JP2010215573A - One-package dental composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-package dental composition enabling easy determination of an end point of air blow. <P>SOLUTION: The one-package dental composition contains (A) a solvent, (B) an acidic compound and (C) a coloring matter, and changes its color by evaporating the solvent (A). Preferably, the dental composition includes a color difference ΔE<SP>*</SP>of ≥3 before and after evaporating the solvent (A) by air blow. The content of the solvent (A) is preferably 5-70 mass% in the dental composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a one-component dental composition containing a solvent and suitable for a one-component dental bonding material, a one-component dental primer, a one-component dental coating material, and the like.

  One-component dental composition containing a solvent used in one-component dental bonding materials, one-component dental primers, one-component dental coating materials, etc. is used in clinical practice by evaporating the solvent by air blowing. Is done. However, when the air blow is insufficient and the solvent remains, clinical problems such as a decrease in adhesive strength occur. This problem is addressed by doctors by blowing air for a sufficient amount of time, but there is a problem that the end point of air blow is difficult to understand.

  As a method for discriminating the end of operation during dental treatment, Patent Document 1 discloses that a surface of a dental structure is wetted with a liquid containing an acid-sensitive dye and water, and an etching composition, a self-etching adhesive, an adhesive Disclosed is a method of applying an acidic material, such as an adhesive composition, to produce a visually observable color change in a portion of the applied dental structure surface.

  Patent Document 2 discloses an adhesive for use in an oral environment, which includes a filler, a curable resin, a curing agent, and a colorant, has an initial color before exposure to actinic radiation, and a chemical An adhesive is disclosed having a final color following exposure to radiation, wherein the initial color is different from the final color.

  Patent Document 3 includes a radical polymerizable monomer and a photopolymerization initiator, the photopolymerization initiator is composed of an α-diketone and a specific dye, and the color tone of the dye is decolorized by photocuring. A photopolymerizable color-changing composition is disclosed.

  However, these are technologies for determining the end of application of an acidic material to a desired position and technologies for determining the end of photocuring, and at present, no technology for determining the end of air blow has been developed.

Special table 2008-505924 Japanese translation of PCT publication No. 2004-510996 JP-A-2-245003

  An object of the present invention is to provide a one-pack type dental composition that can easily determine the end point of air blow.

  The present invention that has achieved the above object includes a solvent (A), an acidic compound (B), and a pigment (C), and a one-pack type dental composition that changes color when the solvent (A) is evaporated. It is.

In the dental composition, when the solvent (A) is evaporated by air blow, the color difference ΔE ^* before and after the evaporation of the solvent (A) is preferably 3 or more. It is preferable that content of the said solvent (A) is 5-70 mass% in a dental composition. In one suitable embodiment of the said dental composition, content of the said solvent (A) is 5-70 mass% in a dental composition, The content is 3 mass of the said solvent (A). %, The color difference ΔE ^* before and after the evaporation of the solvent (A) is 3 or more.

  The dye (C) is preferably a compound having a color change range at a pH of 0.1 to 5.0. The acidic compound (B) is preferably a polymerizable monomer having an acidic group.

  The present invention is also a bonding material using the above one-component dental composition.

  According to the present invention, a one-pack type dental composition that can easily determine the end point of air blow is provided. By using the one-component dental composition of the present invention for dental treatment, an air blowing operation can be performed reliably and efficiently.

  As a result of intensive studies by the present inventors, it has been found that the end point of air blow can be visually determined by blending a specific pigment into a one-component dental composition containing a solvent. Specifically, the basic principle of the present invention is that when a one-component dental composition containing an acidic compound and a solvent is air blown to evaporate the solvent, the concentration of the acidic compound is increased. Although the pH of the composition is lowered, by blending a dye that changes color depending on the pH into the one-pack type dental composition, the dye is discolored using the pH change accompanying the progress of air blow, and the end point of air blow is determined. It is to inform.

Solvent (A)
As the solvent (A), water, an organic solvent, and a mixed solvent thereof can be used. As an organic solvent, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, acetone, tetrahydrofuran, diethyl ether, diisopropyl ether, 1,4-dioxane, methyl ethyl ketone, pentane, hexane , Toluene, chloroform, ethyl acetate, butyl acetate, and the like. Among these, the organic solvent is preferably a water-soluble organic solvent in consideration of both safety to the living body and ease of removal based on volatility. Specifically, ethanol, 2-propanol, 2 -Methyl-2-propanol, acetone, and tetrahydrofuran are preferably used.

