JP6506589B2 - Dental surface treatment composition - Google Patents

Description

  The present invention relates to a dental surface treatment agent composition that can be stably stored over a long period of time. More particularly, the present invention relates to a dental surface treatment composition containing a metal antioxidant together with a transition metal compound. The surface treatment agent used for the dentin includes bonding agent, primer, coating agent, cement, backing agent, coating agent, sealer, sealant and the like.

  In the field of dental treatment, it is necessary to strongly bond dentin, especially dentin, to materials (for example, polymer substances, metals, porcelain etc.) for repairing the dentin, and various adhesives for that purpose are already used. Proposed.

  Such an adhesive generally has a three-component composition of (1) a polymerizable monomer, (2) a polymerization catalyst or polymerization initiator and (3) a filler. Typical examples of such adhesives include (1) mixtures of (meth) acrylic acid esters as polymerizable monomers, and (2) benzoyl peroxide as polymerization catalysts and aromatic tertiary amine systems. Or an adhesive composition comprising a catalyst component in which a sulfinate is added to the mixture and (3) a filler such as a polymer or silica, or (1) (meth) acrylic acid ester as a polymerizable monomer, (2) Adhesive composition comprising a photopolymerization initiator comprising camphorquinone as a photosensitizer and N, N-dimethylaminoethyl methacrylate as a reducing agent, and (3) a filler such as a polymer or silica. And (1) (meth) acrylic acid ester as a polymerizable monomer, (2) tributylborane partial oxide (TBBO) as a polymerization catalyst, and (3) Adhesive compositions comprising fillers such as trimers and silica have been proposed.

  In order to improve the adhesion of such an adhesive to dentin, it has been proposed to use an adhesion promoting monomer or a monomer having an affinity to dentin. Examples of the adhesion-promoting monomer or the monomer having an affinity to the dentin include, for example, 4-methacryloyloxyethoxycarbonylphthalic acid (4-MET) or an acid anhydride thereof (4-META) and 10-methacryloyloxydecyl malonic acid (MAC Examples thereof include monomers having a carboxyl group (or a group capable of being converted to a carboxyl group) such as -10) and monomers having a phosphoric acid group such as 10-methacryloyloxydecyl dihydrogen phosphate.

  In order to obtain such a strong adhesive performance of the adhesive to the dentin, pretreatment of the dentin surface with an etchant or a primer is required. For example, by etching the dentin enamel surface with phosphoric acid or the like and using the above-mentioned adhesive, the adhesive strength and the adhesive durability which have no problem in practical use are obtained.

  In addition, it is known that dentin is etched with a citric acid solution containing ferric chloride, and high adhesion is developed when adhering with an adhesive using TBBO as a polymerization initiator.

  Moreover, in the primer, it apply | coated to the tooth surface conventionally, and it has been used for the purpose of raising the adhesive strength of an adhesive agent and tooth substance. Such a composition is often made to contain an acidic monomer and an amine compound as a polymerization initiator, aiming to initiate a polymerization reaction from the surface of dentin to improve adhesive strength. On the other hand, in order to obtain high adhesion to dentin in particular, pretreatment with a solution containing an acidic monomer and a transition metal compound such as iron or copper is disclosed in JP-A-8-127509. And Patent Document 2 (Japanese Patent Application Laid-Open No. 9-227325), it is widely known. However, the dental adhesive composition described in this patent document does not contain the oxidation inhibitor of the transition metal compound, and problems such as functional deterioration and coloring due to aging deterioration are pointed out.

  Moreover, in patent document 3 (Unexamined-Japanese-Patent No. 2003-12429), after treating sodium hypochlorite-phosphoric acid solution as treatment after caries removal to dentin, ascorbic acid-ferric chloride solution It is shown to apply. However, ascorbic acid according to this patent document aims to neutralize oxidation of the pit wall by sodium hypochlorite, and is not intended to suppress oxidation of ferric chloride. In addition, this solution does not have a composition as a primer and requires complicated steps before applying the adhesive.

JP-A-8-127509 Japanese Patent Application Laid-Open No. 9-227325 Japanese Patent Application Publication No. 2003-12429

  The object of the present invention is to provide a novel tooth surface treatment comprising a transition metal compound which can be adhered to teeth, particularly dentin, by a simple adhesion operation and without gaps even under wet conditions and which is excellent in storage stability. An agent composition is provided.

  In order to solve the above-mentioned problems, the present inventors, by adding to the transition metal compound and water, a compound containing one or more phosphate group and one or more hydroxyl group in one molecule, the tooth substance The composition of the dental surface treatment agent excellent in storage stability was found without affecting the high adhesive strength. Furthermore, it has been found that the storage stability can be further enhanced by the presence of a compound having a hydroxyl group belonging to a conjugated pi electron system having a cyclic structure in the present composition, and the present invention has been completed.

  The present invention relates to a hydroxyl group belonging to a conjugated pi electron system having a transition metal compound and (c1) one or more compounds each containing a phosphoric acid group and an alcoholic hydroxyl group in one molecule, and / or a (d1) cyclic structure. By using a compound having the following, a surface treatment composition that can be stably stored over a long period of time can be obtained.

