stored in a 37 ° C incubator for 3 months in this state. Three months later, the test piece was cut using a low-speed diamond saw, and the cut surface was polished with # 3000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under wet conditions, and then a 1 μm diamond polishing paste was added. Used and polished. After polishing, the test piece was immersed in distilled water, subjected to ultrasonic cleaning to remove the diamond polishing paste adhering to the test piece, and immersed in a pH 5.6 citrate buffer solution for 8 hours. The test piece was taken out and the thickness of the acid-resistant layer formed was examined by observing the adhesion interface between the tooth structure and the pit and fissure filling material in the fractured section with an electron microscope (magnification: 2000 times).

  As shown in Table 4, the tooth surface treating agent (A), acidic group-containing polymerizable monomer (a), crosslinkable polymerizable monomer (b), polymerization initiator (c), hydrophilic polymerization The kit for filling pits and fissures of Examples 18 to 24, which comprises a pit and fissure filling material (B) containing a functional monomer (d), a filler (e) and a fluorine ion releasing substance (f), The tensile adhesive strength for the columnar enamel was 11 MPa or more. In addition, the gloss and coloring of the columnar enamel surface around the pit and fissure filling material were hardly changed compared to those before the treatment. From these facts, the kits for filling pits and fissures of Examples 18 to 24 exhibit excellent adhesion to columnar enamel and do not damage the teeth so much that their luster disappears. It can be seen that the tooth surface is not colored to an unsatisfactory degree.

  In addition, when a pit / fissure cuff filling kit in which a fluorine ion-releasing substance (f) such as NaF or 40PMF is blended with the pit / fissure cuff filling material (B) is used (Examples 18 to 24), An acid resistant layer of 5 μm or more was formed. From this, it can be seen that the kits for filling pits and fissures of Examples 18 to 24 impart resistance to acids to the tooth. In particular, when a pit / fissure block filling kit in which HEMA (hydrophilic polymerizable monomer (d)) is blended with the pit / fissure plug material (B) (Examples 21 to 23), Compared to the case of using the pit and fissure filling material (B) in which HEMA (hydrophilic polymerizable monomer (d)) is not blended in the fistula filling material (B) (Examples 18 to 20) The acid-resistant layer was thick. This is because water penetrates into the highly hydrophilic pit and fissure filling material (B), and fluorine ions dissolved in the water elute on the surface of the pit and fissure filling material (B), and This is because the reaction becomes easy and a large amount of fluoroapatite is produced. In addition, when MDP having excellent adhesion and AMPS having strong deashing power are used in combination as the acidic group-containing polymerizable monomer (a) (Example 24), extremely excellent adhesion is obtained, and acid resistance is also obtained. The layer was thick. The combination of both improves the adhesion and penetration of the pit and fissure filling material into the columnar enamel, and the pit and fissure filling material penetrates deep inside the columnar enamel. This is because a resin-impregnated portion having extremely thick acid resistance is formed at the joint portion with the cleft and groove filling material (resin). Incidentally, the reason why this resin-impregnated portion has acid resistance is that the tooth impregnated with the resin is difficult to dissolve in acid.

(Examples 25 to 28)
Purified water as a tooth surface treating agent (A) was prepared. A plurality of types of pit and fissure filling materials (B) were prepared. A test piece was prepared using a kit for foveal fissure plugging (Examples 25 to 28) composed of these tooth surface treatment agent (A) and a foveal fissure plugging material (B), and for each test piece, The previous gloss test, color test, adhesion test and acid-resistant layer formation test were conducted. Table 5 shows the presence / absence of use of a phosphoric acid etching agent, the composition (parts by weight) of the pit and fissure filling material, and test results.

  As shown in Table 5, the tooth surface treating agent (A), acidic group-containing polymerizable monomer (a), crosslinkable polymerizable monomer (b), polymerization initiator (c), hydrophilic polymerization The pit and fissure block filling kit of Examples 25 to 28, which comprises the pit and fissure blocker (B) containing the functional monomer (d), the filler (e) and the fluorine ion releasing substance (f), The tensile adhesive strength for columnar enamel was 10 MPa or more. In addition, the gloss and coloring of the columnar enamel surface around the pit and fissure filling material were hardly changed compared to those before the treatment. From these facts, the kit for filling the pits and fissures of Examples 25 to 28 exhibits an excellent adhesive force with respect to the columnar enamel, and does not damage the teeth so much that the luster disappears. It can be seen that the tooth surface is not colored to an unsatisfactory degree. Furthermore, when the kit for filling pits and fissures of Examples 25 to 28 was used, an acid-resistant layer of 10 μm or more was formed on the adhesion interface. From this, it can be seen that the pit and fissure filling kits of Examples 25 to 28 impart resistance to acids to the tooth.

