JP2012126666A - Adhesive composition for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for dental use hardenable well even by using an irradiator using an LED light source, and exhibiting excellent adhesiveness to teeth.SOLUTION: This adhesive composition for dental use includes (a) an acid group-containing polymerizable monomer, (b) an iron-arene complex of formula 1, and (c) an organic peroxide, where in the formula, Ris a hydrogen atom or a hydrocarbon group; n is an integer of 0 to 6, when n is ≥2, respective Rs may be the same or different from each other, and the plurality of Rs may together form a condensed aromatic hydrocarbon cyclic group; Xis an anion selected from a halide ion, sulfonic acid ion, BF, PF, AsF, SbF, B(CF)or Ga(CF).

Description

  The present invention relates to a dental adhesive composition for bonding a dental restoration and a tooth substance in the field of dentistry.

  Conventionally, small defects (cavities) caused by dental caries or the like have been treated by being filled with a metal material. However, in recent years, it is possible to give the same color tone as natural tooth color and easy operation. Therefore, instead of the metal material, a resin-based filling mainly composed of a polymerizable monomer, an inorganic filler, and a polymerization initiator is used. Restoration materials have been favored. Recently, a photopolymerization initiator is advantageously used for this resin-based filling restorative material because of its short curing time and operability. As such a photopolymerization initiator, an α-diketone compound such as camphorquinone and an amine compound are used. And phosphorous compounds such as acylphosphine oxide are often used. Of these, α-diketone compounds can be combined with amine compounds to increase the curing speed and deepen the curing depth. It is very useful as a photopolymerization initiator for materials. The light of a dental irradiator effective for activating such a photopolymerization initiator is generally blue light having a wavelength of around 470 nm, and a halogen lamp or a xenon lamp is used as a light source. LED light sources capable of irradiating such single wavelength light have been widely used.

  Further, since such a filling / restoring material itself usually does not have adhesiveness to the teeth, it is generally adhered to the teeth via a dental adhesive. This adhesive material is also composed mainly of a polymerizable monomer and a polymerization initiator, as in the case of the filling restorative material, but has excellent adhesiveness to teeth as a part of the polymerizable monomer. By blending, the adhesion to the teeth is enhanced. It is known that a monomer containing an acidic group is particularly suitable as a polymerizable monomer having excellent adhesion to teeth. The adhesive containing such an acidic group-containing polymerizable monomer as a polymerizable monomer further has a tooth decalcification ability by further containing water. Excellent penetration into teeth. Therefore, if such an adhesive is used, it is usually a complicated pretreatment for improving adhesiveness, that is, a demineralization treatment with an acid aqueous solution, or a polymerizable monomer excellent in affinity to the tooth. Osmosis treatment can also be omitted, which is very advantageous. Also in such a dental adhesive, a photoinitiator is advantageously used as the polymerization initiator because of its short curing time and operability, and α-diketone compounds such as camphorquinone, acylphosphine oxide, and the like. Many phosphorous compounds such as the above are used (Patent Document 1). Recently, an example in which a titanocene photopolymerization initiator is used as an adhesive has also been reported (Patent Document 2). On the other hand, it is known to use an iron arene complex and an organic oxide in combination as an initiator composition that can be similarly used with visible light except for dental adhesive applications (Patent Document 3).

JP 2008-201726 A JP 2007-14579 A JP 59-219307 A

  Since the adhesive containing the acidic group-containing polymerizable monomer has a higher adhesive strength than that not containing the monomer and also has a deashing function, it is as described above. In addition, it was useful to realize the simplification of the bonding operation. However, when camphorquinone and an amine compound are used as the photopolymerization initiator, the amine compound undergoes a neutralization reaction with the acidic group-containing polymerizable monomeric acid group, and the amine compound is deactivated, so the polymerization starts. There was a problem that the activity was lowered and it was not sufficiently photocured. Therefore, a phosphorus polymerization initiator composed of an acyl phosphine oxide having a polymerization initiating activity without using an amine compound is often used. However, since the absorption wavelength of the phosphorus polymerization initiator is shorter than that of the irradiation light of the dental irradiator (around 380 to 400 nm), an LED light source that specifically emits a single wavelength of 470 nm is used. The irradiator used has a problem that the polymerization initiation activity cannot be obtained sufficiently. Moreover, even if a titanocene initiator was used, the actual situation was that sufficient polymerization initiation activity was not obtained. Furthermore, the combination of an iron arene complex and an organic oxide is used in applications other than dental adhesives, compared to the combination of the above-mentioned alpha diketone and amine compound, and a phosphorus polymerization initiator composed of acylphosphine oxide. Due to the poor polymerization activity, it was rarely used for dental applications.

