JP2007254307A - Dental adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental adhesive which realizes excellent adhesion durability and excellent adhesive strength between a repairing material and a tooth without an operation such as a preliminary treatment, when the tooth is repaired in a dentistry field and the like. <P>SOLUTION: This dental adhesive comprises a polymerizable monomer including an acidic group-containing polymerizable monomer, water and a polymerization initiator comprising a photo acid generator, an oxidation type photoradical generator, a condensed multi-cyclic aromatic compound in which at least one hydrogen atom-having saturated carbon atom is bound to a carbon atom adjacent to the condensed carbon atom of a condensed multi-aromatic ring, and an amine compound. The photo acid generator is preferably a diaryl iodonium salt-based compound, and the oxidation type photoradical generator is preferably a diaryl ketone compound, an α-diketone compound or a ketocoumarin compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dental adhesive for realizing excellent bonding strength and bonding durability between a composite resin and a tooth material without performing a pretreatment or the like in the case of restoration of a tooth in the field of dentistry and the like. About.

  For the restoration of teeth damaged by caries or the like, a filling material called a composite resin is mainly used. This composite resin is generally used after being filled in a cavity of a tooth and then cured by polymerization. However, since this material does not have adhesiveness to the tooth itself, a dental adhesive is used in combination. This adhesive material is required to have an adhesive strength sufficient to overcome internal stress generated when the composite resin is cured, that is, tensile stress generated at the interface between the composite resin and the tooth. Otherwise, there is a possibility of not only dropping off due to long-term use in a harsh oral environment but also creating a gap at the interface between the composite resin and the tooth, from which bacteria may invade and adversely affect the dental pulp Because.

  Dental hard tissue consists of enamel and dentin, and clinically requires adhesion to both. Conventionally, for the purpose of improving adhesiveness, a method of pretreating a tooth surface prior to application of an adhesive has been used. As such a pretreatment material, an acid aqueous solution for decalcifying the tooth surface is generally used, and acid aqueous solutions such as phosphoric acid, citric acid and maleic acid have been used. In the case of enamel, the adhesion mechanism with the treated surface is a macro mechanical fit in which the adhesive penetrates and hardens to the rough surface by decalcification of the acid aqueous solution, whereas in the case of dentin Is said to be a micro mechanical fitting in which the adhesive penetrates into the fine voids of the sponge-like collagen fibers exposed on the tooth surface after decalcification and hardens. However, the penetration into collagen fibers is not as easy as the enamel surface, and a penetration promoter called a primer is generally used after treatment with an acid aqueous solution.

  Therefore, in this method, in order to obtain good adhesion strength to both enamel and dentin, before applying the dental adhesive, the etching treatment with the acid aqueous solution and the primer treatment with the penetration enhancer are performed. There was a problem that two-stage pretreatment was necessary and the operation was complicated.

  Under these circumstances, in recent years, as a one-step system-type dental adhesive that exhibits considerably good adhesion to both enamel and dentin without performing these pretreatments, (A) acidic group A dental adhesive comprising a polymerizable monomer component containing a polymerizable monomer, (B) water, and (C) a photopolymerization initiator has been developed (see Patent Documents 1 and 2). In this dental adhesive, the acidic group-containing polymerizable monomer has an acidic group such as a phosphoric acid group and a carboxylic acid group, and (B) tooth decalcification in the presence of water. Since it exhibits it and penetrates well into the dentin and exhibits high affinity, it is possible to obtain a considerably high adhesiveness to the tooth without performing the pretreatment described above.

  Such a dental adhesive is preferably used after being applied to a cavity of a tooth that needs to be restored and then cured by irradiation with light for reasons of operability and the like. A polymerization initiator is used. Usually, an α-diketone compound or a thioxanthone compound is used in combination with various amines. In particular, camphorquinone is used as the α-diketone compound, and reducing properties are used as amines. That use a high N, N-dimethylaminobenzoic acid ethyl ester is widely used since excellent polymerization activity is obtained (see, for example, Patent Document 3).

  On the other hand, as photopolymerization initiators for composite resins that can be polymerized in a very short time by light irradiation and obtain good cured product properties, a photoacid generator, a specific photoradical generator, and a specific condensed polycycle The photoinitiator which consists of a formula aromatic compound was discovered and has already been proposed (refer patent document 4). The photopolymerization initiator has a remarkably high polymerization activity, and is expected as a photopolymerization initiator for dental adhesives that satisfy the above-mentioned dental adhesive strength. However, an example in which this combination of photopolymerization initiators is applied as a dental adhesive is not specifically known. Furthermore, as described above, (A) an acidic group-containing polymerization as a polymerizable monomer component There are no examples of using this in the case of using a monomer containing a functional monomer and further blending (B) water.

Japanese Patent Laid-Open No. 10-236912 Japanese Patent Laid-Open No. 10-245525 JP 60-26002 A JP 2004-196949 A

  As described above, (A) a polymerizable monomer component containing an acidic group-containing polymerizable monomer, (B) water, and (C) a dental adhesive containing a photopolymerization initiator is an etching treatment or primer. Even if no pretreatment is applied, it adheres fairly well to both enamel and dentin and is easy to operate, making it an excellent adhesive. In addition, there is room for further improvement in the mechanical strength of the cured product.

  That is, the dental adhesive contains (B) water, and in the presence of such water, the aforementioned α-diketone compound, thioxanthone compound, and the like are combined with various amines (C ) Photopolymerization initiator, photoacid generator, specific photo radical generator, and (C) photopolymerization initiator in combination with a specific condensed polycyclic aromatic compound, etc. It was found that the resin was not cured at a higher degree of polymerization. Further, when applied to the tooth surface as a dental adhesive, the water content of saliva in the oral cavity also causes a decrease in the activity of the (C) photopolymerization initiator, and (A) the acidic group-containing polymerizable monomer. The acidic group of the monomer is a functional group with strong hydrophilicity and has a strong affinity with moisture in the oral cavity, so that the action is further increased, reducing the adhesive strength with the tooth and the durability of the adhesion. It was.

  In order to solve this problem, it is conceivable to use a photopolymerization initiator (C) that is not easily affected by a decrease in activity due to water. Thus, it is unclear which initiator is effective for the dental adhesive system, and it is difficult to predict how the water will affect the development of its polymerization activity.

  In the background described above, the present invention provides a polymerizable monomer containing the above-mentioned (A) acidic group-containing polymerizable monomer which can be used without performing pretreatment such as etching treatment and primer treatment in the restoration of teeth. In a dental adhesive comprising a monomer component, (B) water, and (C) a photopolymerization initiator, it is intended to further improve the adhesion to the tooth and the mechanical strength of the cured body. .

  The present inventors have intensively studied to solve the above problems. As a result, in the dental adhesive, as a photopolymerization initiator, a photoacid generator, an oxidized photoradical generator, a saturated carbon atom having at least one hydrogen atom is condensed with a condensed polycyclic aromatic ring. The present inventors have found that the above problems can be solved by using a combination of a condensed polycyclic aromatic compound bonded to a carbon atom adjacent to the carbon atom and an amine compound, and the present invention has been completed.

