JPH11139920A - Polymerization-curable composition for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of clearly discriminating both coated site and amount involved therein when applied to the teeth surface, with no developing any colored line at the margin part, and capable of seeing its sure curing on being irradiated with light. SOLUTION: This composition is obtained by compounding a photocurable composition with a coloring matter such as methylene blue or neutral red, wherein the photocurable composition comprises a radical-polymerizable monomer such as triethylene glycol dimethacrylate or 2-hydroxyethyl methacrylate and an α-diketone-based photopolymerization catalyst such as camphorquinone, while the coloring matter develops a color different from that of dentine when compound in the photocurable composition and also causes a color fading on being irradiated with light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable dental curable composition used as an adhesive for realizing high adhesive strength between a restorative material and a tooth material in the field of dental care when restoring a tooth.

[0002]

2. Description of the Related Art In recent years, restoration of tooth material damaged by dental caries and the like has been required to be an aesthetic restoration and a reliable restoration that does not induce secondary caries or dental pulp irritation.

[0003] As a method of performing aesthetic restoration, after removing caries, the tooth surface is pre-treated with an acidic aqueous solution, and the restoration material called a composite resin is bonded to the tooth using a bonding material. (Hereinafter, resin filling restoration). Resin restoration is not only aesthetic,
With the recent improvement in the performance of the pretreatment material and the bonding material, it has become possible to very strongly bond the dentin with the restorative material. For example, Japanese Patent Application Laid-Open No. 8-319209 discloses an adhesive system showing a high adhesive strength of 20 MPa or more to both dentin and enamel.

[0004] On the other hand, if the number of tooth defects is so large that resin filling cannot be repaired, a bridge, crown, onlay,
A prosthesis such as an inlay is mounted with an adhesive material called resin cement. However, it takes a long time to manufacture these prostheses, so that it takes a long time to remove the caries from the tooth material and put it on. During that time, it is necessary to protect the tooth material in some way. Furthermore, since the adhesiveness of the resin cement is not as high as that of the bonding material and there is a possibility of secondary caries due to poor adhesion, it is said that there is a need for some kind of dentin protection. Therefore, for these purposes, a method has been adopted in which a tooth material surface from which dental caries has been removed is immediately coated with a bonding material, and then a prosthesis is mounted with resin cement to reliably protect the tooth material (hereinafter, referred to as a method). Tooth surface coating method).

[0005] From the viewpoint of the above-mentioned reliable restoration, it is necessary to apply a bonding material to the entire exposed tooth surface from which dental caries has been removed and to securely cure the applied bonding material in both the tooth surface coating method and the resin filling restoration. is there.
Also, it is not preferable to form a pool of bonding material at the bottom of the cavity or at the corners, since this also prevents the production and mounting of a prosthesis having good compatibility. However, conventional bonding materials include α such as camphorquinone as a photopolymerization initiator.
-Due to the use of diketones, the color is transparent yellow, and when applied to the tooth surface which is also yellowish, the applied part and the amount of application are determined. There is a disadvantage that it is difficult. Furthermore, there was almost no change in appearance before and after curing, and it was difficult to determine whether or not curing was achieved by irradiating light reliably.

[0006]

As described above, at the time of application to the tooth surface, the applied portion and the applied amount can be clearly discriminated, and no colored line is formed in the margin portion. A bonding material that can be surely cured has not been known so far.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome the above technical problems, and as a result, have found that a dental bonding material composition comprising a radical polymerizable monomer and an α-diketone-based photopolymerization catalyst. Further, by blending a pigment that fades by light irradiation to the product, the applied portion and the applied amount can be clearly distinguished at the time of application to the tooth surface, and there is no formation of a colored line in the margin portion. As a result, the present invention has been found to be a bonding material that can be surely cured by light irradiation, and the present invention has been completed.

That is, the present invention provides a radical polymerizable monomer,
A dental curable composition for dental use, comprising an α-diketone-based photopolymerization catalyst and a dye that fades by light irradiation.

[0009] Since the dental polymerizable and curable composition of the present invention contains a dye that fades upon irradiation with light, it is easy to coat the coated part before curing by irradiation with light due to the difference in color from the tooth material. You can check. In addition, since the above-mentioned color is faded by light irradiation, the degree of curing by light irradiation can be easily grasped as a change in color, and the problem that a margin portion remains as a colored line does not occur.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The radically polymerizable monomer used in the present invention has at least one radically polymerizable unsaturated group in one molecule, and is capable of photopolymerization in the presence of an α-diketone photopolymerization catalyst. There is no particular limitation on the compound that can be polymerized and cured by irradiation, and a known compound can be used.