  Although there is no restriction | limiting in particular as content of a solvent (A) as long as a dental material can be comprised, 5-70 mass% is preferable in a dental composition, and 5-50 mass% is preferable. When the content of the solvent (A) exceeds 70% by mass, the time required for air blowing becomes long, and the fluidity of the dental composition becomes too high, which may hinder the air blowing operation. On the other hand, when the content of the solvent (A) is less than 5% by mass, the dental composition may not easily penetrate into the dentin collagen layer, and a sufficient pH change may not occur before and after solvent evaporation.

  Since the solvent (A) should ionize the acidic compound (B), the solvent (A) is preferably a polar solvent, and the dental composition can easily penetrate into the collagen layer. It is preferable that water is included. It is preferable that the water does not contain impurities that have an adverse effect, and distilled water or ion exchange water is preferable. As content of water, 0.1-80 mass% is preferable in a solvent (A), and 1-60 mass% is more preferable.

Acidic compound (B)
The acidic compound (B) has a function of etching the tooth surface in order to strengthen the adhesion between the dental composition and the tooth substance. When the dental composition contains the acidic compound (B), a one-pack type dental material can be constituted. The acidic compound is not particularly limited as long as it can etch the tooth surface (particularly the dentin surface). For example, hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, formic acid, trifluoroacetic acid, phosphoric acid, pyrroline Acid, polyphosphoric acid, sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, a polymerizable monomer (D) having an acidic group, and the like can be used. These can be used alone or in combination of two or more. The dental composition containing the polymerizable monomer (D) having an acidic group does not become a polymerization inhibitor because the polymerizable monomer (D) itself having an acidic group has a polymerizable group, and has an adhesive performance. This is advantageous. Moreover, the polymerizable monomer (D) which has an acidic group can provide a primer function to a dental composition.

  The polymerizable monomer (D) having an acidic group can be used alone or in combination of two or more. The polymerizable monomer (D) having an acidic group is not particularly limited, but a monofunctional polymerizable monomer having one carboxyl group or its acid anhydride group in the molecule, and a plurality of monomers in the molecule. Monofunctional polymerizable monomer having carboxyl group or acid anhydride group thereof, monofunctional polymerizable monomer having phosphinyloxy group or phosphonooxy group in the molecule (monofunctional radical polymerizable phosphate ester And polyfunctional (bifunctional or higher) polymerizable monomers having these acidic groups.

  Examples of monofunctional polymerizable monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, and N- (meth) acryloyl asparagine. Acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, 6- (meth) acryloyloxyethyl naphthalene-1 , 2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) Acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, -(Meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4- Examples include aminosalicylic acid and the like and compounds obtained by converting the carboxyl group of these compounds into acid anhydride groups.

  Examples of monofunctional polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyl Oxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl -3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, 4- (2- (meth) (Acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimellitate, 4 (Meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 6- (meta ) Acrylyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl -1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 13- (meth) Acryloyloxytridecane-1,1-dicarboxylic acid, 1 - (meth) acrylamide undecanoic 1,1-dicarboxylic acid.

  Examples of monofunctional polymerizable monomers having a phosphinyloxy group or phosphonooxy group in the molecule (sometimes referred to as monofunctional radical polymerizable phosphate esters) include 2- (meth) acryloyloxyethyl Dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2- (Meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acrylamidoethyl dihydrogen phosphate and the like.

  Other monofunctional polymerizable monomers having an acidic group such as 2- (meth) acrylamido-2-methylpropanesulfonic acid, 10-sulfodecyl (meth) acrylate, etc. And other monomers.

  The polyfunctional polymerizable monomer is not particularly limited, but bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- (meth) acryloyloxydecyl) hydrogen phosphate, Bis {2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl} hydrogen phosphate, pentaerythritol tri (meth) acrylate halogenophosphate, dipentaerythritol penta (meth) acrylate halogenophosphate, etc. Are illustrated as preferred.

  As for content of an acidic compound (B), 0.1-50 mass% is preferable in a dental composition. When the content of the acidic compound (B) is less than 0.1% by mass, the acid etching effect or primer treatment effect (when using the polymerizable monomer (D)) may not be obtained, and more preferably 0. 0.5% by mass or more, and more preferably 1% by mass or more. On the other hand, when the compounding quantity of acidic compound (B) exceeds 50 mass%, sufficient sclerosis | hardenability may not be acquired and there exists a possibility of causing the fall of adhesive performance, More preferably, it is 40 mass% or less, More preferably Is 30% by mass or less.