  As the (a1) transition metal compound in the dental surface treatment agent composition of the present invention, known compounds can be used, and specifically exemplified, vanadium bromide, nickel bromide, copper bromide, bromide Iron, bromide such as cobalt bromide, nickel chloride, vanadium chloride, palladium chloride, nickel chloride, titanium chloride, iron chloride, chloride such as iron chloride, cobalt chloride, vanadium fluoride, cobalt fluoride, copper fluoride, nickel fluoride, Fluorides such as potassium titanium fluoride, sulfates such as palladium sulfate, nickel sulfate, titanium sulfate, copper sulfate, iron sulfate, cobalt sulfate etc., nitrates such as nickel nitrate, palladium nitrate, nickel nitrate, iron nitrate, cobalt nitrate, etc. Salts of inorganic acids such as phosphates such as iron phosphate and cobalt phosphate, nickel acetate, copper acetate, cobalt acetate, cobalt benzoate, copper citrate, que Iron acid, potassium titanium oxalate, iron oxalate, cobalt oxalate, iron lactate, iron fumarate, copper acrylate, copper methacrylate, nickel sulfamate, nickel stearate, vanadium stearate, cobalt stearate, vanadium naphthenate, naphthenic acid Salts of organic acids such as cobalt and cobalt gluconate, palladium hydroxide, nickel hydroxide, iron hydroxide, copper hydroxide, hydroxides such as cobalt hydroxide, etc., pi electron organic complexes such as titanocene dichloride, vanadium acetylacetonate And organic complexes with acetylacetone such as nickel acetylacetonate, copper acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, etc. and EDTA, and these transition metal compounds may be of any valence. Among transition metal compounds, compounds of iron, cobalt and copper are preferable, and in particular, compounds of iron and copper are suitably used. The transition metal compounds can also be used alone or in combination.

  Among transition metal compounds, compounds of iron, cobalt and copper are preferable, and in particular, compounds of iron and copper are suitably used. That is, the (a1) transition metal compound in the dental surface treatment agent composition of the present invention is preferably a compound consisting of (a1-1) iron and / or copper, and the odor as mentioned above is preferable. Bromides such as iron bromide and copper bromide, chlorides such as iron chloride and copper chloride, fluorides such as iron fluoride and copper fluoride, sulfates such as iron sulfate and copper sulfate, nitrates such as iron nitrate and copper nitrate , Salts of inorganic acids such as phosphates such as iron phosphate and copper phosphate, iron acetate, copper acetate, iron citrate, iron citrate, iron citrate, iron oxalate, iron oxalate, iron lactate, copper lactate, acrylic acid Salts of organic acids such as iron, copper acrylate, iron methacrylate, copper methacrylate, iron sulfamate, sulfamine copper, iron stearate, copper stearate, iron naphthenate, iron naphthenate, iron gluconate, iron gluconate and the like , Hydroxides such as iron hydroxide and copper hydroxide, iron acetylacetonate, copper acetate It is an organic complex with acetylacetone such as tylacetonate or EDTA, and these transition metal compounds may be of any valence. The transition metal compounds can also be used alone or in combination.

  The amount of the compound (a1) transition metal compound or the compound (a1-1) composed of iron and / or copper in the dental surface treatment agent composition of the present invention is not particularly limited. In consideration of adhesion to the dental resin cement, 0.01 to 10% by weight, preferably 0.05 to 5% by weight, and more preferably 0.1 to 3% by weight in 100% by weight of the dental surface treatment agent. is there. By setting the content in the above-mentioned range, it is possible to obtain particularly excellent adhesive strength to the dental resin cement.

  (B) Water in the dental surface treatment composition of the present invention is used for the purpose of demineralizing tooth substance, and substantially free of impurities harmful to storage stability, biocompatibility and adhesiveness. Preferably, for example, deionized water, distilled water and the like are suitably used.

  The compounding quantity of said (b) water in the dental surface treatment agent composition of this invention is not specifically limited. In addition, when the adhesiveness with the resin cement for dental treatment is taken into consideration, it is 1 to 80% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight in 100% by weight of the dental surface treatment agent. is there. By setting the content in the above-mentioned range, it is possible to obtain particularly excellent adhesive strength to the dental resin cement.

  Compounds containing one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule of the dental surface treatment agent composition of the present invention are, for example, phosphorylated sugar compounds such as adenosine triphosphate, etidronic acid, etc. Phosphonic acids and salts thereof such as sodium salts; glycerophosphate, 3-hydroxy-2-oxopropyl phosphate, glucose-6-phosphate, phenolphthalein phosphate, 11β, 17-dihydroxy-21- (phosphonooxy) pregna-1, Examples thereof include 4-diene-3, 20-dione and salts such as sodium salt thereof; phosphoric acid of ascorbic acid and salts such as sodium salt thereof. Among the present compounds, glycerophosphoric acid and the like are suitably used.

  The compounding quantity of the compound which contains a phosphoric acid group and one or more each of an alcoholic hydroxyl group in one molecule of said (c1) in the dental surface treatment agent composition of this invention is not specifically limited. In consideration of the storage stability of the dental surface treatment agent, 0.01 to 20 wt%, preferably 0.02 to 15 wt%, more preferably 0.03 to 10 wt% in 100 wt% of the dental surface treatment agent It is. The long-term storage stability of the dental surface treatment composition can be obtained by setting the content in the above range.

  The compound (c1-) having a molar mass in the range of 120 to 500 g / mol, in the dental surface treatment agent composition of the present invention, the compound containing one or more phosphoric acid group and one or more alcoholic hydroxyl groups in one molecule of (c1) It is desirable that the compound is 1) and the compounding amount is in the range of 40 or less to the transition metal compound 1 in the weight ratio to the (a1) transition metal compound.

  Compounds having a molar mass of 120 to 500 g / mol each containing one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule (c1-1) include phosphonic acids such as etidronic acid and sodium thereof Salts such as salts; glycerophosphoric acid, 3-hydroxy-2-oxopropyl phosphate, glucose hexaphosphate, phenolphthalein phosphate, 11β, 17-dihydroxy-21- (phosphonooxy) pregna-1,4-diene-3 And 20-dione, and salts thereof such as sodium salts thereof; and ascorbic acid phosphoric acid and salts such as sodium salts thereof and the like. Among the above-mentioned present compounds, glycerophosphoric acid and the like are suitably used.