Specific examples of such radically polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, phenoxyethyl (meth) acrylate, isoborny Water-insoluble monofunctional non-acidic polymerizable monomers such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 2,4-dihydroxybutyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,3,4 -Trihydroxybutyl (meth) acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, diethylene glycol mono (meth) acrylate , Triethylene glycol Mono-functional non-acidic monomers containing a water-soluble hydroxyl group such as mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and pentaethylene glycol mono (meth) acrylate; amino alcohols such as N-methylol (meth) acrylamide (Meth) acrylamides, diacetone (meth) acrylamide, N- (meth)
Water-soluble monofunctional non-acidic polymerizable monomers such as acryloylmorpholine and N-vinylpyrrolidone, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, urethanediol di (meth) acrylate, glycerin-1,
3-di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Fats such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and N, N'-methylenebis (meth) acrylamide Aromatic polyfunctional polymerizable monomers, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane, , 2-bis (4 Methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypenta Ethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxyethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiene) Ethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2,2 Bis (4-methacryloyloxydipropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, and aromatic polyfunctional polymerizable monomers such as acrylates thereof, and (meth) Acrylic acid, 2- (meth) acryloyloxyethyl hydrogen malate, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxy-1,1 -Undecanedicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,
4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, N- (meth)
Carboxylic acid acidic group-containing polymerizable monomers such as acryloylglycine and N- (meth) acryloylaspartic acid;
2- (meth) acryloyloxyethylphenyl hydrogen phosphate, bis ((meth) acryloyloxyethyl) hydrogen phosphate,
(Meth) acryloyloxyethyl dihydrogen
Phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth)
Phosphoric acid group-containing polymerizable monomers such as acryloyloxyhexyl dihydrogen phosphate, phosphonic acid group-containing polymerizable monomers such as vinylphosphonic acid,
And 2- (meth) acrylamido-2-methylpropanesulfonic acid and other sulfonic acid acidic group-containing polymerizable monomers.

These polymerizable monomers may be used alone or in a combination of two or more. However, in consideration of tooth adhesion, operability, production cost, etc., a plurality of polymerizable monomers may be used. It is preferred to use the body in combination. Examples of such combinations include combinations of aliphatic polyfunctional polymerizable monomers and aromatic polyfunctional polymerizable monomers, and water-soluble hydroxyl-containing monofunctional non-acidic monomers. , A combination of aliphatic polyfunctional polymerizable monomers and aromatic polyfunctional polymerizable monomers, aliphatic polyfunctional polymerizable monomers, aromatic polyfunctional polymerizable Combination of monomers and carboxylic acid group-containing polymerizable monomers, water-soluble hydroxyl group-containing monofunctional non-acidic monomers, aliphatic polyfunctional polymerizable monomers, aromatic poly Combinations of functional polymerizable monomers and carboxylic acid acidic group-containing polymerizable monomers, aliphatic polyfunctional polymerizable monomers, aromatic polyfunctional polymerizable monomers and phosphorus Combination of acid acidic group-containing polymerizable monomers, water-soluble hydroxyl group-containing monofunctional non-acidic monomers, aliphatic polyfunctional polymerizable monomers, aromatic polyfunctional Polymerizable monomers and combinations phosphate acidic group-containing polymerizable monomers, a water-soluble hydroxyl group-containing monofunctional non-acidic monomers,
Aliphatic polyfunctional polymerizable monomers, aromatic polyfunctional polymerizable monomers, carboxylic acid acidic group-containing polymerizable monomers and phosphoric acid acidic group-containing polymerizable monomers Combinations are mentioned as suitable combinations. Above all, from the viewpoint of tooth adhesion, a combination containing a carboxylic acid acidic group-containing polymerizable monomer and / or a phosphoric acid acidic group-containing polymerizable monomer is more preferable, and the carboxylic acid acidic group-containing polymerization is preferred. Monomers and / or
Or a combination containing both a phosphoric acid group-containing polymerizable monomer and a water-soluble hydroxyl group-containing monofunctional non-acidic monomer is more preferable, and among those combinations, the carboxylic acid group-containing polymerizable monomer is preferable. It is particularly preferred that the monomers have a plurality of carboxylic acid groups.