  That is, the present invention relates to a dental adhesive comprising (A) a polymerizable monomer containing an acidic group-containing polymerizable monomer, (B) water, and (C) a photopolymerization initiator. The photopolymerization initiator is a (C-1) photoacid generator, (C-2) an oxidized photoradical generator, and (C-3) a saturated carbon atom having at least one hydrogen atom is a condensed polycyclic ring. A dental adhesive comprising a condensed polycyclic aromatic compound bonded to a carbon atom adjacent to a condensed carbon atom of the formula aromatic ring, and (C-4) an amine compound.

  The dental adhesive of the present invention contains water and hardens with high polymerization activity even though the polymerizable monomer component contains an acidic group-containing polysynthetic monomer. Has a high mechanical strength, and can obtain a better dental adhesion strength and adhesion durability.

  Therefore, by using this dental adhesive for the treatment of dental caries, it is possible to firmly bond the tooth substance and the restoration material without pretreatment such as etching treatment and primer treatment. Invasion of caries bacteria from the interface is suppressed, and the recurrence of caries can be highly prevented.

  In the dental adhesive of the present invention (hereinafter, also simply referred to as “the adhesive of the present invention”), (A) the polymerizable monomer component comprises an acidic group-containing polymerizable monomer. This (A) polysynthetic monomer component may consist only of the acidic group-containing polymerizable monomer, but in order to obtain better adhesion and durability to the tooth, From the viewpoint of adjusting the strength of the cured product and the permeability of the adhesive to the tooth structure, it is preferable to further contain a polymerizable monomer having no acidic group. In particular, from the viewpoint of adhesive strength to both enamel and dentin, the content of the acidic group-containing polymerizable monomer in the total polymerizable monomer as the component (A) is 5 to 50% by mass, particularly 10%. It is preferable that it is -30 mass%. When the blending amount of the acidic group-containing polymerizable monomer is small, the adhesive force to the enamel tends to decrease, and conversely, when it is large, the adhesive force to the dentin tends to decrease.

  Here, the acidic group-containing polymerizable monomer is not particularly limited as long as it is a polymerizable monomer having at least one polymerizable unsaturated group and at least one acidic group in one molecule. Can be used. Here, the polymerizable unsaturated group refers to a (meth) acryloyl group and a (meth) acryloyl group such as a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acryloylamino group, a (meth) acryloylthio group; a vinyl group. : Allyl group; styryl group and the like are exemplified.

Moreover, an acidic group here is a phosphinico group {= P (= O) OH}, a phosphono group {—P (═O) (OH) ₂ }, a carboxyl group {—C (═O) OH}, a sulfo group. Not only a free acid group such as (—SO ₃ H) but also an acid anhydride structure (for example, —C (═O) —O—C (═O) —) in which two of the acidic groups are dehydrated and condensed, or An acid halide group in which OH of an acidic group is substituted with a halogen (for example, —C (═O) Cl) or the like, an aqueous solution or a suspension of a polymerizable monomer having the group is a group that exhibits acidity. Show.

  Specific examples of the acidic group-containing polymerizable monomer include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5-aminosalicylic 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-vinylan Perfume acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) Polymerizable monomer having one carboxyl group in the molecule such as acryloyl-4-aminosalicylic acid, and acid anhydrides and acid halides thereof; 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2 -(Meth) acryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4-dicarboxyben Yloxy) propyl succinate, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate, N, O-di (meth) acryloyl tyrosine, 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-acryloyloxybutyl trimellitate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethylnaphthalene -2, 3,6-tricarboxylic anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride, etc. A polymerizable monomer having a plurality of carboxyl groups or acid anhydride groups in the molecule, and acid anhydrides and acid halides thereof (provided that these are compounds having a carboxyl group); 2- (Meth) acryloyloxyethyl dihydrogen phosphate, bis (2- (meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl Dihydrogen phosphate, 6- (meta) Polymerizable monomer having a phosphinicooxy group or phosphonooxy group in the molecule such as acryloyloxyhexyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate (polymerizable acidic phosphorus And acid anhydrides and acid halides thereof; polymerizable monomers having a phosphono group in the molecule such as vinylphosphonic acid and p-vinylbenzenephosphonic acid; 2- (meth) acrylamide- Examples thereof include polymerizable monomers having a sulfo group in the molecule such as 2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and vinylsulfonic acid. In addition to these, JP-A Nos. 54-11149, 58-140046, 59-15468, 58-173175, 61-293951 are disclosed. Dental adhesives disclosed in JP-A-7-179401, JP-A-8-208760, JP-A-8-319209, JP-A-10-236912, JP-A-10-245525, etc. The acidic monomer described as a component of can also be used suitably.

  These acidic group-containing polymerizable monomers may be used alone or in combination of a plurality of types.

  Among the acidic group-containing polymerizable monomers, a polymerizable acidic phosphate ester is particularly preferable in terms of excellent adhesiveness to tooth. Moreover, it is preferable that it is a derivative group of a (meth) acryloyl group as a polymerizable unsaturated group at the point with the favorable polymerizability at the time of light irradiation.

  On the other hand, in the (A) heavy synthetic monomer component, when using a polymerizable monomer other than the acidic group-containing polymerizable monomer (hereinafter also abbreviated as “other heavy synthetic monomer”), As the other polysynthetic monomer, any known radical polymerizable monomer may be used without any limitation as long as it has no acidic group and has a polymerizable unsaturated group. In general, a (meth) acrylate polymerizable monomer is preferably used from the viewpoint of curing speed and mechanical properties of a cured product.

  Specific examples of these other polysynthetic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl Mono (meth) acrylate single amount such as methacrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate Body; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-bis (me (Crylethyloxycarbonylamino) -2,2,4-trimethylhexane, 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane, urethane (meth) acrylate, epoxy (meth) acrylate, etc. Polyfunctional (meth) acrylate monomers; fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, α -Methyl styrene derivative; Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate can be exemplified.

  These other polysynthetic monomers may be used alone or in combination of a plurality of types. From the viewpoint of cured body strength and penetrability into teeth, 2,2-bis (4- ( It is preferable to use a combination of a polycyclic (meth) acrylate such as methacryloyloxypolyethoxyphenyl) propane and a water-soluble polymerizable monomer such as 2-hydroxyethyl (meth) acrylate. The term “sex” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more.

  The (B) water used for the adhesive of the present invention is essential for providing a tooth decalcification action together with the acidic group-containing polymerizable monomer contained in the (A) polymerizable monomer component. The (B) water is preferably substantially free of impurities harmful to storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water.

  The blending amount of (B) water in the adhesive of the present invention is not particularly limited and may be set as appropriate, but (A) 100 mass of polymerizable monomer component containing an acidic group-containing polymerizable monomer. It is preferable that it is 1-50 mass parts with respect to a part, More preferably, it is 10-30 mass parts.