  The (c1-1) compound preferably has a molar mass of 120 to 500 (more preferably 130 to 400, still more preferably 140 to 300) g / mol. Below the lower limit value of the above-mentioned numerical range or above the upper limit value, the water solubility may be reduced, which is not preferable. Also, in consideration of the balance between the realization of the storage stability of the dental surface treatment agent and the adhesion acquisition with the dental resin cement, the weight ratio of the transition metal compound contained in the dental surface treatment agent composition is When it is 1, it is 40 or less, preferably 30 or less, more preferably 20 or less. By setting the content within the above range, it is possible to achieve both the realization of long-term storage stability of the dental surface treatment agent and the acquisition of adhesiveness with the dental resin cement.

  The compound having a hydroxyl group belonging to a conjugated pi-electron system having a cyclic structure (d1) in the dental surface treatment agent composition of the present invention is a conjugated pi-electron system and contains at least a cyclic structure therein. And it is a compound which a hydroxyl group has couple | bonded with the carbon atom which belongs to said system. The conjugated pi electron system has a structure in which a double bond and a single bond are alternately arranged in a linear carbon chain and / or a non-aromatic cyclic carbon chain, and / or a single ring and / or a condensation of an aromatic ring Ring structures are included. The cyclic structure of the conjugated pi-electron system having a cyclic structure may be an aromatic ring (for example, vitamin E) or a non-aromatic ring in which only part of the cyclic structure is unsaturated (for example, vitamin A) It is good. The hydroxyl group belonging to the conjugated pi-electron system indicates that the reduction effect is exhibited under the conjugation effect of the electron system. For that purpose, it is important that a hydroxyl group is bonded to an atom to which the electron system belongs or an atom in the vicinity thereof. Preferably, a hydroxyl group is bonded to the aromatic or unsaturated carbon atom in the cyclic structure. However, when the bonding position of the hydroxyl group in the linear carbon chain can be an aldehyde form by keto enol tautomerism of vinyl alcohol, it can not be directly bonded to unsaturated carbon, but is a saturated carbon adjacent to the unsaturated carbon atom It is necessary to bind to an atom (for example, vitamin A), but such a binding position also belongs to a conjugated pi-electron system, for example, to exhibit an antioxidative effect. The conjugated pi electron system may contain a hetero atom such as oxygen such as a carbonyl group like vitamin C. Also, in the conjugated pi electron system, a plurality of hydroxyl groups may be bonded as in vitamin C, and also in the case where vitamin C is bonded to hydroxyl groups other than the conjugated pi electron system as in vitamin C. good. (d1) Compound Having a Hydroxyl Group Belonging to a Conjugate Pi Electron System Having a Cyclic Structure It is preferable that the compound having reducibility is a compound having reducibility. (d1) Compounds having a hydroxyl group belonging to a conjugated pi electron system having a cyclic structure include catechin, tannin, rutin, chlorogenic acid, ellagic acid, lignan, curcumin, oleocantal, oleuropein, resveratrol, tocopherol, ascorbic acid and the like And their derivatives. Among them, (d1-1) tocopherol derivative and (d1-2) ascorbic acid derivative are preferable because of high storage stability effect.

  The compounding quantity of the compound which has a hydroxyl group which belongs to the conjugated pi electron system which has said (d1) cyclic structure in the dental surface treatment agent composition of this invention is not specifically limited. In addition. When considering the storage stability of the dental surface treatment agent, it is 0.01 to 20% by weight, preferably 0.02 to 15% by weight, and more preferably 0.03 to 10% by weight in 100% by weight of the dental surface treatment agent . The long-term storage stability of the dental surface treatment agent can be obtained by setting the content in the above range.

  Examples of the (d1-1) tocopherol derivative in the dental surface treatment agent composition of the present invention include tocopherol, tocopherol phosphate, tocopherol acetate, tocopherol nicotinate, and tocopherol succinate.

  The compounding amount of the (d1-1) tocopherol derivative in the dental surface treatment agent composition of the present invention is limited to the range of 40 or less with respect to the transition metal compound 1 in the weight ratio to the (a1) transition metal compound. In addition. When the balance between the realization of the storage stability of the dental surface treatment agent and the adhesion of the dental resin cement is taken into consideration, the weight ratio of the transition metal compound contained in the dental surface treatment agent composition is set to 1. In such a case, the (d1-1) tocopherol derivative is 40 or less, preferably 30 or less, and more preferably 20 or less. By setting the content within the above range, it is possible to achieve both the realization of long-term storage stability of the dental surface treatment agent and the acquisition of adhesiveness with the dental resin cement.

  As the (d1-2) ascorbic acid derivative in the dental surface treatment agent composition of the present invention, ascorbic acid, dehydroascorbic acid, 3-O-ethyl-L-ascorbic acid, L-ascorbyl 2,6-dibutyrate, ascorbic acid Acid 2-sulfate disodium, 5,6-O-isopropylidene-L-ascorbic acid, L-ascorbyl 6-palmitate, L-ascorbyl stearic acid ester, L-ascorbyl dipalmitate ester, etc. .

  The compounding amount of the above (d1-2) ascorbic acid derivative in the dental surface treatment agent composition of the present invention is limited to the range of 40 or less weight ratio to the transition metal compound 1 with respect to the (a1) transition metal compound . In addition. When the balance between the realization of the storage stability of the dental surface treatment agent and the adhesion of the dental resin cement is taken into consideration, the weight ratio of the transition metal compound contained in the dental surface treatment agent composition is set to 1. When the (d1-2) ascorbic acid derivative is 40 or less, preferably 30 or less, more preferably 20 or less. By setting the content within the above range, it is possible to achieve both the realization of long-term storage stability of the dental surface treatment agent and the acquisition of adhesiveness with the dental resin cement.