The carboxylic acid acidic group-containing polymerizable monomers in the radical polymerizable monomers containing the carboxylic acid acidic group-containing polymerizable monomers and / or the phosphoric acid acidic group-containing polymerizable monomers. And / or the content of the phosphoric acid group-containing polymerizable monomer is not particularly limited, but is preferably 1 to 85 parts by weight, more preferably 3 to 85 parts by weight in total 100 parts by weight of all the polymerizable monomers. Particularly high dentin adhesion can be obtained when the amount is 75 parts by weight, most preferably in the range of 5 to 65 parts by weight. When the composition further contains a water-soluble hydroxyl-containing monofunctional non-acidic monomer, the content of the water-soluble hydroxyl-containing monofunctional non-acidic monomer is 100% by weight of all polymerizable monomers. It is preferred that the amount be about 5 to 40 parts by weight per part. The carboxylic acid acidic group-containing polymerizable monomers, the phosphoric acid acidic group-containing polymerizable monomers, and the water-soluble hydroxyl group-containing monofunctional non-acidic monomers other than these radical polymerizable monomers. The type of radical polymerizable monomer is not particularly limited, but is preferably an aliphatic polyfunctional polymerizable monomer and / or an aromatic polyfunctional polymerizable monomer.

The polymerization-curable dental composition of the present invention contains an α-diketone-based photopolymerization catalyst for polymerization and curing by light irradiation. By using an α-diketone-based photopolymerization catalyst, the dental curable composition of the present invention can be polymerized and cured by irradiation with visible light.
Furthermore, since the composition is not cured unless irradiated with light, the dental curable composition of the present invention can be stored in a single package.

The α-diketone photopolymerization catalyst used in the present invention is not particularly limited, and known catalysts can be used without any limitation. Specifically, camphorquinone, biacetyl, 2,
3-pentanedione, 2,3-octanedione, benzyl, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, α-naphthyl, β-naphthyl, acenaphthenequinone, 9,10-phenanthrequinone , 1,2-cyclohexanedione and the like. Among these α-diketone polymerization catalysts, camphorquinone is most preferably used because of its high polymerization activity and low toxicity.

[0016] α- in the dental polymerizable curable composition of the present invention
The amount of the diketone polymerization catalyst is not particularly limited as long as the effect as the photopolymerization catalyst is exerted, but in consideration of polymerization activity, physical properties after curing, storage stability, etc. The amount is in the range of 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, and most preferably 0.05 to 100 parts by weight based on 100 parts by weight of the total radical polymerizable monomer. -5 parts by weight.

In the dental curable composition for dental use of the present invention, α
-By further mixing amines as polymerization accelerators with the diketone polymerization catalyst, higher polymerization activity can be obtained. Specific examples of amines having such a polymerization promoting effect include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline,
N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-
Dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethyl Aminobenzoic acid ethyl ester, p-
Amyl dimethylaminobenzoate, N, N-dimethylanthranilic acid methyl ester, N, N
-Dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminoacetophenone, p-dimethylaminophenethyl alcohol, p-
Dimethylaminostilpene, N, N-dimethyl-3,5
-Xylidine, 4-dimethylaminopyridine, N, N-
Dimethyl-α-naphthylamine, N, N-dimethyl-β
-Aromatic tertiary amines such as naphthylamine, tributylamine, tripropylamine, triethylamine,
N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-
Dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
Aliphatic tertiary amines such as 2,2 '-(n-butylimino) diethanol;

Among these amines, aromatic tertiary amines are preferably used because of their high polymerization promoting effect.

It is also preferable to use barbituric acids or thiobarbituric acids as a polymerization accelerator. Specific examples of such barbituric acids or thiobarbituric acids include 5-methylbarbituric acid, 5-methylthiobarbituric acid, 5-butyl barbituric acid,
Butylthiobarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3,5-trimethylthiobarbituric acid, and the like.

Examples of the polymerization accelerator include organic phosphorus compounds such as tri-n-butylphosphine, thioureas such as allylthiourea, and thiols such as 1-octadecanethiol, cyclohexylmercaptan, thiophenol and mercaptobenzoxazole. Are also preferably used.

Further, organic peroxides, azo compounds, sulfinates and borates can be blended as a polymerization accelerator.