Dye (C)
In the present invention, as the dye (C), one that changes color according to the pH change before and after the evaporation of the solvent (A) is used, and preferably a compound having a color change range at pH 0.1 to 5.0 is used. . Such a compound is not particularly limited as long as it has a color change range at pH 0.1 to 5.0, and is methyl orange, methyl yellow, metacresol purple, thymol blue, cresol red, picric acid, methyl violet, congo red, 2 , 4-dinitrophenol, 2,5-dinitrophenol, methanyl yellow, paraxylenol blue, acid orange, pentamethoxy red, benzyl orange, tetrabromophenol blue, bromochlorophenol blue, bromophenol blue, ethyl orange, bromocresol Green, acid red, lactoid, tetrabromophenolphthalein ethyl ester potassium salt and the like are exemplified as preferable ones. Among these, the pigment (C) having an appropriate color change range may be employed in consideration of the pH value before the solvent (A) transpiration of the dental composition and the pH value after the solvent (A) transpiration. .

  For example, a dye (C) that changes color at the pH value of the dental composition, which can be said to have sufficiently evaporated the solvent (A), may be used. In clinical practice, the solvent (A) is evaporated as much as possible by air blowing. However, in consideration of the burden on the patient, the solvent (A) is not so much that the surface of the applied dental composition is undulated by air blowing. ) Has been evaporated and the air blow has been completed, and a slight amount of the solvent (A) is contained. The smaller the solvent content, the better the adhesive strength of the dental composition. When the air blow is further advanced for a time that does not burden the patient, the content of the solvent (A) is 3% by mass or less. Reach up to. Therefore, in one preferred embodiment, the content of the solvent (A) that makes the surface of the applied dental composition no longer corrugated, the content of the solvent (A) is more than 3% by mass A dye (C) that changes color at the pH value of the dental composition when high is used. In this embodiment, if the color tone of the dental composition changes, the physician may end the air blow.

  In another embodiment, at the pH value of the solvent content dental composition just prior to the surface of the applied dental composition becoming wavy, in order to inform the physician that the air blow endpoint is near You may use the pigment | dye (C) which changes color. In this embodiment, if the color tone of the dental composition changes, the doctor recognizes that the end point of the air blow is close, and if the air blow is performed for about several seconds, the air blow can be terminated.

  In still another embodiment, two or more kinds of dyes having different pH change range and color tone may be used in combination so that the degree of evaporation of the solvent can be determined stepwise.

  In addition, when there is no pigment (C) having an appropriate color change range, the pH value of the dental composition can be adjusted by appropriately changing the type and content of the acidic compound (B).

  As for content of a pigment | dye (C), 0.000001-1 mass% is preferable in a dental composition. When the content of the dye (C) is less than 0.000001% by mass, it may be difficult to discriminate discoloration, more preferably 0.00005% by mass or more, and further preferably 0.0001% by mass or more. It is. On the other hand, when the content of the dye (C) exceeds 1% by mass, aesthetics due to coloring may be a problem, more preferably 0.05% by mass or less, and even more preferably 0.1% by mass. % Or less.

The one-pack type dental composition of the present invention is characterized in that the color tone changes when the solvent (A) is evaporated. Regarding the degree of change in color tone, when the solvent (A) is evaporated by air blowing, the color difference ΔE ^* before and after the evaporation of the solvent (A) is preferably 3 or more. This air blow is usually performed at room temperature (eg, 25 ° C.). In the present invention, the color difference refers to the expression ΔE ^* = ((L ₁ ^* −L) for two samples (color stimuli) using coordinates L ^* , a ^* , b ^* in the L ^* a ^* b ^* color system. _{^{2 *) 2 + (a 1}} * -a 2 *) 2 + (a 1 * -b 2 *) 2) 1/2
This means the color difference ΔE ^* (ΔE ^* ab) obtained more (see JIS Z8729).

When the change in color tone is confirmed by evaporating the solvent (A) by air blow, the reference for the content of the remaining solvent (A) is, for example, 3 mass%. Therefore, in a preferred embodiment of the one-pack type dental composition of the present invention, the content of the solvent (A) is 5 to 70% by mass in the dental composition, and the solvent (A) is contained in the dental composition. When the amount is 3% by mass, the color difference ΔE ^* before and after the transpiration of the solvent (A) is 3 or more.