  In the present invention, either (c1) a compound having one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule, or (d1) a compound having a hydroxyl group belonging to a conjugated pi electron system having a cyclic structure. Although the effects of the invention can be obtained by selecting and using, it is more preferable to use both in combination. Or (c1) a combination of a compound having one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule and a reducing agent other than (d2) and (d1), or (d1) a conjugated pi electron having a cyclic structure The effects of the invention can be achieved by a combination of a compound having a hydroxyl group belonging to the system and a chelating agent other than (c2) and (c1).

  (c2) As chelating agents other than (c1), edetate salts such as EDTA, 2Na, EDTA3Na, EDTA4Na (ethylenediaminetetraacetate); hydroxyethylethylenediamine triacetates such as HEDTA3Na; pentetrate (diethylenetriamine pentaacetate) Phytic acid; sodium oxalate; polypolyamino acids such as polyaspartic acid and polyglutamic acid; polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, hexametaphosphoric acid, phosphoric acid and salts thereof such as sodium salts thereof; citric acid, alanine, dihydroxyethyl glycine And salts such as gluconic acid, salicylic acid, succinic acid, malic acid, tartaric acid and sodium salts thereof.

  (d2) As a reducing agent other than (d1), an ergocalcic acid having primary carbon and tertiary carbon in a pi-electron conjugated system, and having a hydroxyl group in a ring structure constituting atom partially sharing the structure with the pi-electron conjugated system Examples thereof include vitamin D groups such as ferolol and cholecalciferol (which have an effect according to (d1)), glutathione containing sulfur atoms, and sodium sulfite.

The (e) polymerizable monomer used in the dental surface treatment agent composition of the present invention includes an acidic group-containing polymerizable monomer and an acidic group-free polymerizable monomer.
The acidic group-containing polymerizable monomer is a monomer containing at least one acidic group such as a carboxylic acid group, a phosphoric acid group, a sulfonic acid group and a phosphonic acid group in one molecule. Further, it is preferable that at least one radically polymerizable unsaturated group such as acryloyl group, methacryloyl group, styryl group, vinyl group and allyl group is contained in one molecule as the polymerizable group.

  Among the above acidic group-containing polymerizable monomers, those containing a carboxylic acid group include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids, and examples thereof include (meth) acrylic acid, maleic acid, P-vinylbenzoic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 2-methacryloyloxyethyl 3'-methacryloyloxy 2 '(3,4-dicarboxybenzoyloxy) propyl succinate (MTS) , 2-methacryloyloxyethyl hydrogen maleate, 1,4-di (meth) acryloyloxymethyl pyromellitic acid, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid, 4- (meth) acryloyl Oxymethyltrimellitic acid and its anhydride, -(Meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxy butyl trimellitic acid and its anhydride, 4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid and its anhydride 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, N, O-di (meth) acryloyl tyrosine, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N -(Meth) acryloyl p-aminobenzoic acid, N-(meth) acryloyl O-aminobenzoic acid, N-(meth) acryloyl 5- aminosalicylic acid, N-(meth) acryloyl 4- aminosalicylic acid, 2 or 3 or 4 -(Meth) acryloyloxybenzoic acid, 2-hydroxyethyl (meth) Addition product of acrylate and pyromellitic dianhydride, 2- (3,4-dicarboxybenzoyloxy) 1,3-di (meth) acryloyloxypropane, 4-[(2-hydroxy-3- (meth)) Acryloyloxypropyl) amino] phthalic acid, 3 or 4- [N-methyl N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid and the like can be mentioned. Among these, dicarboxylic acids are preferably used, and 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10), 2-methacryloyloxyethyl 3'-methacryloyloxy 2 '(3,4-dicarboxybenzoyloxy) Propyl succinate (MTS), 4-methacryloyloxyethyl trimellitic anhydride (4-META), 4-acryloyloxyethyl trimellitic acid (4-AET) and the like are more preferably used.

  Moreover, as a polymerizable monomer containing a phosphoric acid group, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl acid phosphate, 2 and 3- (meth) acryloyloxy Propyl acid phosphate, 4- (meth) acryloyl butyl acid phosphate, 6- (meth) acryloyl oxybutyl acid phosphate, 8- (meth) acryloyl oxydecyl acid phosphate, 10- (meth) acryloyl oxydecyl acid phosphate, 12- ( Meta) acryloyloxydodecyl acid phosphate, bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) Acryloyloxyethyl phenyl acid phosphate (Phenyl-P), may be mentioned 2- (meth) acryloyloxyethyl p- ethoxyphenyl acid phosphate and the like. The phosphate group in these compounds can be replaced by a thiophosphate group. Among these compounds, 2-methacryloxyethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl acid phosphate and the like are preferably used.

  Furthermore, as a polymerizable monomer containing a sulfone group, for example, 2-sulfoethyl (meth) acrylate, 2-methyl-2- (meth) acrylamidopropane sulfonic acid, 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, 1,1- Dimethyl-2-sulfoethyl (meth) acrylamide, 3-methoxy-1-sulfo-2-propyl (meth) acrylate and the like can be mentioned. Among these, 2-methyl-2- (meth) acrylamidopropane sulfonic acid is preferably used.