The amount of these polymerization accelerators is not particularly limited. However, considering the polymerization acceleration effect, the physical properties after curing, and the storage stability of the dental curable composition for dental use of the present invention, etc. The amount is preferably in the range of 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, most preferably 100 parts by weight of the total radical polymerizable monomer. It is in the range of 0.05 to 5 parts by weight.

These polymerization accelerators can be used as a mixture of two or more.

The dental polymerizable and curable composition of the present invention makes it easy to identify the coated portion, and it can be confirmed that the composition has been cured by irradiating light surely and does not cause an aesthetic problem after curing. In order to achieve the above, a dye that fades by light irradiation (hereinafter, referred to as a photobleachable dye) is blended. The photobleachable dye used in the present invention has a different color from the case where it is not blended (hereinafter, referred to as coloring) when blended in the polymerizable and curable composition for dental use. The compound is not particularly limited as long as it is a compound that fades or changes colorless to pale yellow or a state close to it by light irradiated to cure the polymerization curable composition for use, and a known compound can be used.

The coloring and fading behavior of the photobleachable dye cannot be unconditionally specified because it changes depending on various factors such as the acid strength, dielectric constant, polarity, oxygen content, and moisture content of the environment. Whether the dye to be dyed has the above-described light-induced discoloration property is subjected to a light irradiation test in advance on a dental polymerization curable composition containing the dye, and the difference in color before and after light irradiation is observed. Thus, it can be easily determined.