(Comparative Example 5)
After removing the crown of the extracted human molar, especially the pits and fissures (columnar enamel) using the tooth surface cleaning brush (above-mentioned “brush cone”), the crown surface (columnless) Enamel) was coated with 35% phosphoric acid aqueous solution. After standing for 10 seconds, the decalcified columnar enamel component and phosphoric acid were washed away with running water, and the moisture on the surface of the tooth was evaporated with a dental air syringe (three-way syringe). Next, the pit and fissure filling material was applied to the pit and fissure using a small brush, left still for 5 seconds, and then irradiated with light for 20 seconds with a dental light irradiator ("JETLITE 3000" mentioned above). The pit and fissure filling material was cured to obtain a test piece. About this test piece, the previous glossiness test and coloring property test were done.

  Also, after removing the surface of the extracted human anterior labial side (columnar enamel) using a tooth surface cleaning brush (the “brush cone” above), the surface of the crown (columnar enamel) is then removed. A 35% aqueous phosphoric acid solution was applied. After standing for 10 seconds, the demineralized columnar enamel component and phosphoric acid are washed away with running water, and the moisture on the surface of the tooth is evaporated with a dental air syringe (three-way syringe), then the front teeth A 150 μm thick adhesive tape having a 3 mm diameter round hole was attached to the center on the lip side. In the round hole, we apply a foveal fissure filling material, let it stand for 5 seconds, and then coat it with a release film (Kuraray Co., Ltd., “Eval”), then place and slide glass In this state, light was irradiated for 20 seconds with a dental light irradiator (the above-mentioned “JETLITE 3000”) to cure the pit and fissure filling material. One end face (circular cross section) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm was adhered to this hardened surface using a dental resin cement (the above-mentioned “Panavia fluorocement”), and a test piece was obtained. It was. The previous adhesion test was performed on this test piece.

  Table 6 shows the presence / absence of the use of the phosphoric acid etching agent, the presence / absence of the use of the tooth surface treatment agent (A), the composition of the adhesive (parts by weight), the used pit and fissure filling material, and the test results.

(Comparative Examples 6 and 7)
After removing the crown of the extracted human molar, especially the pits and fissures (columnar enamel) using the tooth surface cleaning brush (above-mentioned “brush cone”), the crown surface (columnless) To the enamel, an adhesive composed of MDP (20 parts by weight), ethanol (Comparative Example 6) or HEMA (Comparative Example 7) (55 parts by weight), and purified water (25 parts by weight) was applied. After leaving still for 30 seconds, volatile components were evaporated to such an extent that the fluidity of the adhesive disappeared with a dental air syringe (three-way syringe). Next, the pit and fissure filling material was applied to the pit and fissure using a small brush, left still for 5 seconds, and then irradiated with light for 20 seconds with a dental light irradiator ("JETLITE 3000" mentioned above). The pit and fissure filling material was cured to obtain a test piece. About this test piece, the previous glossiness test and coloring property test were done.

  In addition, after removing the surface of the extracted human front lip side (columnless enamel) using a tooth surface cleaning brush (the “Brush Cone” above), a 3 mm diameter circle is placed in the center of the front lip side. A 150 μm thick adhesive tape with holes was attached. In the round hole, an adhesive composed of MDP (20 parts by weight), ethanol (Comparative Example 6) or HEMA (Comparative Example 7) (55 parts by weight), and purified water (25 parts by weight) was applied. After leaving still for 30 seconds, volatile components were evaporated to such an extent that the fluidity of the adhesive disappeared with a dental air syringe (three-way syringe). Next, a crevice fissure filling material was applied on the adhesive, allowed to stand for 5 seconds, and then covered with a release film (trade name “EVAL” manufactured by Kuraray Co., Ltd.), and then a slide glass was placed. In this state, the adhesive and the pit and fissure filling material were cured by irradiating with a dental light irradiator (the above-mentioned “JETLITE 3000”) for 20 seconds. One end face (circular cross section) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm was adhered to this hardened surface using a dental resin cement (the above-mentioned “Panavia fluorocement”), and a test piece was obtained. It was. The previous adhesion test was performed on this test piece.

  Table 6 shows the presence / absence of the use of the phosphoric acid etching agent, the presence / absence of the use of the tooth surface treatment agent (A), the composition of the adhesive (parts by weight), the used pit and fissure filling material, and the test results.

(Comparative Example 8)
After removing the extracted human crown, especially the pit and fissures (columnar enamel), using a toothbrush cleaning brush (see above “Brush Cone”), the pit and fissure filling material Apply to the surface of the pits and fissures (columnar enamel surface) using a small brush, let stand for 5 seconds, and then irradiate with a dental light irradiator (above “JETLITE 3000”) for 20 seconds. The pit and fissure filling material was cured to obtain a test piece. About this test piece, the previous glossiness test and coloring property test were done.