  The greatest feature of the present invention is that in the above-mentioned (A) polymerizable monomer component containing an acidic group-containing polymerizable monomer and (B) a dental adhesive containing water, the weight of the component (A) (C) as a photopolymerization initiator for polymerizing a synthetic monomer, (C-1) a photoacid generator, (C-2) an oxidized photoradical generator, and (C-3) at least one hydrogen atom. A system comprising a combination of a condensed polycyclic aromatic compound in which a saturated carbon atom has a carbon atom adjacent to a condensed carbon atom of the condensed polycyclic aromatic ring, and (C-4) an amine compound is employed. In the point. Thereby, water is contained as in the adhesive, and the polymerization activity is highly maintained even though the acidic group of the acidic group-containing polymerizable monomer has a composition that is compatible with water in the oral cavity. As a result, the cured body has excellent mechanical strength, and exhibits excellent adhesive strength and excellent adhesion durability with respect to the tooth. Hereinafter, each of these components will be described.

(C-1) Photoacid generator (C-1) The photoacid generator used in the adhesive of the present invention is a compound that can directly generate Bronsted acid or Lewis acid by irradiation with light such as ultraviolet rays, and is publicly known. These compounds are used without any limitation, and specific examples include diaryliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and halomethyl-substituted S-triazine conductors. In the present invention, among the above photoacid generators, the diaryl iodonium salt photoacid generator is excellent in that the polymerization activity is particularly high. A typical diaryliodonium salt compound is represented by the following general formula (3).

(In the above ^formulas, the R ^7, R 8, ^{R 9} and ^{R 10} are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group or a nitro group, M ^- Is a halide ion, p-toluenesulfonate ion, perfluoroalkylsulfonate ion, tetrafluoroborate ion, tetrakispentafluorophenylborate ion, tetrakispentafluorophenylgallate ion, hexafluorophosphate ion, hexafluoroarsenate ion, Hexafluoroantimonate ion.)
The diaryl iodonium salt compound shown by these is mentioned.

Here, examples of the halogen atom for R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a fluoro group, a chloro group, a bromo group, and an iodo group. Moreover, as an alkyl group, a C1-C10 thing, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group decyl group, is preferable. Moreover, as an aryl group, a C6-C14 thing, such as a phenyl group, p-methylphenyl group, p-chlorophenyl group, a naphthyl group, is preferable. As the alkenyl group, those having 2 to 14 carbon atoms such as vinyl group, allyl group, isopropenyl group, butenyl group, 2-phenylethenyl group, 2- (substituted phenyl) ethenyl group and the like are preferable. Moreover, as an alkoxy group, a C1-C6 thing of a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is preferable. Furthermore, as the aryloxy group, those having 6 to 14 carbon atoms such as phenoxy, p-methoxyphenyl and p-octyloxyphenyl are preferable.

This diaryliodonium salt-based compound is a diaryliodonium salt-based compound in which M ⁻ is a hexafluorophosphate ion or a tetrakispentafluorophenylborate ion, particularly from the viewpoint of solubility in monomers and low nucleophilicity. Compounds are preferably used.

  Specific examples of the diaryliodonium salt compound represented by the general formula (1) include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, p-isopropyl. Phenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium, Chloride such as p-phenoxyphenyl phenyl iodonium, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophthal Examples thereof include phenyl borate, tetrakispentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like.

  Further, specific examples of other photoacid generators preferably used in the present invention include sulfonium salt compounds such as dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4- Hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8-dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl-4-phenylthiophenyl Chloride such as sulfonium, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakis Examples thereof include pentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate salt.

  Specific examples of the sulfonate compound include benzoin tosylate, α-methylol benzoin tosylate, o-nitrobenzyl p-toluenesulfonate, p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like. Specific examples of the halomethyl-substituted -S-triazine conductor include 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S- Examples include triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, and the like.

  These photoacid generators may be used alone or in combination.

(C-2) Oxidized photoradical generator The (C-2) oxidized photoradical generator used in the adhesive of the present invention is a compound that generates a radical upon excitation by light irradiation. So-called hydrogen abstraction radical generator that generates radicals by extracting hydrogen from the hydrogen donor by means of self-cleavage by excitation (self-cleavage radical generator), and then the radicals from the hydrogen donor The mechanism of generating active radical species by excitation by light irradiation, such as the type that extracts hydrogen and the one that is excited by light irradiation to directly extract electrons from the electron donor to become radicals, is due to the action of an oxidant ( Any known compound may be used as long as it can be reduced).

  Examples of the hydrogen abstraction type radical generator include a diaryl ketone compound, an α-diketone compound, and a ketocoumarin compound.

  Specific examples of the diaryl ketone compound include 4,4-bis (dimethylamino) benzophenone, 9-fluorenone, 3,4-benzo-9-fluorenone, 2-dimethylamino-9-fluorenone, and 2-methoxy-9-. Fluorenone, 2-chloro-9-fluorenone, 2,7-dichloro-9-fluorenone, 2-bromo-9-fluorenone, 2,7-dibromo-9-fluorenone, 2-nitro-9-fluorenone, 2-acetoxy- 9-fluorenone, benzanthrone, anthraquinone, 1,2-benzanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 1-dimethylaminoanthraquinone, 2,3-dimethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone , 2-chloroant Laquinone, 1,5-dichloroanthraquinone, 1,2-dimethoxyanthraquinone, 1,2-diacetoxy-anthraquinone, 5,12-naphthacenequinone, 6,13-pentacenequinone, xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2, 4-Diethylthioxanthone, 2-chlorothioxanthone, 9 (10H) -acridone, 9-methyl-9 (10H) -acridone, dibenzosuberone and the like can be mentioned.

  Specific examples of α-diketone compounds include camphorquinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, 9,10-phenanthrenequinone, acenaphthenequinone, etc. are mentioned.

  Examples of ketocoumarin compounds include 3-benzoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-methoxybenzoyl) 7-methoxy-3-coumarin, and 3-acetyl- Examples thereof include 7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3,3′-coumarinoketone, 3,3′-bis (7-diethylaminocoumarino) ketone, and the like.

  An example of a type in which radicals are generated by self-cleavage by light irradiation and the radicals extract hydrogen from a hydrogen donor is trichloroacetophenone.

  Xanthene compounds, acridine compounds, phenazine compounds, and the like are those that are excited by light irradiation to directly extract electrons from the electron donor and become radicals. Examples of xanthene compounds include eosin compounds, erythrosine compounds, rose bengal, etc. Examples of the acridine compound include acridine, 9-phenylacridine, benz [a] acridine, and acridine orange. Examples of the phenazine compound include phenazine, benz [a] phenazine, and the like.

  Among the various oxidized photo radical generators, compounds having absorption in visible light are preferable from the viewpoint of high activity even when irradiated with visible light, which is widely used for dentistry, and have a maximum absorption wavelength at 350 to 800 nm. More preferred are compounds. Furthermore, a hydrogen abstraction type photoradical generator is preferred in that the polymerization activity when irradiated with light is higher than that of other compounds, and among them, diaryl ketone compounds, α-diketone compounds or ketocoumarin compounds are particularly preferred. preferable.

  These oxidized photo radical generators may be used alone or in combination of a plurality of types.