  The one-component dental composition of the present invention may contain components other than the above (A) to (C) depending on the application. Components other than the above include a polymerizable monomer (E) having one polymerizable group and one or more hydroxyl groups (having no acidic group), a crosslinkable polymerizable monomer (F) ( Examples thereof include polymerizable monomer components such as those having no acidic group, polymerization initiator (G), polymerization accelerator (H), filler (I) and the like.

  The one-component dental composition of the present invention is configured to contain a polymerizable monomer in order to impart the necessary curability as a dental material. For that purpose, a polymerizable monomer (D) may be used for the acidic compound (B), a polymerizable monomer (E) having one polymerizable group and one or more hydroxyl groups, and a crosslinking agent. A polymerizable monomer such as a polymerizable monomer (F) may be blended. A plurality of types of polymerizable monomers can be used in combination.

Polymerizable monomer (E) having one polymerizable group and one or more hydroxyl groups
Since the polymerizable monomer (E) is highly hydrophilic and easily penetrates into the dentin collagen layer, when the dental composition of the present invention contains the polymerizable monomer (E), the primer function is Imparted and increased adhesive strength. The polymerizable group of the polymerizable monomer (E) is preferably a (meth) acryl group or a (meth) acrylamide group from the viewpoint of easy radical polymerization. The polymerizable monomer (E) is used as a component of the dental composition. However, since the oral cavity is a moist environment, there is a possibility that the polymerizable group may be detached due to hydrolysis or the like. In consideration of irritation to the living body of the detached polymerizable group, the polymerizable group is preferably a methacryl group or a methacrylamide group.

  The polymerizable monomer (E) is not particularly limited as long as it can be used for dental use, and can be used alone or in appropriate combination of two or more. Examples of the polymerizable monomer (E) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10 -Hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N -(Dihydroxyethyl) (meth) acrylamide and the like are mentioned. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meta) are preferred from the viewpoint of improving the penetration of dentin into the collagen layer. ) Acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate preferably, particularly preferably 2-hydroxyethyl methacrylate.

  Although the compounding quantity of the said polymerizable monomer (E) is not specifically limited, 1-90 mass% is preferable among all the polymerizable monomer components. A dental composition in which the blending amount of the polymerizable monomer (E) is in such a range has good penetration of dentin into the collagen layer and good adhesive strength. When the blending amount of the polymerizable monomer (E) is less than 1% by mass, the contribution of the polymerizable monomer (E) to the penetration of the dentin into the collagen layer may not be obtained, and the adhesive strength is low. May decrease. The blending amount of the polymerizable monomer (E) is more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more. On the other hand, when the compounding quantity of a polymerizable monomer (E) exceeds 90 mass%, there exists a possibility that sufficient sclerosis | hardenability may not be obtained but the mechanical strength of hardened | cured material may fall. For this reason, there exists a possibility that adhesive strength may fall. The blending amount of the polymerizable monomer (E) is more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

Crosslinkable polymerizable monomer (F)
When the dental composition of the present invention contains a crosslinkable polymerizable monomer (F), there are advantages such as an increase in adhesive strength.

  The crosslinkable polymerizable monomer (F) is not particularly limited as long as it can be used for dental use, and can be used alone or in combination of two or more. Although it does not specifically limit as a crosslinkable polymerizable monomer (F), An aromatic compound type bifunctional polymerizable monomer, an aliphatic compound type bifunctional polymerizable monomer, trifunctionality The above polymerizable monomers are exemplified.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane), 2,2-bis ( 4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentae) Xylphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2 -(4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) Propane, 1,4-bis (2- (meth) acryloyl Oxyethyl) pyromellitate and the like.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane and 2,2,4-trimethylhexamethylene Screw 2-carbamoyloxy-ethyl) dimethacrylate (commonly known as "UDMA"), and the like.

  Examples of tri- or higher functional polymerizable monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) Examples include bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate and 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

  Although the compounding quantity of a crosslinkable polymerizable monomer (F) is not specifically limited, 1-90 mass% is preferable in all the polymerizable monomer components. If the amount of the crosslinkable polymerizable monomer (F) is less than 1% by mass, sufficient adhesive strength may not be obtained, more preferably 2% by mass or more, and even more preferably 5%. It is at least mass%. On the other hand, when the blending amount of the crosslinkable polymerizable monomer (F) exceeds 90% by mass, there is a risk that the penetration of the composition into the collagen layer of the dentin becomes insufficient and high adhesive strength cannot be obtained. More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

Polymerization initiator (G)
When the dental composition of the present invention contains a polymerization initiator (G), curability is improved. The polymerization initiator (G) can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental applications are preferably used. In particular, polymerization initiators for photopolymerization and chemical polymerization are used singly or in appropriate combination of two or more.

  Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyls Examples include ether compounds and α-aminoketone compounds.

  Among the (bis) acylphosphine oxides used as the photopolymerization initiator, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi -(2,6-dimethylphenyl) phosphonate and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  The water-soluble acylphosphine oxides used as the photopolymerization initiator preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion, or ammonium ion in the acylphosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of the water-soluble acyl phosphine oxides include monomethyl acetyl phosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethyl benzoyl phosphonate / sodium, monomethyl (1-oxobutyl) phosphine. Phosphonate sodium, monomethyl (2-methyl-1-oxopropyl) phosphonate sodium, acetyl phosphonate sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxy Methoxyphosphinyl) -4-oxobutanoate sodium salt, methyl-4-oxophosphonobutanoate mononatrium salt, acetyl phenyl phosphinate Thorium salt, (1-oxopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphite Nate sodium, methyl (1,1-dimethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium Methyl-4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl- 1,3-dioxolan-2-yl) fu Sphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium Salt, acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-diethoxyethyl) methyl phosphonite sodium salt, methyl (2-methyloxathio) Lan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phos Finate sodium salt, (1-methoxyvinyl) methyl phosphinate sodium salt, ( 1-ethylthiovinyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) phosphinate sodium salt, methyl (2-methylperhydro-1,3 -Thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidine-2) -Yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl methyl phosphinate oxime, sodium oxalate, acetyl methyl phosphinate -O-benzyl oxime Sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate nato Um salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenylhydrazoneethyl) phosphinate sodium salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methylphosphine Finate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl Methyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate・ Dodecyl Anidine salt, (1,1-dimethoxypropyl) methylphosphinate-isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2, 4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl)- Methyl phosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt Etc. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of the thioxanthones or quaternary ammonium salts of thioxanthones used as the photopolymerization initiator include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H- Thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- ( 3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trime Ru-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals used as the photopolymerization initiator include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the α-diketone used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′- Examples thereof include oxybenzyl and acenaphthenequinone. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Examples of the coumarin compound used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 3-benzoyl-5. , 7-Dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) Coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscuc Marine, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl Nzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin , 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- ( 4-methoxybenzoyl) coumarin, 3- (4-nitrobe) Zoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- [ (3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxy) Coumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3 -(2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethi Ruamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3′-carbonylbis (7-dibutylaminocoumarin), 3 , 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3 6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2 , 3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, etc. 3109 JP, compounds described in JP-A-10-245525 can be cited.

  Among the above-mentioned coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

  Examples of the anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like.

  Examples of benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones used as the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, a dental composition having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

  Of the polymerization initiator (G), an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

  Examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

  Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1, 1,3,3-tetramethylbutyl hydroperoxide and the like.

  Examples of the diacyl peroxide used as the chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.

  Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  Peroxyketals used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, etc. Can be mentioned.

  Peroxyesters used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.

  Examples of the peroxydicarbonate used as the chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples include peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

  Among these organic peroxides, diacyl peroxide is preferably used from the comprehensive balance of safety, storage stability, and radical generating ability, and among them, benzoyl peroxide is particularly preferably used.

  Although the compounding quantity of a polymerization initiator (G) is not specifically limited, From viewpoints, such as sclerosis | hardenability of a dental composition, 0.001-30 mass% with respect to 100 mass% of whole quantity of a polymerizable monomer component. Is preferred. When the compounding quantity of a polymerization initiator (G) is less than 0.001 mass%, superposition | polymerization may not fully advance and there exists a possibility of causing the fall of adhesive force, More preferably, it is 0.05 mass% or more. On the other hand, when the blending amount of the polymerization initiator (G) exceeds 30% by mass, if the polymerization performance of the polymerization initiator itself is low, there is a possibility that sufficient adhesive strength may not be obtained, and further from the composition. Since precipitation may be caused, it is more preferably 20% by mass or less.

Polymerization accelerator (H)
When the dental composition of the present invention contains a polymerization accelerator (H), the curability is further improved. The combined use with the polymerization initiator (G) is particularly effective. As the polymerization accelerator (H), amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, Examples thereof include bisulfite and thiourea compounds.