As an example of a typical phosphonic acid, vinyl phosphonic acid can be mentioned.
These acidic group-containing polymerizable monomers can be used as a mixture of two or more, if necessary.
Among the above-mentioned acidic group-containing polymerizable monomers, a polymerizable monomer containing a carboxylic acid group and a polymerizable monomer containing a phosphoric acid group are preferable because they are excellent in adhesiveness to tooth substance, and both of them are more preferable. It is more preferable to combine them.

  Moreover, the acidic group non-containing polymerizable monomer is preferably a so-called crosslinking monomer having at least two, preferably 2 to 4 radically polymerizable groups (preferably acryloyl and methacryloyl groups). is there. Suitable examples include 1,6-bis [2-methacryloyloxyethoxycarbonylamino] -2,4,4-trimethylhexane (UDMA), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), dimethacrylate Acid polyethylene glycol (eg, PEG-400-dimethacrylate), 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) -phenyl] propane (bis-GMA), 1,6-bis [2 -Acryloyl-oxyethoxycarbonyl-amino] -2,4,4-trimethylhexane, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate (eg, PEG-400-diacrylate), trimeta Methylol trimethylolpropane, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, propoxylated bisphenol-A-dimethacrylate and butanediol dimethacrylate, butanediol diacrylate, dimethacrylate 1, 10-decanediol (D3MA), 1,10-decanediol diacrylate, 1,12-dodecanediol dimethacrylate and 1,12-dodecanediol diacrylate (these are (meth) acrylic acid and the corresponding diol or (Obtained by transesterification with a polyol). As acid group-containing polymerizable monomers, hydrolysis resistant crosslinking monomers are also suitable, for example, urethanes of 2-hydroxyethyl methacrylate and diisocyanates (for example, 2,2,4-trimethylhexamethylene diisocyanate and Isophorone diisocyanate); crosslinkable pyrrolidone (eg, 1,6-bis (3-vinyl-2-pyrrolidonyl) hexane); commercially available bisacrylamide or bis (meth) acrylamide (eg, methylenebisacrylamide, ethylenebisacrylamide) N, N'-diethyl-1,3-bis (acrylamido) propane, 1,3-bis (methacrylamido) propane, 1,4-bis (acrylamido) butane and 1,4-bis (acryloyl) piperazine ,They are, A diamine to react with strong (meth) may be synthesized by reaction with acrylic acid chloride).

  The compounding quantity of said (e) polymerizable monomer in the dental surface treatment agent composition of this invention is not specifically limited. In consideration of adhesion to the dental resin cement, it is 1 to 70% by weight, preferably 3 to 60% by weight, and more preferably 5 to 50% by weight in 100% by weight of the dental surface treatment agent. is there. By setting the content in the above-mentioned range, it is possible to obtain particularly excellent adhesive strength to the dental resin cement.

  In the case where the acid group-containing polymerizable monomer is contained in 100% by weight of the polymerizable monomer (e), the content ratio is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, and still more preferably Is 10 to 20% by weight. When adhesion to the dental resin cement is taken into consideration, demineralization of the tooth surface is insufficient when the value is below the lower limit of the above numerical range, and when the upper limit is exceeded, the tooth surface is overdeashed, Any of them is not preferable because it causes a decrease in adhesion.

  (e) When 100% by weight of the polymerizable monomer contains an acid group-free polyfunctional polymerizable monomer, its content ratio is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, and further preferably Preferably, it is 10 to 20% by weight. Below the lower limit of the above numerical range, the polymerizability becomes insufficient, and when the upper limit is exceeded, sufficient solubility can not be obtained due to excessive addition of the monomers, and each component precipitates. It is not preferable.

  The water-soluble organic solvent (f) in the dental surface treatment agent composition of the present invention is an alcohol such as methanol, ethanol or propanol; ethers such as dimethoxyethane, 1,2-dimethoxyethane, tetrahydrofuran (THF) and dioxane Ketones such as acetone and methyl ethyl ketone; sulfoxides such as N, N-dimethyl sulfoxide (DMSO); and amides such as N, N-dimethylformamide (DMF).

  The compounding quantity of the said (f) water-soluble organic solvent in the dental surface treatment agent composition of this invention is not specifically limited. In addition. When considering the solubility of the surface treatment agent-containing component and the adhesion to the dental resin cement, it is 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 100% by weight of the dental surface treatment agent. Is 5 to 30% by weight. By setting the content in the above range, it is possible to achieve both the realization of the solubility of the surface treatment agent-containing component and the acquisition of excellent adhesion to the dental resin cement.

  As a polymerization initiator (g) in the dental surface treatment agent composition used in the present invention, a polymerization initiator is blended in order to polymerize a radically polymerizable monomer. As a polymerization initiator, both a photoinitiator and a chemical polymerization initiator can be used. In addition, two or more of these polymerization initiators can be used in combination. Among these, as the photopolymerization initiator, known ones can be used without any limitation. Representative photopolymerization initiators include combinations of α-diketones and secondary amines, combinations of acyl phosphine oxides, acyl phosphine oxides and secondary amines, combinations of thioxanthones and secondary amines , combinations of α-amino acetophenones and secondary amines, combinations of aryl borates and photoacid generators, and the like. On the other hand, as a chemical polymerization initiator, it is possible to use any known one which is composed of two or more components and all components are mixed immediately before use to generate a polymerization active species at around room temperature. For example, organic peroxides / amines, organic peroxides / amines / organic sulfinic acids, organic peroxides / amines / aryl borates, aryl borates / acidic compounds, and barbituric acid derivatives / copper compounds / What consists of various combinations, such as a halogen compound, is mentioned.