(C-3) a condensed polycyclic aromatic compound in which a saturated carbon atom having at least one hydrogen atom is bonded to a carbon atom adjacent to the condensed carbon atom of the condensed polycyclic aromatic ring (hereinafter simply referred to as condensed polycyclic aromatic compound). Also called a cyclic aromatic compound.)
(C-3) The condensed polycyclic aromatic compound used in the adhesive of the present invention is a condensed polycyclic aromatic ring in which a plurality of aromatic rings such as a naphthalene ring and an anthracene ring are condensed. At least a carbon atom adjacent to a carbon atom (a carbon atom shared by a plurality of rings) (a carbon atom bonded to a condensed carbon atom, which is also an atom constituting a condensed polycyclic aromatic ring), Any aromatic compound having a structure in which a saturated carbon atom having one hydrogen atom is bonded is not particularly limited, and any known compound can be used. (Hereinafter also referred to simply as the condensed polycyclic aromatic compound of the present invention)
In the condensed polycyclic aromatic compound, a carbon atom that can be bonded to a saturated carbon atom having at least one hydrogen atom that is located next to a carbon atom shared by a plurality of rings is, for example, a naphthalene ring. If the carbon atoms numbered as Nos. 1, 4, 5, and 8 are anthracene rings, the 1, 4, 5, 8, 9 and 10 carbon atoms are 1, and if the phenanthrene rings are 1, The 4, 5, 8, 9 and 10 carbon atoms correspond to this.

  In the condensed polycyclic aromatic compound of the present invention, the condensed polycyclic aromatic ring moiety may have any known structure, and only a hydrocarbon ring such as a naphthalene ring, anthracene ring, phenanthrene ring, or azulene ring is condensed. Or a ring in which heterocycles are condensed such as a naphthyridine ring, or a ring in which both a hydrocarbon ring and a heterocycle are condensed, such as a quinoline ring. The number is not particularly limited as long as two or more rings are condensed. From the viewpoint of polymerization activity and availability, it should have at least one hydrocarbon ring (that is, a condensed hydrocarbon ring or a condensed hydrocarbon ring and a heterocyclic ring). Preferably, it is more preferably composed only of hydrocarbon rings, and particularly preferably only condensed benzene rings. For the same reason, the number of condensed aromatic rings is preferably a condensed 2-6 ring, more preferably a condensed 3-6 ring. In contrast, a non-condensed aromatic ring such as a single benzene ring or pyridine ring cannot improve the polymerization activity, and the effects of the present invention cannot be obtained.

  In addition, the form in which the saturated carbon atom having at least one hydrogen atom is bonded to the carbon atom constituting the condensed polycyclic aromatic ring is not particularly limited, such as methyl anthracene and dichloromethyl anthracene. It may be bonded as a part of a substituent such as an unsubstituted alkyl group or a substituted alkyl group substituted with at least one hydrogen atom on the carbon atom bonded to the condensed polycyclic aromatic ring. However, it may exist as a part of a non-aromatic ring further condensed to a condensed polycyclic aromatic ring, such as acenaphthene and acanthrene.

  Examples of such an unsubstituted alkyl group include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, pentyl group, isopentyl group, hexyl group, and decyl group. Examples are groups. Further, the substituent in the substituted alkyl group substituted with at least one hydrogen atom on the carbon atom bonded to the condensed polycyclic aromatic ring is not particularly limited, and any known substituent may be used. Further, the number of substituents is not particularly limited. Examples of such a substituted alkyl group include a methoxymethyl group, a 1-methoxyethyl group, a 1-methoxypropyl group, a dimethoxymethyl group, a diethoxymethyl group, and a dibutoxymethyl group having 1 to 10 carbon atoms; phenyl Arylalkyl groups having 7 to 15 carbon atoms such as methyl group, p-tolylmethyl group, 1-phenylethyl group, 1-phenylpropyl group, diphenylmethyl group, bis (p-tolyl) methyl group; allyl group, methallyl group, C1-C10 alkenyl groups such as 1-methylallyl group and 1-methylmethallyl group; C3-C10 alkenylalkyl groups such as diallylmethyl group and dimethallylmethyl group; hydroxymethyl group, 1-hydroxyethyl group, 1- Carbon number such as hydroxypropyl group, 1-hydroxypentyl group, 1-hydroxydecyl group 1-10 hydroxyalkyl groups; chloromethyl groups, bromomethyl groups, dichloromethyl groups, dibromomethyl groups, 1-chloroethyl groups, 1-chloropropyl groups and other halogenoalkyl groups having 1 to 5 carbon atoms; acetoxymethyl groups, benzoyl groups C2-C10 acyloxyalkyl groups such as oxymethyl group, diacetyloxymethyl group, 1-acetyloxyethyl group, 1-acetyloxypropyl group; ethylthiomethyl group, butylthiomethyl group, 1-ethylthioethyl group C1-C10 alkylthioalkyl groups such as 1-butylthioethyl group; C1-C10 mercaptoalkyl groups such as mercaptomethyl group, 1-mercaptoethyl group, 1-mercaptopropyl group, etc. Illustrated.

  When a saturated carbon atom having at least one hydrogen atom is present as a part of a non-aromatic ring condensed so as to be bonded to a condensed polycyclic aromatic ring, the condensation mode is ortho-condensation or ortho-peri-condensation. Either is good. The non-aromatic ring includes a saturated hydrocarbon ring such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. In addition, these non-aromatic rings may have unsaturated carbon or hetero atoms such as oxygen, nitrogen, sulfur, etc., but in that case, a saturated carbon atom having at least one hydrogen atom, At least one of the ring elements must be contained. Examples of such non-aromatic rings include unsaturated hydrocarbon rings such as cyclopentene ring, cyclohexene ring, cycloheptene ring, 1,2-cycloheptadiene ring, cyclooctene ring, 1,2-cyclooctadiene ring, 1 , 3-cyclooctadiene ring, etc., and as heteroatom-containing rings, oxygen-containing rings such as oxetane ring, tetrahydrofuran ring, tetrahydropyran ring, etc., nitrogen-containing rings such as azetidine ring, pyrrolidine ring, piperazine ring, etc. Methylene sulfide ring, tetrahydrothiophene ring, tetramethylene sulfide ring, etc. (in addition, these names are names in a state in which they are not condensed with a condensed polycyclic aromatic ring. May change). So that these rings are bonded to the condensed polycyclic aromatic ring as described above, and the saturated carbon atom having at least one hydrogen atom is bonded to the carbon atom adjacent to the condensed carbon atom of the condensed polycyclic aromatic ring. It only needs to be condensed. In addition, when these rings have an unsaturated bond, the unsaturated bond may be condensed so as to be shared with the condensed polycyclic aromatic ring, or it may be condensed so as to remain as other portions. You may do it.

  When present as an unsubstituted or substituted alkyl group, it is preferably present as part of an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. In addition, when present as a part of a non-aromatic ring condensed to a condensed polycyclic aromatic ring, the non-aromatic ring is a 5- to 7-membered ring (ring atoms of the condensed polycyclic aromatic ring A 5- to 7-membered non-aromatic hydrocarbon ring is more preferable.

  On the other hand, when the substituent is not bonded to the condensed polycyclic aromatic ring or when the non-aromatic ring is not condensed, the effect of improving the polymerization activity cannot be obtained. In addition, even if a substituent or a non-aromatic condensed ring exists, a group bonded to a condensed polycyclic aromatic ring with an unsaturated carbon atom such as a vinyl group or a phenyl group, or a carbon such as a methoxy group When only a group bonded by an atom other than the above exists, the effect of improving the polymerization activity cannot be obtained. Similarly, even if it is a saturated carbon atom, it does not have a hydrogen atom on a carbon atom bonded to a condensed polycyclic aromatic ring such as a t-butyl group, a trichloromethyl group, or a 1,1-dichloroethyl group ( Even in the case of carbon atoms that are all substituted, the effect of improving the polymerization activity cannot be obtained.