  The amines used as the polymerization accelerator (H) are classified into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Amine and the like. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among these, N-methyldiethanolamine and triethanolamine are more preferably used.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (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, 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, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4- Examples include butyl dimethylaminobenzoate. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of the sulfinic acid and salts thereof used as the polymerization accelerator (H) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfine. Acid calcium, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylben Sulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid Examples include lithium, calcium 2,4,6-triisopropylbenzenesulfinate, and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable. .

  The borate compound used as the polymerization accelerator (H) is preferably an aryl borate compound. Specific examples of suitably used aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl ] Boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxy) Phenyl) boron, trialkyl (m-butyloxyphenyl) boron, Alkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) A) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinori Examples thereof include a nium salt and a butyl quinolinium salt.

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl. Boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and di Sodium salt, lithium salt, potassium salt of rualkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt butylquinolinium salt, etc. .

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri ( p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoal Rutri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl, n-octyl, n-dodecyl, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, A butyl quinolinium salt etc. are mentioned.

  Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron. Tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) ) Boron, Tetrakis (p-butylphenyl) boron, Tetrakis (m-butylphenyl) boron, Tetrakis (p-butyloxyphenyl) boron, Tetrakis (m-butyloxyphenyl) boron, Tetrakis (p-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-Butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetra Examples include methylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt.

  Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. These aryl borate compounds may be used alone or in combination of two or more.

  Examples of the barbituric acid derivative used as the polymerization accelerator (H) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, and 5-butyl. Barbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1 , 3-Dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3 -Dimethyl-5-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl -1-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methyl barbituric acid, 5-propyl barbituric acid, 1,5-diethyl barbituric acid, 1-ethyl-5-methylbarbi Tool acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1 -Cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and these (Especially alkali metals or alkaline earth metals are preferred) The salt of Luo barbiturates, e.g., sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

  Particularly preferred barbituric acid derivatives include 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, And sodium salts of these barbituric acids.

  Examples of the triazine compound used as the polymerization accelerator (H) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s- Lyazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy] -4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

  Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable from the viewpoint of polymerization activity, and 2-phenyl-4 is preferable from the viewpoint of storage stability. , 6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( Trichloromethyl) -s-triazine. The above triazine compounds may be used alone or in combination of two or more.

  As the copper compound used as the polymerization accelerator (H), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound used as the polymerization accelerator (H) include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. It is done. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound used as the polymerization accelerator (H) is preferably IV-valent and / or V-valent vanadium compounds. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003, such as phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V) The compound described in -96122 is mentioned.

  Examples of the halogen compound used as the polymerization accelerator (H) include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Are preferably used.

  Examples of aldehydes used as the polymerization accelerator (H) include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde, and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

  Examples of the thiol compound used as the polymerization accelerator (H) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Examples of the sulfite used as the polymerization accelerator (H) include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

  Examples of the bisulfite used as the polymerization accelerator (H) include sodium bisulfite and potassium bisulfite.

  Examples of the thiourea compound used as the polymerization accelerator (H) include 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′— Diethylthiourea, N, N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthio Examples include urea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like.

  Although the compounding quantity of a polymerization accelerator (H) is not specifically limited, From viewpoints, such as sclerosis | hardenability of a dental composition, 0.001-30 mass% with respect to 100 mass% of whole quantity of a polymerizable monomer component. Is preferred. When the blending amount of the polymerization accelerator (H) is less than 0.001% by mass, the polymerization does not proceed sufficiently and there is a possibility of causing a decrease in adhesive strength, and more preferably 0.05% by mass or more. On the other hand, when the blending amount of the polymerization accelerator (H) exceeds 30% by mass, if the polymerization performance of the polymerization initiator itself is low, there is a possibility that sufficient adhesive strength may not be obtained, and further from the composition. Since precipitation may be caused, it is more preferably 20% by mass or less.

Filler (I)
Depending on the embodiment, the dental composition of the present invention may further contain a filler (I). Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or in combination of two or more. Can be used as a mixture. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and 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 can also be used individually or in mixture of 2 or more types. The shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the inorganic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Examples of the shape of the inorganic filler include an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the composition, it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler is a particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. Is a filler having an average homogeneity of 0.6 or more divided by its maximum diameter. The average particle diameter of the spherical filler is preferably 0.1 to 5 μm. When the average particle size is less than 0.1 μm, the filling rate of the spherical filler in the composition is lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.