  The compounding quantity of said (g) polymerization initiator in the dental surface treatment agent composition of this invention is not specifically limited. In addition. When the adhesiveness with the dental resin cement is taken into consideration, it is 0.01 to 10% by weight, preferably 0.03 to 5% by weight, and more preferably 0.05 to 3% by weight in 100% by weight of the dental surface treatment agent. By setting the content in the above-mentioned range, it is possible to obtain particularly excellent adhesive strength to the dental resin cement.

  As the thickener (h) used in the present invention, conventionally known thickeners can be used. For example, the polymer compound soluble in the dental surface treatment agent of the present invention can be dissolved and thickened, or the filler can be dispersed and thickened.

  As the above-mentioned polymer compound, conventionally known polymer compounds which can be dissolved in the dental pretreatment agent of the present invention can be appropriately selected and used in consideration of the thickening effect and storage stability. As such a polymer compound, an organic solvent is further added to the dental pre-treatment agent of the present invention, and polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate and polybutyl methacrylate. It is possible to increase the viscosity by dissolving a non-water-soluble polymer such as polyvinyl acetate or the like, but a method of dissolving a water-soluble polymer and thickening it is more preferable because a high thickening effect can be obtained.

  As such a water-soluble polymer, conventionally known polymers can be used without limitation as long as they are water-soluble. Examples of the cationic water-soluble polymer include water-soluble polymers containing polyethyleneimine, polyallylamine, polyvinylamine, dimethylaminoethyl dextran, imidazole group and the like. Examples of anionic water-soluble polymers include xanthan gum, carrageenan, sodium alginate, gum arabic, pectin and carboxyvinyl polymers, as well as polysaccharides such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparan sulfate and salts thereof Etc. can be mentioned. Examples of nonionic water-soluble polymers include cellulose lower alkyl ether compounds such as methyl cellulose, hydroxymethyl cellulose and hydroxypropyl cellulose, vinyl compounds such as polyvinyl pyrrolidone and polyvinyl alcohol, polysaccharides such as pullulan and starch, and derivatives thereof, polyglucosyl Polyacrylamide such as oxyethyl methacrylate, polyethylene oxide, or polyoxyalkylene glycol such as polyoxyethylene glycol, polyoxypropylene glycol, block copolymer of polyoxyethylene glycol and polyoxypropylene glycol, and the like can be mentioned.

  The weight average molecular weight and the molecular weight distribution of the polymer compound described above are not particularly limited. In addition, not only one type of polymer used as a thickener may be used, but also two or more types may be mixed and used.

  Moreover, it can be used as a thickener by dispersing the filler in the dental surface treatment agent of the present invention. Fillers used for dental applications are generally classified into organic fillers, inorganic fillers and organic-inorganic composite fillers. The material of the organic filler includes, for example, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene , Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc., which may be used alone or in combination of two or more. It can be used as a mixture of The shape of the organic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.

  Materials of the inorganic filler include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. . These may also be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.

  The organic-inorganic composite filler is obtained by adding a monomer compound to the above-described inorganic filler in advance, forming a paste, polymerizing and then pulverizing. As the organic-inorganic composite filler, for example, a TMPT filler (a compound obtained by mixing and polymerizing trimethylolpropane methacrylate and a silica filler and then grinding) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.

  The compounding quantity of the said (h) thickener in the dental surface treatment agent composition of this invention is not specifically limited. In addition. When the adhesiveness with a resin cement is considered, it is 0.01 to 30% by weight, preferably 0.03 to 20% by weight, and more preferably 0.05 to 10% by weight in 100% by weight of the dental surface treatment agent. By setting the content in the above range, it is possible to obtain particularly excellent adhesive strength to resin cement.

Furthermore, specific examples of other components that may be added to the dental surface treatment agent composition of the present invention include polymerization inhibitors, pigments, dyes and the like.
As a polymerization inhibitor, hydroquinone monomethyl ether, hydroquinone, 4-tert-butylphenol and the like can be added.
As the pigment and the dye, known dyes and pigments can be blended in the dental curable composition or the dental surface treatment composition.

  The dental surface treatment agent composition formulated in such a composition is excellent in the storage stability, and when the composition is dropped for 50 days after storage at 45 ° C., oxidation of the transition metal component occurs. It exhibits a property substantially free of coloring or gelation that is the cause. Specifically, a complex is formed by the coordination bond between the transition metal and the phosphoric acid group of the compound containing the phosphoric acid group or the alcoholic hydroxyl group of the compound containing the alcoholic hydroxyl group, thereby stabilizing the transition metal. It is possible to prevent oxidation by doing. Under the present circumstances, since the dental surface treating agent of this invention is a composition containing water, in order to maintain water solubility after complex formation, the compound ((c1) in one molecule which contains a hydroxyl group in the molecule It is considered to be preferable to use a compound having one or more phosphoric acid groups and one or more alcoholic hydroxyl groups. Further, by adding a compound having a hydroxyl group belonging to a conjugated pi electron system having a (d1) cyclic structure, it can be expected that the present compound functions as an antioxidant for the transition metal component.

  On the other hand, in a dental surface treatment agent composition comprising a mixture containing (a1) a transition metal compound and (b) water, a composition other than the present invention ((c1) a phosphoric acid group and an alcoholic hydroxyl group in one molecule) Or (d1) compounds prepared by using a compound having one or more groups and / or a compound having a hydroxyl group belonging to a conjugated pi electron system having a cyclic structure (d1) are already colored or gelled, or Since it is in a state of being easily colored and gelled, when stored at 45 ° C. for 50 days, the coloring due to the oxidation of the transition metal component is remarkably observed, or the gelation results in that it can not be dropped. Therefore, the dental surface treatment composition of the above composition, which is substantially free of oxidation of the transition metal component, is thus created for the first time according to the present invention, and the present invention provides such a dental surface treatment. An agent composition is also provided.