  In addition, a saturated carbon atom having at least one hydrogen atom as described above may be bonded to a condensed polycyclic aromatic ring, and at least one of them is a condensed polycyclic aromatic as described above. It must be bonded to the carbon atom adjacent to the fused carbon atom in the ring. When the saturated carbon atom having at least one hydrogen atom is bonded only to a carbon atom adjacent to the condensed carbon atom of the condensed polycyclic aromatic compound, sufficient polymerization activity cannot be obtained.

  Further, the condensed polycyclic aromatic ring portion of the condensed polycyclic aromatic compound of the present invention may be substituted with a hydroxyl group, a halogen atom, a mercapto group, a t-butyl group, a trichloromethyl group or the like.

As a compound which can be suitably used as such a condensed polycyclic aromatic compound, the following general formula (1)
R ¹ R ² CH-A- (R ³ ) _n (1)
{In the above formula, A is an n + 1 valent aromatic hydrocarbon group in which 2 to 6 benzene rings are condensed, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, or a carbon number 1 to 10 monovalent organic residues, and R ³ is a halogen atom, a hydroxyl group, a mercapto group, or a monovalent organic residue having 1 to 10 carbon atoms, or R ¹ , R ² , R ^3. Or two of R ³ may be bonded together to form a non-aromatic ring, n is an integer of 0 to 6, and n is 2 or more R ³ may be different from each other, and the group represented by (R ¹ R ² CH—) is bonded to the carbon atom adjacent to the condensed carbon atom of the condensed polycyclic aromatic ring represented by A. is doing. }
The condensed polycyclic aromatic compound shown by these is mentioned.

  In the above formula, A is an n + 1 valent aromatic hydrocarbon group in which 2 to 6 benzene rings are condensed. Specific examples of the aromatic hydrocarbon group include a naphthalene ring in which two benzene rings are condensed; an anthracene ring or a phenanthrene ring in which three benzene rings are condensed; a naphthacene in which four benzene rings are condensed. Ring, 1,2-benzanthracene ring, chrysene ring, pyrene ring, etc .; as the condensed five benzene rings, benzo (a) pyrene ring, benzo (e) pyrene ring, benzo (g) pyrene ring, benzo ( h) a pyrene ring, a benzo (i) pyrene ring, a perylene ring, a pentacene ring, a pentaphen ring, or a picene ring; an aromatic hydrocarbon group derived from a hexaphen ring, a hexacene ring, or the like as a condensed 6 benzene ring. Illustrated.

In the above formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, or a monovalent organic residue having 1 to 10 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The monovalent organic residue having 1 to 10 carbon atoms includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aryl group, and a substituted group. Or an unsubstituted alkenyl group, a dialkylamino group, etc. are illustrated.

  Examples of the unsubstituted alkyl group include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, and hexyl group. Examples are groups.

  The substituent substituted on the substituted alkyl group may be any known group. Specific examples include alkoxy groups such as methoxy group and ethoxy group; aryl groups such as phenyl group and tolyl group; vinyl groups, 1 -1-alkenyl group such as propenyl group; hydroxyl group; halogen atom such as fluorine atom, chlorine atom and bromine atom; acyloxy group such as acetyloxy group and benzoyloxy group; alkylthio group such as ethylthio group and butylthio group; mercapto group and the like Is exemplified.

  More specifically, examples of substituted alkyl groups substituted with such groups include methoxymethyl group, 1-methoxyethyl group, 1-methoxypropyl group, dimethoxymethyl group, diethoxymethyl group, dibutoxymethyl group, and the like. An alkoxyalkyl group having 1 to 10 carbon atoms; an arylalkyl group having 7 to 10 carbon atoms such as phenylmethyl group, p-tolylmethyl group, 1-phenylethyl group, 1-phenylpropyl group; vinyl group, allyl group, methallyl An alkenyl group having 2 to 10 carbon atoms such as a group, 1-methylallyl group and 1-methylmethallyl group; an alkenylalkyl group having 3 to 10 carbon atoms such as a diallylmethyl group and a dimethallylmethyl group; a hydroxymethyl group, a 1-hydroxyethyl group, A C1-C10 hydroxyalkyl group such as a 1-hydroxypropyl group; a chloromethyl group, Lomomethyl group, dichloromethyl group, trichloromethyl group, dibromomethyl group, 1-chloroethyl group, 1-chloropropyl group and other halogenoalkyl groups having 1 to 10 carbon atoms; acetoxymethyl group, benzoyloxymethyl group, diacetyloxymethyl group C1-C10 acyloxyalkyl groups such as 1-acetyloxyethyl group, 1-acetyloxypropyl group; ethylthiomethyl group, butylthiomethyl group, 1-ethylthioethyl group, 1-butylthioethyl group, etc. And an alkylthioalkyl group having 1 to 10 carbon atoms; a mercaptoalkyl group such as a mercaptomethyl group, a 1-mercaptoethyl group, and a 1-mercaptopropyl group.

  Examples of the substituted or unsubstituted alkoxy group and the substituted or unsubstituted alkylthio group include an alkoxy group derived from the above substituted or unsubstituted alkyl group and an alkylthio group (for example, from a methyl group, a methoxy group, A methylthio group is derived), preferably an alkoxy group having 1 to 10 carbon atoms or an alkylthio group.

  Examples of the substituted or unsubstituted aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, a tolyl group, and a xylyl group. Examples of the substituted or unsubstituted alkenyl group include a vinyl group and an allyl group. The alkenyl group having 2 to 10 carbon atoms is exemplified, and examples of the dialkylamino group include dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino group and diethylamino group.

Among the groups represented by (R ¹ R ² CH—) in which R ¹ and R ² are bonded as described above, those having 20 or less carbon atoms are preferable in terms of polymerization activity, and those having 10 or less carbon atoms. Is particularly preferred. Specific examples of such groups include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, isopentyl, and hexyl groups. Methoxymethyl group, 1-methoxyethyl group, 1-methoxypropyl group, dimethoxymethyl group, diethoxymethyl group having 1 to 10 carbon atoms; phenylmethyl group, p-tolylmethyl group, 1-phenylethyl group; , 1-phenylpropyl group, diphenylmethyl group, bis (p-tolyl) methyl group and other arylalkyl groups having 7 to 15 carbon atoms; allyl group, methallyl group, 1-methylallyl group, 1-methylmethallyl group, etc. An alkenyl group having 3 to 10 carbon atoms; an alkenyl alkyl having 3 to 10 carbon atoms such as a diallylmethyl group and a dimethallylmethyl group A hydroxyalkyl group having 1 to 10 carbon atoms such as hydroxymethyl group, 1-hydroxyethyl group, 1-hydroxypropyl group; chloromethyl group, bromomethyl group, dichloromethyl group, dibromomethyl group, 1-chloroethyl group, 1- C 1-10 halogenoalkyl groups such as chloropropyl group; C 2-10 carbon atoms such as acetoxymethyl group, benzoyloxymethyl group, diacetyloxymethyl group, 1-acetyloxyethyl group, 1-acetyloxypropyl group An acyloxyalkyl group; an alkylthioalkyl group having 1 to 10 carbon atoms such as an ethylthiomethyl group, a butylthiomethyl group, a 1-ethylthioethyl group, or a 1-butylthioethyl group; a mercaptomethyl group, a 1-mercaptoethyl group, 1 -Mercaptoal having 1 to 10 carbon atoms such as mercaptopropyl group Group, and the like.