  In order to adjust the fluidity | liquidity of a composition, you may use the said inorganic filler, after surface-treating beforehand with well-known surface treatment agents, such as a silane coupling agent, as needed. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The organic-inorganic composite filler used in the present invention is obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, forming a paste, polymerizing, and pulverizing. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) 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. From the viewpoint of handling property and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  The compounding quantity of the filler (I) used for this invention is not specifically limited, 1-500 mass% is preferable with respect to 100 mass% of whole quantity of a polymerizable monomer component. Since the suitable compounding amount of the filler (I) varies greatly depending on the embodiment to be used, the filler according to each embodiment (in addition to the description of the specific embodiment of the dental composition of the present invention described later) A suitable blending amount of I) will be shown.

  In addition, the dental composition of the present invention contains a pH adjuster, a polymerization inhibitor, a UV absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired. Also good.

  Next, the usage form of the one-pack type dental composition of the present invention will be described. The one-part dental composition of the present invention is suitable for dental materials such as a one-part dental bonding material, one-part dental primer, and one-part dental coating material, which are air blown at the time of use. Can be used. Hereinafter, a configuration example of a one-component dental bonding material, a one-component dental primer, and a one-component dental coating material will be described.

One-part dental bonding material When the dental composition of the present invention is used for a one-part dental bonding material, for example, the dental composition is (A) 5 to 50% by mass in the dental composition, (B) (D) 0.1-50 mass%, (C) 0.000001-1 mass%, (E) 0-50 mass%, (F) 0-50 mass may be included. Alternatively, the dental composition is (A) 5 to 70% by mass, (B) (other than (D)) 0.1 to 50% by mass, (C) 0.000001 to 1% by mass in the dental composition, (E) 10-50 mass% and (F) 0-50 mass may be included. The dental composition further comprises (G) 0.001 to 30% by mass, (H) 0.001 to 30% by mass, and (I) 1 with respect to 100% by mass of the total amount of polymerizable monomer components. It is preferable to contain -20 mass%.

One-pack type dental primer When the dental composition of the present invention is used for a one-pack type dental primer, for example, the dental composition is (A) 5 to 70% by mass in the dental composition (B ) As (D) 0.1-50 mass%, (C) 0.000001-1 mass%, (E) 0-50 mass%, (F) 0-50 mass may be included. Alternatively, the dental composition is (A) 5 to 70% by mass, (B) (other than (D)) 0.1 to 50% by mass, (C) 0.000001 to 1% by mass in the dental composition, (E) 10-50 mass% and (F) 0-50 mass may be included. The dental composition further comprises (G) 0.001 to 30% by mass, (H) 0.001 to 30% by mass, and (I) 1 with respect to 100% by mass of the total amount of polymerizable monomer components. It is preferable to contain -20 mass%.

One-part dental coating material When the dental composition of the present invention is used for a one-part dental coating material, for example, the dental composition is (A) 5 to 50% by mass in the dental composition. (B) (D) 0.1-50 mass%, (C) 0.000001-1 mass%, (E) 0-50 mass%, (F) 0-50 mass may be included. Alternatively, the dental composition is (A) 5 to 70% by mass, (B) (other than (D)) 0.1 to 50% by mass, (C) 0.000001 to 1% by mass in the dental composition, (E) 10-50 mass% and (F) 0-50 mass may be included. The dental composition further comprises (G) 0.001 to 30% by mass, (H) 0.001 to 30% by mass, and (I) 1 with respect to 100% by mass of the total amount of polymerizable monomer components. It is preferable to contain -20 mass%.

  The one-pack type dental composition of the present invention can be used according to a known method. For example, the one-component dental composition of the present invention is applied to a target site according to a known method. Next, the solvent (A) is evaporated by air blowing. Since the present invention is a dental composition, air blow is preferably performed using a dental air syringe. The air blow pressure is preferably 0.001 to 1 MPa. If the air blow pressure is less than 0.001 MPa, the air blow is too weak and it may take too much time to evaporate the solvent, more preferably 0.02 MPa or more, and even more preferably 0.05 MPa or more. It is. On the other hand, when the air blow pressure exceeds 1 MPa, the air blow is too strong and it may be difficult to evaporate the solvent, more preferably 0.8 MPa or less, and even more preferably 0.5 MPa or less.