Specific examples of the photobleachable dye which can be used in the present invention include methylene blue, amaranth, erythrosin, pneucoxin, phloxine, rose bengal,
Acid Red, Tartrazine, Sunset Yellow F
CF, Fast Green FCF, Brilliant Blue F
CF, indigo carmine, phenolphthalein, sulfophthalein, aile violet, methyl orange,
Fluorescein, methyl viologen, indophenol, jimrosbetaine, eosin Y, rhodamine B, thionin, neutral red, toluidine blue O, indosialine green, sulfobromophthalein, uranine, lysole rubin B, lake red C, lysole red, Tetrachlortetrabromfluorescein, Brillian Lake Red R, Deep Maroon, Toluidine Red, Tetrabrom Fluorescein, Herringdon Pink CN, Fast Acid Magenta, Permanent Red, Dibromo Cleoresin, Permanent Orange, Diiodo Fluorescein, Uranine, Quinoline Yellow WS, Alizarin Cyanine Green F, Quinizarin Green SS, Pyranin Conch, Light Green SF
Yellow, Patent Blue NA, Calvathrene Blue, Alphazurin FG, Resorcinol Brown, Alizurin Purple SS, Violamin R, Brilliant Fast Scarlet, Permanent Red F5R, Ponceau SX, Fast Red S, Oil Orange SS, Polar Yellow 5
G, Fast Light Yellow 3G, Naphthol Green B, Guinea Green B, Sudan Blue B, Alizur Purple, Naphthol Blue Black, Crocin, Crocin Blue, Oleoresin Paprika, Chlorophyll, Cartamine, Safflower Yellow, Beet Red, Laccanic Acid, Rubia Color, Lina Blue, Direct First Yellow GC, Direct First Orange, Direct First Scarlet 4BS, Clorantin Fast Red 6BLL, Direct Sky Blue 5
B, Serious Supra Blue BRR, Direct First Turquoise Blue GL, Direct Copper Blue 2B, Coplantin Green G, Direct First Black D, Milling Yellow O, Acid Brilliant Scarlet 3R, Acid Violet 5B, Azaline Direct Blue A2G, Acid Cyanin 6
B, Acid Cyanine 5R, Acid Cyanine Green G, Milling Brown 3G, Acid First Black VLG, Acid Black WA, Cationic Yellow 3G, Cationic Golden Yellow GL, Cationic Flavin 10G, Cationic Yellow 5GL, Cationic Orange R, Cationic Brown 3GL , Cationic pink F
G, cationic brilliant red 4G, cationic red GTL, cationic red BLH, cationic red 6B,
Cation Red 5B, Cation Blue 5G, Cation Blue GRL, Cation Blue, GLH, Cation Navy Blue RLH, Alizarin, Chrome First Blue MB, Chrome First Brown KE, Chrome Black P2B, Chrome Black T, Fast Scarlet G Base, Variamine Blue B base, naphthol AS, naphthol AS-G, bat yellow GCN, bat orange RRTS, indigo, bat blue RSN, bat blue BC, bat brilliant green FFB, bat olive green B, bat olive T, batch olive T, bat grey M , Disperse First Yellow G, Disperse Pink RF, Disperse Blue F
FR, Disperse Blue Green B, Disperse Yellow 5G, Disperse Golden Yellow GG, Disperse Yellow RL, Disperse Yellow 3G,
Disperse Orange B, Disperse Yellow Brown 2R, Disperse Fast Rubin 3B, Disperse Red FB, Disperse Red FL, Disperse Red GFL, Disperse Brilliant Pink RE
L, Disperse Violet HFRL, Disperse Blue FB, Disperse Cois Blue GL, Disperse Navy Blue 2GL, Disperse Developer, Fluorescent Brightener WG, Fluorescent Brightener ERN, Fluorescent Brightener AT, Full Orescent Brightener SA, Solvent Orange G, Solvent Fast Yellow 3R
E, Solvent Fast Red B, Solvent Fast Blue HFL, Reactive Yellow 3G, Reactive Orange 2R, Reactive Red 3B, Reactive Scarlet 2G, Reactive Blue 3G, Reactive Blue R, Reactive Blue BR, Reactive Turquoise GF, Reactive Brilliant Blue R, Reactive Black B, Fast Yellow G,
Fast Yellow 10G, Disazo Yellow AAA, Disazo Yellow AAAX, Flavance Yellow, Chromophthal Yellow GR, Methine Yellow, Sunset Yellow Lake, Anthrapyrimidine Yellow, Isoindolinone Yellow R, Quinophthalone Yellow, Dinitroaniline Orange, Pyrazolone Orange, Diani Cidin orange, Persian orange lake, benzimidazolone orange HL, perinone orange, pyranthrone orange, para red, naphthol red FRR, toluidine red, naphthol carmine FB, naphthol red M, naphthol red BS, naphthol red RN, pyrazolone red, permanent Red 2B, Risor Red, Bon Lake Red C, Lake Red C, Brilliant Carmine 6B Brilliant Carmine 3B, Bordeaux 10B, Bon Maroon M, brilliant scarlet G, Rhodamine 6G Lake, madder lake, thioindigo Bordeaux, Naphthol Red FGR, brilliant carmine BS, quinacridone magenta, perylene vermilion, Naphthol Carmine FBB, perylene red B
L, Chromophtal scarlet, Anthuanthrone Red, Naphthol Red F5RK, Erythrosin Lake, Dianthraquinonyl Red, Perylene Red, Perylene Maroon, Benzimidazolone Carmine HF4C,
Perylene scarlet, amaranth lake, quinacridone red E, pyranthrone red, rhodamine B lake, methyl violet lake, alizarin maroon lake, quinacridone red, dioxazine violet, thioindigo magenta, victoria blue lake,
Victoria Blue 6G Lake, Phthalocyanine Blue,
Alkaline Blue G, Indanthrone Blue, Brilliant Green Lake, Malachite Green Lake, Phthalocyanine Green, Pigment Green B, Phthalocyanine Green 6Y, Benzimidazolone Brown HF
R, aniline black, diarylide yellow H10
G, diarylide yellow HR, carbazole violet, metacresol purple, bromophenol blue, crystal violet, gentian violet, bromocresol green, bromothymol blue and the like.

Among these photobleachable dyes, compounds which form a blue or red hue when incorporated into a dental polymerizable curable composition are used for the yellow color of the α-diketone photopolymerization catalyst. Since the color is different from the color of the system, it is preferable to easily determine the applied portion and to determine whether or not the curing is completely completed.

In the dental curable composition for dental use of the present invention, acidic groups such as carboxylic acid group-containing polymerizable monomers or phosphoric acid group-containing polymerizable monomers are considered from the viewpoint of tooth adhesion. As described above, it is preferable to use a radical polymerizable monomer having the following formula.In such a case, a compound which is stable even under acidic conditions is used as the photobleachable dye. Is preferred. Stability under such acidic conditions, whether discoloration or fading occurs when held for a long time without light irradiation, or whether sufficient fading occurs when irradiated with light after long-term storage Can be determined by

The amount of the photobleachable dye in the dental polymerizable curable composition of the present invention depends on the type of radical polymerizable monomer, α-diketone photopolymerization catalyst, etc. It may be appropriately determined in consideration of the ease of discoloration and the polymerizability of the dental polymerizable curable composition, but is generally 1 to 100 parts by weight of the radical polymerizable monomer in total.
It is preferable to add 0.00001 part by weight, particularly 0.1 to 0.0001 part by weight.