In the above formula, R ³ is a halogen atom, a hydroxyl group, a mercapto group, or a monovalent organic residue having 1 to 10 carbon atoms, and specific examples thereof are the same as those described above for R ¹ and R ^2. . In the above formula, n is an integer of 0 to 6, and when n is 2 to 6, the groups represented by R ³ may be the same or different.

In the above formula, any two selected from R ¹ , R ² , and R ³ or R ³ may be bonded together to form a non-aromatic ring. A plurality of these non-aromatic rings may be present, and in that case, they may be different from each other.

Specific examples of the case where R ¹ and R ² are bonded together to form a ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, tetrahydropyran ring, tetrahydrofuran ring, etc. What is present is exemplified.

In addition, when R ¹ or R ² and R ³ are bonded together to form a ring, or when R ⁷ is combined together to form a ring, these rings are fused with the above-described condensed A. A non-aromatic ring fused with the cyclic aromatic hydrocarbon ring is formed. Such a ring is not particularly limited, and may be a hydrocarbon ring or a heterocyclic ring. Specifically, a saturated carbon atom having at least one hydrogen atom is bonded to a condensed polycyclic aromatic ring. It is as illustrated as a case where it exists as a part of the non-aromatic ring condensed in this way.

R ³ may be bonded to any position of the condensed polycyclic aromatic hydrocarbon ring represented by A, but the group represented by (R ¹ R ² CH—) is a fused group represented by A. Must be attached to the carbon atom adjacent to the fused carbon atom of the polycyclic aromatic ring.

Examples of the (C-3) condensed polycyclic aromatic compound that is preferably used include that 1-methylnaphthalene, 1-ethylnaphthalene, and any of R ¹ , R ^2, and R ³ are not bonded to each other; Naphthalene derivatives such as 1,4-dimethylnaphthalene; phenanthrene derivatives such as 4,5-dimethylphenanthrene and 1,8-dimethylphenanthrene; 1-methylanthracene, 9-methylanthracene, 9-ethylanthracene, 9,10- Dimethylanthracene, 9,10-diethylanthracene, 9-methoxymethylanthracene, 9- (1-methoxyethyl) anthracene, 9-hexyloxymethylanthracene, 9,10-dimethoxymethylanthracene, 9-dimethoxymethylanthracene, 9-phenyl Methyl anthracene, 9- (1 Naphthyl) methylanthracene, 9-hydroxymethylanthracene, 9- (1-hydroxyethyl) anthracene, 9,10-dihydroxymethylanthrane, 9-acetoxymethylanthracene, 9- (1-acetoxyethyl) anthracene, 9,10- Diacetoxymethylanthracene, 9-benzoyloxymethylanthracene, 9,10-dibenzoyloxymethylanthracene, 9-ethylthiomethylanthracene, 9- (1-ethylthioethyl) anthracene, 9,10-bis (ethylthiomethyl) Anthracene, 9-mercaptomethylanthracene, 9- (1-mercaptoethyl) anthracene, 9,10-bis (mercaptomethyl) anthracene, 9-ethylthiomethyl-10-methylanthracene, 9-methyl-10 Phenylanthracene, 9-methyl-10-vinylanthracene, 9-allylanthracene, 9,10-diallylanthracene, 9-chloromethylanthracene, 9-bromomethylanthracene, 9-iodomethylanthracene, 9- (1-chloroethyl) anthracene 9- (1-bromoethyl) anthracene, 9- (1-iodoethyl) anthracene, 9,10-dichloromethylanthracene, 9,10-dibromomethylanthracene, 9,10-diiodomethylanthracene, 9-chloro-10- Methylanthracene, 9-chloro-10-ethylanthracene, 9-bromo-10-methylanthracene, 9-bromo-10-ethylanthracene, 9-iodo-10-methylanthracene, 9-iodo-10-ethylanthracene, 9- Anthracene derivatives such as methyl-10-dimethylaminoanthracene, 7,12-dimethylbenz (a) anthracene, 7,12-dimethoxymethylbenz (a) anthracene; 5,12-dimethylnaphthacene, 7-methylbenzo (a) Pyrene, 3,4,9,10-tetramethylperylene, 3,4,9,10-tetrakis (hydroxymethyl) perylene, 6,13-dimethylpentacene, 8,13-dimethylpentaphene, 5,16-dimethylhexa Examples thereof include derivatives of condensed polycyclic aromatic hydrocarbons in which 4 to 6 benzene rings are condensed, such as cene and 9,14-dimethylhexaphene.

Examples of those in which R ¹ and R ² are bonded to each other to form a ring include 9-cyclohexylanthracene, 9,10-dicyclohexylanthracene and the like, and R ¹ or R ² and R ³ are bonded. Examples of the ring forming groups include acenaphthene, phenalene, acephenanthrene, aceanthrene, acenaphthenone, 1,2,3,4-tetrahydrophenanthrene, benzo [e] phthalane, benzo [f] chroman, benzo [f] isochroman N-methylbenzo [e] indoline, N-methylbenzo [e] isoindoline, colanthrene, violanthrene, isoviolanthrene and the like.

  These condensed polycyclic aromatic compounds may be used alone or in combination.

(C-4) Amine Compound The (C-4) amine compound in the present invention is polymerized in the presence of an aqueous acid solution in the polymerization initiator comprising the above (C-1), (C-2) and (C-3). It is essential to prevent a decrease in activity, and as the amine compound, known amine compounds can be used without any limitation, and primary amines, secondary amines and tertiary amines can be mentioned. In terms of odor and the like, tertiary amine compounds are preferable. These amine compounds include an amine compound in which one or more aromatic groups are directly bonded to a nitrogen atom (hereinafter also referred to as an aromatic amine compound) and an amine compound having no aromatic group directly bonded to a nitrogen atom ( Hereinafter, it is also referred to as an aliphatic amine compound).

  As the aromatic amine compound, known aromatic amine compounds can be used without any limitation. Specifically, aromatic primary amine compounds such as aniline and toluidine; N-methylaniline, N-methyl-p-toluidine Aromatic secondary amine compounds such as: N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di There may be mentioned tertiary amine compounds such as (β-hydroxyethyl) -p-toluidine, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate and amyl p-dimethylaminobenzoate.

  Among these, tertiary aromatic amine compounds are preferable from the viewpoint of odor and the like in consideration of use for dental use. Furthermore, an aromatic tertiary amine compound represented by the following general formula (2) is used in that it exhibits high polymerization activity, maintains polymerization curability, and can exhibit high cured product properties. Is more preferable.

(In the formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
In the general formula (2), each independently ^{R 4} and ^{R 5,} is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an n-hexyl group.