  As described above, a photopolymerization initiator having a high polymerization initiation activity for blue light near 470 nm is found, and by using this, it is cured well even with an irradiator using an LED light source, and is used for teeth. Developing a dental adhesive composition that exhibits excellent adhesion was a major challenge.

  The inventors of the present invention have made extensive studies to overcome the above technical problems. As a result, surprisingly, very high polymerization initiation can be achieved by combining an iron arene complex and an organic oxide as the photoinitiator composition and using an acidic group-containing polymerizable monomer as the polymerizable monomer. As a result, it was found that high adhesive strength can be obtained in a dental adhesive, and the present invention has been completed.

  That is, the present invention is a dental adhesive composition comprising a) an acidic group-containing polymerizable monomer, b) an iron arene complex, and c) an organic peroxide.

  The photopolymerization initiator composition contained in the dental adhesive composition of the present invention maintains a high polymerization initiation activity even in the presence of an acidic group-containing polymerizable monomer, and further in the irradiation light of a dental irradiator. Also exhibits sufficient polymerization initiating ability. Therefore, even when an irradiator using an LED light source that specifically emits light having a single wavelength of 470 nm is used, high polymerization initiation activity can be obtained.

  Therefore, the dental adhesive composition of the present invention has a high polymerization activity regardless of the light source of the dental irradiator, and by using this high polymerization initiating ability, a high adhesive strength can be realized, and the tooth and composite It is useful as an adhesive that can be bonded to a dental restoration such as a resin or a prosthesis.

  The a) acidic group-containing polymerizable monomer component contained in the dental adhesive composition will be described. The acidic group-containing polymerizable monomer contained in the dental adhesive composition according to this embodiment is particularly a compound having at least one acidic group and one radical polymerizable unsaturated group in one molecule. It is not limited, A well-known compound can be used. Here, the acidic group is a functional group having a pKa of less than 5 and capable of dissociating active protons, and specifically includes a carboxyl group, a sulfo group, a phosphone group, a phosphoric acid monoester group, a phosphoric acid diester group, and the like. Can be mentioned. Among these, as an acidic group having high adhesiveness to a tooth, a carboxyl group, a phosphoric acid monoester group or a phosphoric acid diester group is more preferable, and a phosphoric acid monoester group or a phosphoric acid diester group is most preferable.

  Specific examples of such acidic group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl hydrogen maleate, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- ( (Meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxyethyl-1,1-undecanedicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3 , 4-Dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid, etc. Carboxylic acid acidic radical polymerizable monomers; 2- (meth) acryloyloxyethylpheny Hydrogen phosphate, bis ((meth) acryloyloxyethyl) hydrogen phosphate, (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl Phosphoric acid group-containing radical polymerizable monomers such as dihydrogen phosphate; Phosphonic acid group-containing radical polymerizable monomers such as vinylphosphonic acid; Styrenesulfonic acid, 3-sulfopropane (meth) acrylate, And sulfonic acid acidic group-containing polymerizable monomers such as 2- (meth) acrylamido-2-methylpropanesulfonic acid. Moreover, these acidic group-containing polymerizable monomers may be used in combination of two or more if necessary.

  The amount of the acidic group-containing polymerizable monomer is not particularly limited, and the entire polymerizable monomer component may be composed only of the acidic group-containing polymerizable monomer, but it penetrates into the tooth of the adhesive. From the standpoint of adjusting the properties and improving the strength of the cured product, it is preferable to use in combination with an acidic group-free polymerizable monomer. Even when these acidic group-free polymerizable monomers are used in combination, from the viewpoint of improving the adhesive strength to both enamel and dentin, in these all polymerizable monomer components, these acidic group-containing radical polymerizations It is preferable to use it in the range of 5 mass% or more of the functional monomer, more preferably 5 to 80 mass%, particularly preferably in the range of 10 to 60 mass%.