In the dental polymerization-curable composition of the present invention, it is also possible to adjust the hue and the color tone at the time of color development or fading by mixing several types of photobleachable dyes.

In order to control the mechanical strength and fluidity of the dental curable composition of the present invention, inorganic or organic fine particles, reactive or non-reactive polymers or oligomers, etc. may be blended. It is possible.

The method for preparing the dental polymerizable and curable composition of the present invention is not particularly limited, and the above components may be weighed and placed in a container and stirred and mixed under light shielding.

The specific mode of use of the dental polymerization-curable composition of the present invention is not particularly limited as long as it is for dental use, and it can be used for composite resins, sealants, etc.
The effect is best exhibited when used as a bonding material.

When the dental curable composition of the present invention is used as a bonding material, after pretreatment of the tooth surface with some pretreatment material, the dental curable composition is treated with the treated surface. It may be used after coating and light irradiation.

[0035]

The composition of the present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In addition, the application part discrimination test, the cured part discrimination test, the margin part coloring test, the adhesion strength measurement, and the adjustment of the dental polymerization curable composition were performed by the following methods.

(1) Discrimination Test of Applied Area The lip surface of the extracted bovine anterior teeth was ground with a # 800 water-resistant abrasive paper to form a flat surface, and the dental curable composition for dental use of the present invention was applied thereto for about 50 hours. It was thinly applied to a thickness of １５０150 μm. This was observed with the naked eye, and it was confirmed whether the applied portion could be clearly distinguished. The case where it could be clearly distinguished was evaluated as O, and the case where it was unclear was evaluated as X.

(2) Test for discriminating hardened part A test piece coated with a dental curable composition was prepared in the same manner as in the test for discriminating the coated part. Only a part of the applied dental polymerization curable composition was irradiated with light for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) to be cured. The cured portion and an uncured portion not exposed to light were compared with the naked eye to confirm whether a cured portion and an uncured portion could be distinguished. The case where it could be clearly distinguished was evaluated as O, and the case where it was unclear was evaluated as X.

(3) Margin Coloring Test The incisal corners of the extracted bovine anterior teeth were ground with # 800 water-resistant abrasive paper and dried with compressed air. (Prepared by Tokuyama Co., Ltd.) After performing a predetermined treatment with an attached primer, the dental curable compositions of Examples and Comparative Examples were applied. 10 with visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation)
After the light irradiation for 2 seconds, a dental composite resin (Palphique Esterite, manufactured by Tokuyama Corporation) was laid thereon, and light irradiation was again performed for 30 seconds with a visible light light irradiator. After the margin portion was lightly polished with a silicon point (HP13S, manufactured by Matsukaze), it was visually confirmed whether or not an unnatural coloring line was present.を indicates that the composition was the same as the case where the polymerizable curable composition containing no photobleachable dye was used, or was in a state without any discomfort.

FIG. 1 shows a schematic view of the form of the test piece.

(4) Measurement of Enamel and Dentin Bond Strength Within 24 hours after sacrifice, the bovine anterior tooth was removed, and water was injected.
The enamel or dentin plane was cut out with emery paper No. 0 so as to be parallel to the lips. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and a double-sided tape having a hole having a diameter of 3 mm was fixed to the tooth surface. A primer attached to Tokusomak Bond 2 (manufactured by Tokuyama Corporation) was applied to the dentin plane of the hole, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 5 seconds. Subsequently, each of the dental compositions of Examples and Comparative Examples was thinly applied, and was cured by irradiating with a visible light irradiator for 10 seconds. afterwards,
After forming a simulated cavity by fixing a paraffin wax having a thickness of 0.5 mm and a hole having a diameter of 8 mm so as to be at the same center on the circular hole, a dental composite resin (Palphique Esterite, (Manufactured by Tokuyama Corporation) and irradiated with light for 30 seconds using a visible light irradiator to produce an adhesion test piece.

Further, a stainless steel rod having a hole at the upper end was placed on a composite resin of the test piece with a resin cement (Bistite Resin Cement, Inc.).
(Made by Tokuyama) and left in the air for 15 minutes. Subsequently, the adhesive test piece was placed in water at 37 ° C for 24 hours.
After immersion for an hour, the crosshead speed was 1 mm / mi using a tensile tester (Autograph, manufactured by Shimadzu Corporation).
n, and the tensile adhesive strength between the teeth and the composite resin was measured.