  Here, the state in which there is substantially no coloration caused by the oxidation of the transition metal component is most preferably a state in which there is no change in color tone in the composition by visual observation. In the present invention, a material that does not affect the use as a dental surface treatment agent and in which a slight color change that causes no cosmetic problems occurs is accepted as a state in which the color is not substantially changed. Ru.

  In the confirmation test (storage stability evaluation test) of the above-mentioned dental surface treatment agent hard to be colored, the storage period carried out at 45 ° C. for 50 days is about room temperature storage of the dental surface treatment agent composition at 25 ° C. It corresponds to storage for 2 years, and the stable storage over this long term demonstrates the practicability of this dental surface treatment agent composition.

  The purpose of use of the dental surface treatment agent composition produced by the composition of the present invention is not particularly limited, but various dental prostheses such as resin, ceramic, metal and the like, and (meth) acrylate-based adhesive of tooth substance Particularly preferred are primer compositions used to pretreat dentin, especially dentin, prior to use and adhesion.

  As the (meth) acrylate adhesive described above, a composition containing a radical polymerizable monomer such as a (meth) acrylate monomer as a main component and containing a polymerization initiator is known for dental use. Any adhesive may be used. As such a dental adhesive, typically, there is a resin cement for dental use and the like.

  Specifically, as the radical polymerizable monomer, the (e) polymerizable monomer described in the dental surface treatment agent composition of the present invention is mainly used. Moreover, as the polymerization initiator, the photopolymerization initiator, the chemical polymerization initiator, or the thermal polymerization of an amount effective for curing the polymerization initiator described in (g) above of the dental surface treatment agent composition of the present invention An initiator is blended. For example, the dental adhesive as described in Unexamined-Japanese-Patent No. 1996-73816, Unexamined-Japanese-Patent No. WO2008 / 140103 etc. is mentioned.

Such a dental adhesive is usually in the form of an uncured paste and is cured through photopolymerization, chemical polymerization and the like, and is used for bonding dental prostheses and tooth material.
The dental surface treatment agent composition of the present invention is preferably used to pretreat the dentin and to bond the various prostheses to the dentin using the (meth) acrylate dental resin cement as described above.

  Specifically, the acidic group-containing polymerizable monomer, the polyfunctional polymerizable monomer having no acidic group, or the single monomer having no acidic group described as the blending component of the surface treatment agent composition of the present invention It is a curable composition which has (meth) acrylate type monomers, such as a functional polymerizable monomer, as a main component, and contains a photoinitiator and a chemical polymerization initiator. In addition, in many cases where mechanical strength is required, in such a case, an inorganic filler similar to that described as the compounding component of the dental composite material is contained in an amount of about 25 to 75% by mass. It is preferred to use.

  Specific examples of the above-mentioned polymerization initiator include an α-diketone such as camphor quinone and a tertiary amine such as ethyl dimethylaminobenzoate and a tertiary amine such as N, N-dimethylaminoethyl methacrylate as a photopolymerization initiator. -A dye comprising a diketone / tertiary amine polymerization initiator, a pigment such as coumarin, a photoacid generator such as trichloromethyl group-substituted s-triazine, and an aryl borate compound such as tetraphenylborate / amine salt / photoacid generation Agent / aryl borate compound photopolymerization initiator can be mentioned. Moreover, as a chemical polymerization initiator, in addition to a peroxide / amine type polymerization initiator comprising a peroxide such as benzoyl peroxide and a tertiary amine such as N, N-diethanol-p-toluidine, an acid polymerization initiator Polymerization initiator consisting of compound / aryl borate compound; polymerization initiator consisting of acidic compound / aryl borate compound / metal complex; polymerization initiator consisting of acidic compound / aryl borate compound / metal complex / organic peroxide; part of tributylborane Examples thereof include alkyl metal compounds such as oxides; and barbituric acid initiators such as n-butyl barbituric acid / copper chloride.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples.
The dental surface treatment composition of Examples 1 to 4 having the composition shown below was prepared as follows. All values are by weight (parts by weight) unless otherwise stated.
[(a1) transition metal compound]
Ferrous chloride tetrahydrate
[(b) water]
Distilled water
[(c1) a compound containing one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule]
Glycerophosphate disodium tetrahydrate
[(d1) Compound Having Hydroxyl Group Belonging to Conjugate Pi Electron System Having a Cyclic Structure]
± -α-tocopherol ascorbic acid
[(e) polymerizable monomer]
4-META
2-Hydroxyethyl methacrylate (HEMA)
UDMA
[(f) Water-soluble organic solvent]
acetone
[Polymerization inhibitor]
Dibutylhydroxytoluene (BHT)

(Adjustment of Examples 1 to 4 and Comparative Example 1)
The raw materials shown in Table 1 were mixed at normal temperature (25 ° C.) to prepare a homogeneous solution. The solution was prepared in a glass sample bottle with a volume of 100 ml. Then, it was filled in a light-shielding resin-made closed container and used for evaluation of adhesion performance and evaluation of heat stability performance.

(Evaluation of adhesion performance)
In the present invention, the adhesion performance is evaluated as follows unless otherwise specified.
As an example of the adhesion test method, bovine dentin is ground to a water-resistant emery paper No. 180 under water injection and finger pressure to obtain a smooth surface, and then compressed air is blown to remove water. The bonding area was defined on the ground surface thus formed to be 4.8 mm in diameter.

  The dental surface treatment agent composition of each of the examples and comparative examples described in Table 1 was applied to this prescribed surface with a sponge and left for 20 seconds, and then compressed air was sprayed for about 5 seconds. Thereafter, a dental resin cement was applied, and the acrylic cylinder was crimped for 5 seconds under finger pressure.