  As long as the non-acidic group-containing polymerizable monomer that can be used in the present invention has at least one polymerizable unsaturated group in the molecule, a known compound can be used without any limitation. Specific examples include methyl (meth) acrylate (meaning methyl acrylate or methyl methacrylate; the same shall apply hereinafter), ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth). Acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meta ) Acrylate, mono (meth) acrylate monomers such as 2- (meth) acryloxyethyl acetylacetate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethyl 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- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, Polyfunctional (meta) such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate ) Acrylate-based single amount And the like can be given. Furthermore, as a non-acidic monomer, a polymerizable monomer other than the (meth) acrylate monomer can be mixed and polymerized. Examples of these other polymerizable monomers include fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, α-methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, allyl diglycol carbonate and the like. These polymerizable monomers can be used alone or in admixture of two or more.

  In addition, when using water and a highly hydrophobic polymerizable monomer described later, amphiphilic monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are used. It is preferable in terms of adhesive strength to prevent separation of water and to have a uniform composition.

  In the present invention, b) the iron arene complex absorbs light by light irradiation, and the ligand on the iron atom is exchanged with the organic peroxide to activate the organic oxide, and the polymerization initiating species is appear. Therefore, as the iron arene complex that can be used in the present invention, any known one can be used without any limitation as long as it absorbs light and the ligand is exchanged. Among these, an iron arene complex represented by the following formula 1) is preferable because of its high ligand exchange ability.

(R ³ is a hydrogen atom or a hydrocarbon group, n is an integer of 0-6, and when n is 2 or more, each R ³ may be the same or different, and a plurality of R ³ Together may form a condensed aromatic hydrocarbon ring group, and X- represents a halide ion, a sulfonate ion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B ( C ₆ F ₅ ) ₄ ⁻ or an anion selected from Ga (C ₆ F ₅ ) ₄ ^— .
Here, the hydrocarbon group for R ³ is not particularly limited, and preferred examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, and an aryl group. Here, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, isopropyl group. And straight chain or branched chain groups such as a group, an isobutyl group, a 1-methylpropyl group, and a 2-ethylhexyl group. Further, the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Further, the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms, specifically, vinyl group, 2-methylvinyl group, butadiene-1-yl group, butadiene-2- Yl group, cyclohexen-3-yl group and the like. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 8 carbon atoms. Specific examples include ethynyl group, propyn-1-yl group, and 1-butyn-1-yl group. It is done. Furthermore, the aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms constituting the aromatic ring, and specifically includes a phenyl group, naphthalen-1-yl group, naphthalene-2- Yl group, anthracene-9-yl group and the like. Among these hydrocarbon groups, an alkyl group is particularly preferable, and one having 1 to 3 carbon atoms is most preferable. These may each have one or more substituents, specifically, alkoxy groups such as methoxy group and ethoxy group, acyl groups such as acetyl group and propionyl group, acetoxy group and propionyloxy group An acyloxy group, a halogen atom such as a fluorine atom or a chlorine atom.

N is an integer of 0 to 6, more preferably an integer of 0 to ^3. When n is 2 or more, each R ³ may be the same or different. Further, when n is 2 or more, a plurality of R ³ (usually alkenyl groups) together form an aromatic hydrocarbon ring group, and R ³ is condensed with the substituted benzene ring. It may be.

In the present invention, b) the iron arene complex is particularly preferably used because it has excellent solubility in the polymerizable monomer, and X- in the above formula (1) is BF ₄ ⁻ or PF _{6. ^{-, AsF 6 -, SbF 6}} -, B (C 6 F 5) 4 -, or _{Ga (C 6 F 5) 4} - is. Specific examples of such compounds

Among them, the compound represented by the following formula is most preferable because it has excellent solubility and is less colored after curing.

  The compounding quantity of these iron arene complexes is 0.01-10 mass parts with respect to 100 mass parts of all the polymerizable monomers, More preferably, it is 0.1-5 mass parts.

  Two or more of these iron arene complexes may be used in combination.

  The c) organic peroxide in the present invention is not particularly limited, and conventionally known ones can be used without any limitation. As typical organic peroxides, known hydroperoxides, peroxyketals, ketone peroxides, alkylsilyl peroxides, diacyl peroxides, peroxyesters, and the like can be used.

  Among them, since the reactivity with the iron arene complex is higher, the following formula 2)

(R ¹ is an alkyl group, and R ² is a hydrogen atom or a trialkylsilyl group.)
An organic oxide represented by is more preferable.