  In the present invention, when the solvent (A) is evaporated by air blow, the color tone of the dental composition changes. Therefore, the air blowing time may be determined based on a change in color tone, and varies depending on the air blowing pressure, the solvent content of the dental composition, etc., but is usually about 0.1 to 180 seconds.

  After air blowing, the polymerizable monomer may be polymerized and cured by light irradiation or the like, and a dental composite resin, dental cement, or the like may be further used depending on the treatment form.

  By using the one-component dental composition of the present invention for dental treatment, the end point of air blow can be easily determined, and the air blow operation can be performed efficiently and reliably.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.

(1) Preparation of one-component bonding material Each component was mixed at room temperature to prepare a one-component bonding material composition. The composition is shown in Table 1.

MDP: 10-methacryloyloxydecyl dihydrogen phosphate Bis-GMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane HEMA: 2-hydroxyethyl methacrylate BAPO: bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide CQ: camphorquinone JJA: 4-N, N-dimethylaminobenzoic acid ethyl ester TTA: triethanolamine BHT: Dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol)
R972: Inorganic filler, Nippon Aerosil "R972"

  Examples of the dye include methyl orange (Examples 1 and 2), methyl yellow (Examples 3 and 4), metacresol purple (Examples 5 and 6), thymol blue (Examples 7 and 8), and cresol red (Examples). 9,10) was used. Furthermore, the thing which did not add a pigment | dye was prepared as Comparative Examples 1 and 2.

(2) Color difference measurement Preparation of a color difference measurement sample was performed as follows. A cellophane seal on a glass plate and a donut-shaped metal ring with a hole having a diameter of 1 cm were sequentially installed. The one-component bonding material composition prepared above was poured into the hole with a dropper, and a cellophane seal and a glass plate were placed in this order. Finally, two glass plates were sandwiched between the clips and fixed. Thereafter, the sample prepared above was placed on a white reflectance standard (that is, a white background), and color measurement was performed. A color difference meter Σ90 (Nippon Denshoku Industries Co., Ltd. product) was used as the measuring device.

L ^* , a ^* , and b ^* color systems were used for color representation. The L ^* , a ^* , b ^* color system includes a positive X axis that displays red, a negative X axis that displays green, a positive Y axis that displays yellow, a negative Y axis that displays blue, and An XYZ three-dimensional color space having a Z axis with a starting point of 50 in the range from 0 (black) to 100 (white) is used as a reference.

Next, under light shielding, 0.5 g of the one-component bonding material composition was weighed into a plastic container, and air with an air pressure of 0.1 MPa was wiped for 10 seconds to evaporate the solvent. The solvent content of the obtained composition was 3% by mass, and color measurement was performed on this composition according to the method described above. From these results, ΔE ^* was determined. ΔE ^* is a calculation of the total color change in the three-dimensional color space, and is expressed by the following equation.
ΔE ^* = ((L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (a ₁ ^* −b ₂ ^* ) ² ) ^1/2
In the above formula, the subscript “1” indicates the state before air blow, and “2” indicates the state after air blow.

The one-component bonding material of the example, unlike the one-component bonding material of the comparative example, has a color difference ΔE ^* of 3 or more, and the change in color tone before and after transpiration by air blow can be easily confirmed visually. did it.

  The one-part dental composition of the present invention is suitable for dental materials such as a one-part dental bonding material, one-part dental primer, and one-part dental coating material, which are air blown at the time of use. It is.

Claims (7)

  A one-pack type dental composition comprising a solvent (A), an acidic compound (B), and a pigment (C), the color of which changes when the solvent (A) is evaporated. The one-pack type dental composition according to claim 1, wherein when the solvent (A) is evaporated by air blow, the color difference ΔE ^* before and after the evaporation of the solvent (A) is 3 or more.   The one-component dental composition according to claim 1 or 2, wherein the content of the solvent (A) is 5 to 70 mass% in the dental composition. When the content of the solvent (A) is 5 to 70% by mass in the dental composition and the solvent (A) is evaporated by air blow until the content becomes 3% by mass, the solvent The one-pack type dental composition according to claim 1, wherein the color difference ΔE ^* before and after the transpiration of (A) is 3 or more.   The one-pack type dental composition according to any one of claims 1 to 4, wherein the dye (C) is a compound having a color change range at a pH of 0.1 to 5.0.   The one-component dental composition according to any one of claims 1 to 5, wherein the acidic compound (B) is a polymerizable monomer having an acidic group.   A bonding material using the one-pack type dental composition according to claim 1.