For each test, the tensile adhesive strength of eight pieces was measured by the above method, and the average value thereof was defined as the tensile adhesive strength.

(5) Preparation of Polymerizable Dental Curable Composition Under light shielding, a mixture of the following radical polymerizable monomer and α-diketone-based photopolymerization catalyst (hereinafter referred to as photocurable composition) A
And B were adjusted. The photocurable composition A or B is used as it is (Comparative Examples 1 and 2) or a predetermined amount of a dye is blended into the photocurable composition A or B to stir and homogenize (Each Example and Comparative Example 3) ) A dental polymerization curable composition was prepared.

Photocurable composition A: 11-methacryloyloxyundecane-1,1-dicarboxylic acid: 10 parts by weight 2,2-bis (4- (3-methacryloyloxy-2-humanoxyfluorooxy) phenyl) phenyl: 35 parts by weight Triethylene glycol dimethacrylate: 35 parts by weight 2-Hydroxyethyl methacrylate: 20 parts by weight Camphorquinone: 0.4 parts by weight Ethyl p-dimethylaminobenzoate: 1.0 part by weight Photocurable composition Product B ・ 2,2-bis (4- (3-methacryloyloxy-2-human peroxyfluoro) phenyl) fluoro: 48 parts by weight ・ Triethylene glycol dimethacrylate: 32 parts by weight ・ 2-hydroxyethyl methacrylate: 20 parts by weight ・Camphorquinone: 0.5 parts by weight ・ 4-dimethylaminoacetophenone To 101.4 parts by weight of 1.0 part by weight Example 1 photocurable composition A, methylene blue trihydrate were blended 0.036 part by weight, to prepare a dental polymerizable curable composition. Using this composition, a coating portion discrimination test, a cured portion discrimination test, a margin portion coloring test method, and measurement of enamel and dentin adhesive strength were performed.
The results are shown in Table 1.

Examples 2 to 6 The physical properties of each of the polymerizable dental curable compositions having the compositions shown in Table 1 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0046]

[Table 1]

Examples 1 to 6 show the results when a dye which fades by light irradiation is used in the photocurable composition used. In each case, since the dental polymerization-curable composition was colored blue or red, the coated portion could be easily identified. In addition, when these dental polymerizable curable compositions were cured by light irradiation, where light was sufficiently irradiated and a sufficient effect occurred, the color faded to pale yellow, so that the cured part and the uncured part were Not only was discrimination easy, but also formation of a particularly unnatural colored line in the margin was not recognized. Also, regarding the adhesive strength, no significant difference was observed in comparison with Comparative Examples 1 and 2 in which the photobleachable dye described below was not blended, and it was confirmed that no inconvenience was caused by the blending of the photobleachable dye. Was done.

Comparative Examples 1 and 2 Various tests were performed using only the photocurable composition A or B without blending the photobleachable dye. The results are shown in Table 1. Although no coloring of the margin was observed, the discrimination of the coated portion and the discrimination of the cured portion were extremely poor, and were clearly inferior to those of the examples.

Comparative Example 3 0.01 parts by weight of carbon black was added as a coloring agent to 101.5 parts by weight of the photocurable composition A, and various tests were performed. The results are shown in Table 1. In this case, no fading occurred due to light irradiation, so the coated part could be clearly distinguished, but it was extremely difficult to distinguish between the cured and uncured parts, and a clear black line was formed in the margin. It was not aesthetic.

[0050]

[Effects] The dental polymerizable and curable composition of the present invention can clearly discriminate the applied portion and the applied amount at the time of application to the tooth surface, and there is no formation of a colored line in the margin portion. It has the characteristic that it can be seen that it has been hardened by irradiation. Therefore, when the polymerizable dental curable composition of the present invention is used as a bonding material at the time of restoring defective tooth material, it is possible to surely protect the tooth material without affecting the aesthetics particularly at the margin. .

[Brief description of the drawings]

FIG. 1 is a schematic view of a test piece in a margin portion coloring test.

Claims (1)

[Claims] 1. A polymerizable dental curable composition comprising a radical polymerizable monomer, an α-diketone-based photopolymerization catalyst, and a dye that fades upon irradiation with light.