In general formula (2), R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an n-hexyl group.

  Specific examples of the aromatic amine compound represented by the general formula (2) include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzyl. Aniline, 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-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester and the like.

  Specific examples of the aliphatic amine compound preferably used in the present invention include aliphatic primary amine compounds such as n-butylamine, n-hexylamine and n-octylamine; aliphatics such as dibutylamine. Secondary amine compounds; aliphatic tertiary amine compounds such as triethylamine, tributylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, etc. can be mentioned, but aliphatic tertiary compounds are preferred. A tertiary amine compound, more preferably a tertiary aliphatic amine compound having a radically polymerizable functional group such as N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate.

  Any of these amine compounds may be used, and different types of amine compounds may be used in combination, but at least one aromatic amine compound is preferably used, and one or more aromatic compounds may be used. It is particularly preferable to use an aliphatic amine compound in combination with one or more aliphatic amine compounds. By using an aromatic amine compound and an aliphatic amine compound in combination, coloring is reduced when the cured product is exposed to ultraviolet light such as sunlight, compared to the case of using only an aromatic amine compound, Curing activity is improved as compared with the case of using only an amine compound.

  Most preferably, it is a combination of an aromatic tertiary amine compound represented by the general formula (2) and a tertiary aliphatic amine compound having a radical polymerizable functional group.

The blending amount of the (C) photopolymerization initiator used in the present invention is not particularly limited, but (C--100 parts by mass of the polymerizable monomer containing the acidic group-containing polymerizable monomer (C- 1) 0.1 to 10.0 parts by mass of a photoacid generator, (C-2) 0.01 to 5.0 parts by mass of an oxidized photoradical generator, (C-3) a condensed polycyclic aroma The group compound is preferably 0.01 to 5.0 parts by mass, and the (C-4) amine compound is preferably 0.1 to 15.0 parts by mass, more preferably the component (C-1) is 0.5 to 0.5 parts by mass. 5.0 parts by mass, (C-2) component is 0.05 to 1.0 part by mass, (C-3) component is 0.05 to 1.0 part by mass, and (C-4) component is 0.5. -7.0 parts by mass.
Further, when an aromatic amine compound and an aliphatic amine compound are used in combination as the amine compound which is the component (C-4), the mass of both within the range of the blending amount of the component (C-4). The ratio of 1 to 20% by mass for the former and 80 to 99% by mass for the latter, and more preferably 5 to 10% by mass for the former and 90 to 95% by mass for the latter is a viewpoint that particularly improves the curing activity. To preferred.

  The dental adhesive of the present invention exhibits its effect if the components (A) to (C) are blended, but the dental adhesive is used as necessary within the range not impairing the effect of the present invention. Other components known as a composition component of the composition, for example, a water-soluble organic solvent, an ultraviolet absorber, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, an inorganic filler, and the like may be blended.

  As the water-soluble organic solvent, known organic solvents can be used without any limitation as long as they exhibit water-solubility. The term “water-soluble” as used herein means that the solubility in water at 20 ° C. is 20 g / 100 ml or more. Specific examples of such water-soluble organic solvents include methanol, ethanol, propanol, isopropyl alcohol, acetone, methyl ethyl ketone, and the like. A plurality of these organic solvents can be mixed and used as necessary. In view of harmfulness to living organisms, ethanol, propanol or acetone is preferable.

  The method for producing the dental adhesive of the present invention is not particularly limited, and may be performed according to a known method for producing a dental adhesive, and is generally blended under an inert light such as red light. All the ingredients are weighed and mixed well until a homogeneous solution is obtained.

  The dental adhesive of the present invention is used for the purpose of adhering a composite resin and a tooth substance filled in a cavity of a restoration part of a tooth when a tooth damaged by caries or the like is repaired. As the composite resin, known ones can be used without limitation, but in general, a (meth) acrylate polymerizable monomer is used as a curable component, and a polymerization initiator such as a photopolymerization initiator and a filler are blended therein. Is used.

  The specific usage method may also follow the usage method of a well-known dental adhesive material, for example, apply | coat the adhesive material of this invention to the dentine used as the to-be-adhered body which removed the carious part, 5-60 Lightly blown with compressed air etc. after standing for about a second, then irradiated with visible light using a dental irradiator, polymerized and cured, then filled with a restoration such as a composite resin to be attached, photocured Just do it.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The compound used in Examples and Comparative Examples and their abbreviations are shown in (1), the polymerization activity evaluation method for the polymerization initiator used in the adhesive of the present invention is shown in (2), and the bending strength measurement method for the cured product. Is shown in (3), and the method for measuring the enamel and dentin bond strength is shown in (4).
(1) Abbreviation and structure (A) Polymerizable monomer component containing an acidic group-containing polymerizable monomer Acidic group-containing polymerizable monomer
PM: Mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate
MDP; 10-methacryloyloxydecyl dihydrogen phosphate
11, 10-dicarboxyundecyl methacrylate 4META; 4-methacryloyloxyethyl trimellitic acid Other polymerizable monomer D2.6E; 2,2-bis (4- (methacryloyloxypolyethoxyphenyl) propane 3G; Triethylene glycol dimethacrylate HEMA; 2-hydroxyethyl methacrylate (C) photopolymerization initiator (C-1) photoacid generator DPISB; diphenyliodonium hexafluorophosphate DPIPB; p-isopropylphenyl-p-methylphenyliodonium tetrakispenta Fluorophenylborate DPSB; diphenylsulfonium hexafluorophosphate BTC; benzoin tosylate TCT; 2,4,6-tris (trichloromethyl) -S-triazine (C-2) oxidized light Dical generator CQ; camphorquinone AnQ; anthraquinone RC; 3,3′-bis (7-diethylaminocoumarino) ketone (C-3) condensed polycyclic aromatic compound DMAn; 9,10-dimethylanthracene 9MAn; Methylanthracene (C-4) amine compound Aromatic amine DMBE; p-dimethylaminobenzoic acid ethyl ester DMPT; N, N-dimethyl-p-toluidine aliphatic amine DMEM; N, N-dimethylaminoethyl methacrylate DEEM; N, N-diethylaminoethyl methacrylate
NMA; N, N-dimethylaniline (2) Polymerization activity evaluation method 3.0 g of the adhesive material of the present invention is placed in a 5 ml sample tube bottle, and a dental light irradiator (TOKUSO POWER LITE, Inc. ) For 2 minutes. Evaluation was made in three stages according to the curing depth of the cured body immediately after irradiation. In other words, ◎ when the depth of cure has reached 20 mm, ○ if the depth of cure is 15 mm or more and less than 20 mm, ● if the cure depth is 10 mm or more and less than 15 mm, partially cured, but the cure depth reaches 10 mm Those that were not treated were evaluated as Δ, and those that gelled but did not have sufficient hardness, or were not cured at all, were evaluated as ×.
(3) Bending strength measurement method of cured body The Teflon (registered trademark) mold frame is filled with the adhesive of the present invention and pressed with polypropylene, and the entire surface is exposed to light for 30 seconds × 3 times. In this way, light irradiation was performed by closely contacting polypropylene with Toxo power light. Subsequently, it was made to adhere to polypropylene from the opposite side in the same manner and irradiated with light for 30 seconds × 3 times to obtain a cured product. Using # 800 water-resistant abrasive paper, the cured body was adjusted to a 2 × 2 × 25 mm prism shape, and this sample piece was mounted on a testing machine (manufactured by Shimadzu Corp., Autograph AG5000D). Three-point bending strength was measured at 1 mm / min.
(4) Method for measuring enamel and dentin bond strength Remove the anterior teeth of the cow within 24 hours after slaughtering, and sharpen the enamel and dentin planes in parallel with the lip with a # 600 emery paper under water flow. I put it out. Next, air is blown onto these surfaces for about 10 seconds to dry, and then a double-sided tape with a hole having a diameter of 3 mm is fixed to the flat surface, followed by paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm. A simulated cavity was formed by fixing to the same center on the circular hole. The adhesive of the present invention was applied in the simulated cavity and left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Next, the adhesive was cured by irradiating with a visible light irradiator (Powerlight, manufactured by Tokuyama Dental Co., Ltd.) for 10 seconds. Further, a dental composite resin (Palfique Estelite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to prepare an adhesion test piece.