Here, the alkyl group of R ¹ preferably has 1 to 20 carbon atoms. Specifically, primary alkyl groups such as methyl group, ethyl group, propyl group and butyl group; secondary alkyl groups such as isopropyl group and 1-methylpropyl group; t-butyl group and 1,1-dimethylethyl group And tertiary alkyl groups such as cyclohexyldimethylmethyl group, 1,1, -dimethylbutyl group and 1,1,3,3-tetramethylbutyl group. Among these alkyl groups, those having 1 to 5 carbon atoms are more preferable. These alkyl groups may further have a substituent, and specific examples include alkenyl groups such as vinyl groups, and aryl groups such as phenyl groups and tolyl groups. Furthermore, the substituent may be a hydroperoxide group or a silyl peroxide group. In this case, the organic oxide represented by the formula (3) has a plurality of peroxides in the same molecule. Become. Further, R ² is preferably a trialkylsilyl group in which each alkyl group has 1 to 5 carbon atoms, and specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.

  Specific examples of such organic peroxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane 2,5 -Dihydroperoxide, cumene hydroperoxide, 1,1-dimethylbutyl hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyltrimethylsilyl peroxide, 1 , 1-dimethylbutyltrimethylsilyl peroxide and the like. Of these, hydroperoxide is most preferred.

  The amount of the organic peroxide is not particularly limited, but is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the total polymerizable monomer. Most preferably, it is 0.5-5 mass parts.

  These organic oxides may be used in combination of two or more.

  The adhesive composition of the present invention may contain d) water in order to promote decalcification of the tooth. The water preferably contains substantially no impurities harmful to storage stability, biocompatibility and adhesiveness, and examples include deionized water and distilled water.

  The blending amount of the water is not particularly limited, but is preferably 5 to 900 parts by mass with respect to 100 parts by mass of the total polymerizable monomer in the adhesive composition. It is more preferable that

  In addition, when the adhesive composition of the present invention is applied to the tooth surface, these waters are usually used after being removed by air blowing before the adhesive composition is cured.

  In the adhesive composition of the present invention, other polymerization initiators may be blended. In particular, when used as a dental adhesive, a photopolymerization initiator is preferred because it can be polymerized and cured at an arbitrary timing. Photopolymerization initiators include α-diketones such as camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, 2,4 -Thioxanthones such as diethylthioxanthone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, 2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1- ( 4-morpholinophenyl) -pentanone-1,2-benzyl-die Α-aminoacetophenones such as tilamino-1- (4-morpholinophenyl) -pentanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Acylphosphine oxide derivatives such as trimethylpentylphosphine oxide are preferably used.

  These photopolymerization initiators are preferably used in combination with a polymerization accelerator. As the polymerization accelerator, N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, 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-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N -Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, -Dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethyl Tertiary amines such as aminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, barbituric acids such as 5-butyl barbituric acid, 1-benzyl-5-phenylbarbituric acid, dodecyl mercaptan, penta Erythritol Tet It can be exemplified mercapto compound such as tetrakis (thioglycolate).

  In particular, when α-diketones such as camphorquinone are used as other polymerization initiators, it is usual to use tertiary amines as polymerization accelerators.

  The blending amount of such other polymerization initiator is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer component.

  Furthermore, in addition to the polymerization initiator and the polymerization accelerator, an electron acceptor such as an iodonium salt, trihalomethyl-substituted S-triazine, or phenanthylsulfonium salt compound may be added.

  Moreover, when using as a dental adhesive, it is possible to add an inorganic filler. Examples of the inorganic filler include silica, zirconia, titania, silica / zirconia, silica / titania, and fluoroaluminosilicate glass.

  These inorganic fillers can be hydrophobized with a surface treatment agent typified by a silane coupling agent, thereby improving compatibility with the polymerizable monomer and improving mechanical strength and water resistance. The hydrophobization method may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, etc. hexamethyldisilazane is preferably used.

  The compounding quantity of these inorganic fillers is the range of 2-400 mass parts normally with respect to 100 mass parts of polymerizable monomer components, More preferably, it is 5-100 mass parts. When adjusting especially as a composite resin adhesive, it is the range of 2-50 mass parts, More preferably, it is 5-30 mass parts.

  Moreover, a volatile organic solvent may be mix | blended with these adhesive compositions. Here, as the volatile organic solvent, those which are volatile at room temperature and water-soluble can be used. The term “volatile” as used herein means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. The term “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more, and it is preferably compatible with water at 20 ° C. in an arbitrary ratio. Examples of such volatile water-soluble organic solvents include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable.

  The compounding amount of these volatile organic solvents is usually in the range of 2 to 400 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer component.