  After curing by chemical polymerization (TBB, BPO) and photopolymerization (camphor quinone), in order to confirm the compatibility of the dental resin cement containing various polymerization initiators with the dental surface treatment agent composition according to the present invention The evaluation of the adhesion performance of Specifically, as an example of a dental resin cement used for adhesive performance evaluation, a super bond (manufactured by Sun Medical) containing TBB as a polymerization initiator and SEcure (manufactured by Sun Medical) containing BPO and camphor quinone were used. .

  The Superbond and SEcure were mixed, and then placed on a specified surface, and the acrylic cylinder was pressed under finger pressure for 5 seconds, and then allowed to stand at room temperature for 1 hour (chemical polymerization). In addition, the components of SEcure are kneaded by the same method, mounted on the specified surface, and after pressing the acrylic cylinder with finger pressure for 5 seconds, it is polymerized by radiation (20 seconds) with the dental polymerization lamp (Morita) (Photopolymerization).

  After applying thermal stimuli of 5 ° C. and 55 ° C. 5,000 times to each test body, a tensile test was conducted at a crosshead speed of 2 mm / min to calculate the adhesive strength. In this test method, it can be judged that the dentin tensile bond strength is 5.0 MPa or more and that it is established as a dental pretreatment agent used for a dental resin cement.

(Evaluation of heat stability performance)
In the present invention, the evaluation of the thermal stability is carried out as follows unless otherwise specified.
Each of the primer composition prepared in each example and comparative example was stored at 45 ° C. for 50 days. Subsequently, the degree of coloring of each solution was examined by measuring the color difference of the above-mentioned primer composition using a color difference meter (manufactured by Konica Minolta).
The results of the adhesive performance evaluation and the thermal stability evaluation of Examples 1 to 4 and Comparative Example 1 are shown in Table 1.

  From the results of Table 1, it is considered that the compositions of the respective Examples and Comparative Examples sufficiently retain the performance as a dental surface treatment agent with respect to adhesion to a dental material using a dental resin cement. In addition, since no difference was observed in tooth adhesion performance between the compositions of the respective Examples and Comparative Examples, a compound having one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule and a cyclic structure were found. It was shown that there is no influence such as adhesion inhibition by the compound having a hydroxyl group belonging to the conjugated pi electron system.

  The storage stability evaluation test of the primer composition prepared above was carried out, and after storage at 45 ° C. for 50 days, evaluation with a color difference meter is “a *: −0.55, b *: 0.85” in Example 1, Example 2, "a *: -0.35, b *: 0.74", Example 3 "a *: -0.37, b *: 0.73", Example 4 "a *: -0.31, b *:-0.19", In Comparative Example 1, "a *: 1.53, b *: 4.25".

  As apparent from comparison of the results of Examples 1 to 3 and Comparative Example 1, the oxidation of iron in Examples 1 to 3 containing disodium glycerophosphate and (±) -α-tocopherol or ascorbic acid, respectively, Since the value which shows the red (a *) and yellow (b *) which caused B. was lower than the comparative example 1, coloring property was suppressed. Furthermore, for Example 4 in which both disodium glycerophosphate and (±) -α-tocopherol were contained, Example 1, Example 2 in which each of them was contained alone, and ascorbic acid were contained alone. The result that color resistance is higher than Example 3 was obtained.

  The present invention provides a surface treatment composition that can be stably stored over a long period of time. The dental surface treating agent composition of the present invention is a dental dental treating agent considering the applicability to various dental surface treating agents such as bonding agent, primer, coating agent, cement, backing, covering agent, sealer, sealant, etc. Very useful in the field.

Claims (10)

(c1) glycerophosphoric acid or its sodium salt as a compound containing (a1) a transition metal compound, (b) water, and (c1) one or more phosphate group and one or more alcoholic hydroxyl groups in one molecule Dental surface treatment agent composition characterized by containing. (c1-1) glycerophosphoric acid or a sodium salt thereof as a compound containing (a1) a transition metal compound, (b) water, and (c1) one or more of a phosphoric acid group and an alcoholic hydroxyl group in one molecule (D1) A dental surface treatment agent composition comprising (d1-1) ascorbic acid and / or tocopherol as a compound having a hydroxyl group belonging to a conjugated pi electron system having a cyclic structure.   The dental surface treatment agent composition according to claim 1 or 2, wherein the (a1) transition metal compound is a compound consisting of (a1-1) iron and / or copper. The dental surface treatment agent according to any one of claims 1 to 3, wherein the weight ratio of the (c1-1) glycerophosphoric acid or the sodium salt thereof is 40 or less with respect to the (a1) transition metal compound 1. Composition. The dental surface treatment agent composition according to claim 2 or 3 , wherein the (d1-1) ascorbic acid and / or tocopherol is in a range of 40 or less with respect to the (a1) transition metal compound 1 in a weight ratio. The (c1-1) glycerophosphoric acid or its sodium salt, and the (d1-1) ascorbic acid and / or tocopherol are each independently selected from the group consisting of
The dental surface treatment agent composition according to claim 2 or 3 , wherein the weight ratio is 40 or less with respect to the (a1) transition metal compound 1.   The dental surface treatment agent composition according to any one of claims 1 to 6, further comprising (e) a polymerizable monomer.   The dental surface treatment agent composition according to any one of claims 1 to 7, further comprising (f) a water-soluble organic solvent.   The dental surface treatment agent composition according to any one of claims 1 to 8, further comprising (g) a polymerization initiator.   The dental surface treatment agent composition according to any one of claims 1 to 9, further comprising (h) a thickener.