  After immersing the above-mentioned adhesion test piece in 37 ° C. water for 24 hours, using a tensile tester (Autograph, manufactured by Shimadzu Corp.), it is pulled at a crosshead speed of 2 mm / min, and the tensile bond strength between the tooth and the composite resin is measured. did. Four tensile bond strengths per test were measured by the above method, and the average value was defined as the bond strength. Moreover, the adhesion test piece produced similarly was immersed in water at 4 ° C. and 60 ° C. for 1 minute alternately in a thermal shock tester, and after 3000 times, the tensile adhesive strength was measured in the same manner as described above. The value was defined as the adhesive strength after durability.

Example 1
(A) 2.5 g PM as component, 4.0 g D-2.6E, 1.5 g 3G, and 2.0 g HEMA, (B) 1.5 g water as component (C-1) 0.25 g DPISB as component, 0.02 g CQ as component (C-2), 0.01 g DMAn as component (C-3), 0.04 g DMBE as component (C-4), and 0. Using 4 g of DMEM, these were mixed to prepare the adhesive of the present invention. The composition of this adhesive is shown in Tables 1 and 2.

  Using the obtained adhesive, the polymerization activity, the bending strength of the cured body, the enamel, the dentin adhesive strength, and the adhesive strength after durability were measured. The evaluation results are shown in Table 3.

Examples 2-25
In accordance with the method of Example 1, adhesives having different compositions were prepared. Tables 1 and 2 show the composition of the adhesive, and Table 3 shows the polymerization activity, the bending strength of the cured product, and the adhesive strength evaluation results.

Comparative Examples 1-10
In accordance with the method of Example 1, adhesives having different compositions were prepared. Tables 4 and 5 show the composition of the adhesive, and Table 6 shows the evaluation results of polymerization activity, bending strength of the cured product, and adhesive strength.

  Examples 1 to 25 are blended so that each component satisfies the constitution shown in the present invention, but in any case, it has high polymerization activity and bending strength of the cured product. In addition, the adhesive strength to the tooth has a good value including after durability.

  On the other hand, Comparative Examples 1 and 2 are cases where α-diketone compounds and amines that are currently widely used as photopolymerization initiators are used, but the polymerization activity is low, and the bending of the cured product is low. The strength and the adhesive strength to the tooth are reduced.

  Comparative Example 3 uses an acid group-containing polymerizable monomer that is a component (A) using a photopolymerization initiator obtained by removing the amine compound that is the component (C-4) from the photopolymerization initiator used in the present invention. And (B) the case where it does not contain water as component B, it is possible to obtain good results in the polymerization activity and the bending strength of the cured product, but it contains an acidic group-containing polymerizable monomer necessary for the decalcification of teeth. Since it does not contain a meter and water, it cannot provide adhesive strength to the tooth. Comparative Example 4 is a case where water is added to the adhesive shown in Comparative Example 3, but the polymerization activity is lowered and the bending strength of the cured product is lowered. Comparative Example 5 is a case where an acidic group-containing polymerizable monomer and water necessary for tooth decalcification were added to the adhesive shown in Comparative Example 3, but the polymerization activity was the same as that of Comparative Example 4. Similarly, the bending strength of the hardened body and the adhesive strength of the tooth are further lower than those of Comparative Example 4.

  Comparative Examples 6 to 8 were a photoacid generator as component (C-1), an oxidized photoradical generator as component (C-2), and a condensed polycyclic aromatic compound as component (C-3). Although it is a case where any one of the compounds is lacking, the polymerization activity is lowered, and the bending strength of the cured product and the adhesive strength to the tooth are greatly inferior to those of Examples 1 to 25.

  In Comparative Example 9, since the polymerizable monomer as the component (A) does not contain an acidic group-containing polymerizable monomer, the polymerization activity and the bending strength of the cured product have good values. The demineralization power of the tooth is weak and the adhesive strength after the initial and durability is lowered.

In Comparative Example 10, since water as component (B) is not blended, although the polymerization activity and the bending strength of the cured product have good values, the decalcification power of the tooth is weak and it is against the tooth. Adhesive strength is reduced.

Claims (5)

  (A) In a dental adhesive comprising a polymerizable monomer containing an acidic group-containing polymerizable monomer, (B) water, and (C) a photopolymerization initiator, the (C) photopolymerization initiator is (C-1) a photoacid generator, (C-2) an oxidized photoradical generator, and (C-3) a saturated carbon atom having at least one hydrogen atom is condensed with a condensed polycyclic aromatic ring. A dental adhesive comprising a condensed polycyclic aromatic compound bonded to a carbon atom adjacent to a carbon atom, and (C-4) an amine compound.   (C-1) The dental adhesive according to claim 1, wherein the photoacid generator is a diaryliodonium salt compound.   (C-2) The dental adhesive according to claim 1 or 2, wherein the oxidized photoradical generator is at least one selected from the group consisting of a diaryl ketone compound, an α-diketone compound or a ketocoumarin compound. (C-3) The condensed polycyclic aromatic compound has the following general formula (1):
R ¹ R ² CH-A- (R ³ ) _n (1)
{In the above formula, A is an n + 1 valent aromatic hydrocarbon group in which 2 to 6 benzene rings are condensed, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, or a carbon number 1 to 10 monovalent organic residues, and R ³ is a halogen atom, a hydroxyl group, a mercapto group, or a monovalent organic residue having 1 to 10 carbon atoms, or R ¹ , R ² , R ^3. Or two of R ³ may be bonded together to form a non-aromatic ring, n is an integer of 0 to 6, and n is 2 or more R ³ may be different from each other, and the group represented by (R ¹ R ² CH—) is bonded to the carbon atom adjacent to the condensed carbon atom of the condensed polycyclic aromatic ring represented by A. is doing. }
The dental adhesive according to claim 1, which is a condensed polycyclic aromatic compound represented by the formula: (C-4) The amine compound is represented by the following general formula (2)

(In the formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The dental adhesive according to claim 1, comprising a combination of an aromatic tertiary amine compound represented by the above and a tertiary aliphatic amine compound having a radical polymerizable functional group.