  In addition, after removing the surface of the extracted human front lip side (columnless enamel) using a tooth surface cleaning brush (the “Brush Cone” above), a 3 mm diameter circle is placed in the center of the front lip side. Adhesive tape with a thickness of 150 μm having a hole was applied, and a pit and fissure filling material was applied in the round hole using a small brush, and left standing for 5 seconds, and then it was released from a release film (manufactured by Kuraray Co., Ltd.). After coating with a product name “EVAL”), a slide glass is placed and pressed, and in this state, light is irradiated for 20 seconds with a dental light irradiator (“JETLITE 3000” mentioned above), and a fissure is formed. The filling material was cured. One end face (circular cross section) of a stainless steel cylindrical rod having a diameter of 5 mm and a length of 1.5 cm was adhered to this hardened surface using a dental resin cement (the above-mentioned “Panavia fluorocement”), and a test piece was obtained. It was.

  Table 6 shows the presence / absence of the use of the phosphoric acid etching agent, the presence / absence of the use of the tooth surface treatment agent (A), the composition of the adhesive (parts by weight), the used pit and fissure filling material and the test results.

  As shown in Table 6, in the adhesion method of Comparative Example 5 in which the pit and fissure filling material was applied after the phosphoric acid etching treatment, the luster disappeared in the teeth due to excessive decalcification due to the phosphoric acid etching treatment. The damage was big enough to do. In the bonding method of Comparative Examples 6 and 7 bonded using an adhesive without performing phosphoric acid etching treatment, the surface of the teeth (no-column enamel) around the pit and fissure plugging material is colored yellow by the colorant. However, the aesthetics clearly decreased compared to that before the treatment. The adhesion method of Comparative Example 8 in which the pit and fissure filling material was directly applied to the surface of the pit and fissure part without using the phosphoric acid etching agent, the adhesive, and the tooth surface treatment agent (A) showed extremely good adhesion. There wasn't.

(Comparative Example 9)
Water (purified water), MDP (20 parts by weight), 3G (40 parts by weight), U4TH (40 parts by weight), TMDPO (2 parts by weight), CQ (0.5 parts by weight), DMBE (1 part by weight) And a composition comprising BHT (0.1 part by weight) were mixed at a weight ratio of 1: 1 to prepare a pit / fissure filling material containing water. A test piece is prepared using a kit for filling a pit and fissure with the purified water as a tooth surface treatment agent and the above-mentioned pit and fissure filling material, and the gloss test and coloring test are performed on the test piece. And an adhesion test was performed. In this adhesion method using the water-containing pit and fissure filling material, no loss of gloss or coloring was observed, but the tensile strength was 2.6 MPa, and the adhesion was not very good. From this result, it can be seen that when water is contained in the pit and fissure filling material, the adhesiveness is significantly lowered. Further, the kit for filling the pit and fissures prepared in Example 1 and the kit for filling the pit and fissures prepared in Comparative Example 9 were each put in a propylene container and kept in a thermostat kept at 50 ° C. for 30 days. Stored. Subsequently, a test piece was prepared using each, and the previous adhesiveness test was performed on these test pieces. The tensile bond strength of the test piece prepared using the kit for filling the pits and fissures prepared in Example 1 is 13.0 MPa, and is prepared using the kit for filling pits and fissures prepared in Comparative Example 9. The tensile bond strength of the test piece was 0.2 MPa. From this result, it can be seen that storage stability is significantly reduced when water is contained in the pit and fissure filling material.

Since the kit for filling the pit and fissure according to the present invention can fill the pit and fissure part without using an acid etching agent or an adhesive, it is extremely useful as a caries prevention material for the pit and fissure part.

Claims (5)

  A tooth surface treating agent (A) comprising an aqueous solution of water or an inorganic substance having a pH of 5 to 9, an acidic group-containing polymerizable monomer (a), a crosslinkable polymerizable monomer (b) and a polymerization initiator (c). A kit for filling a pit and fissure containing the pit and fissure filling material (B) containing neither water nor polymerizing organic solvent.   The inorganic substance is sodium chloride, lithium chloride, potassium chloride, sodium bromide, calcium chloride, calcium bicarbonate, sodium bicarbonate, calcium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, sodium dihydrogen phosphate, diphosphate phosphate Potassium hydrogen, calcium hydrogen phosphate, disodium hydrogen phosphate, sodium borate, sodium dihydrogen phosphite, potassium dihydrogen phosphite, sodium fluoride, calcium fluoride, lithium fluoride, potassium fluoride, fluoride The kit for filling pits and fissures according to claim 1, which is an inorganic salt selected from the group consisting of tin, sodium monofluorophosphate and potassium monofluorophosphate.   The kit for filling pits and fissures according to claim 1 or 2, wherein the pit and fissure filling material (B) further contains a hydrophilic polymerizable monomer (d).   The kit for filling a pit and fissure according to any one of claims 1 to 3, wherein the pit and fissure filling material (B) further contains a filler (e).   The pit and fissure filling kit according to any one of claims 1 to 4, wherein the pit and fissure filling material (B) further contains a fluorine ion-releasing substance (f).