  These volatile organic solvents are also used by removing by air blowing before the adhesive composition is cured when the adhesive composition of the present invention is applied to the tooth surface, similarly to the water. Is done.

  Furthermore, in the adhesive composition of the present invention, an organic thickening material such as a polymer compound such as polyvinyl pyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, or the like is used as long as it does not deteriorate the performance of the adhesive composition of the present invention, if necessary. It is possible to add. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and used as necessary.

Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples. Abbreviations and abbreviations shown in the examples are as follows.
Abbreviations and abbreviations [acidic group-containing polymerizable monomers derived from phosphoric acid]
PM1: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate PM: 2: 1 mixture of PM1 and PM2 MDP: 10-methacryloyloxydecyl dihydrogen phosphate [others Acidic group-containing polymerizable monomer]
MAC-10: 11- (Meth) acryloyloxyethyl-1,1-undecanedicarboxylic acid [polymerizable monomer containing no acidic group]
BisGMA: 2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate [volatile water-soluble organic solvent]
IPA: isopropyl alcohol [iron arene complex]
CPF: (η ⁶ -cumene) (η ⁵ -cyclopentadien-1-yl) iron (II) hexafluorophosphate

[Organic peroxide]
POH: 1,1,3,3-tetramethylbutyl hydroperoxide PUH: cumene hydroperoxide PBS: t-butyltrimethylsilyl peroxide [other photopolymerization initiator]
CQ: camphorquinone TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BTPO: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide CPT: bis (η ⁵ -2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (IV)
[Tertiary amine]
DMBE: ethyl 4-dimethylaminobenzoate DMEM: 2-dimethylaminoethyl methacrylate [polymerization inhibitor]
BHT: 2,6-di-t-butyl-p-cresol

In the following examples and comparative examples, various measurements were performed by the following methods.
(1) Adhesion test method The bovine front teeth were removed within 24 hours after slaughtering, and the enamel and dentin planes were cut out with a # 600 emery paper so as to be parallel to the labial surface in the water. Next, these surfaces were dried by blowing compressed air for about 10 seconds, and then a double-sided tape with a 3 mm diameter hole was fixed to either the enamel or dentin plane, and then the thickness was 0.5 mm. A paraffin wax having an 8 mm hole was fixed on the circular hole so as to be in the same center, thereby forming a simulated cavity. A composite resin adhesive is applied to the simulated cavity and left to stand for 20 seconds. The compressed air is blown for about 10 seconds to dry, and the dental LED visible light irradiator (LE Demetron, manufactured by Kerr) is used. Irradiated with light for 10 seconds. Further, a dental composite resin (Estellite 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, which was stored in 37 ° C. water overnight.

After that, using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), the tensile strength was measured at a crosshead speed of 2 mm / min, and the tensile bond strength between the enamel or dentin and the composite resin was measured. Four tensile bond strengths per test were measured by the above method, and the average value was defined as the bond strength.
(2) Bending strength measurement method Remove water and organic solvent from the composite resin adhesive with a rotary evaporator, then pour it into a 2mm x 2mm x 25mm polytetrafluoroethylene mold and insert it between PP sheets. Using an LED visible light irradiator (LE Demetron, manufactured by Kerr), each of the three front and back surfaces was irradiated with light for 10 seconds. The obtained cured product was stored in 37 ° C. water overnight.

  Thereafter, a three-point bending strength was measured using a universal testing machine (Autograph, manufactured by Shimadzu Corporation) at a crosshead speed of 1 mm / min and a distance between supporting points of 20 mm. For each test, five three-point bending strengths were measured by the above method, and the average value was taken as the bending strength.

Example 1
2.5 g PM as a polymerizable monomer, 3.0 g BisGMA, 2.0 g 3G and 2.5 g HEMA, 0.1 g CPF as a polymerization initiator, 0.15 g POH, 1 Using 0.5 g of distilled water and 0.03 parts by mass of BHT as other components, these were stirred and mixed for 3 hours to obtain an adhesive for composite resin comprising the adhesive composition of the present invention.

  The adhesive was subjected to bending strength measurement and adhesion test. The composition of the adhesive and the evaluation results are shown in Table 1.

Examples 2-8
In accordance with the method of Example 1, adhesives having different compositions shown in Table 1 were prepared.

  The obtained adhesive for composite resin was subjected to bending strength measurement and adhesion test. The composition and results of the adhesive are shown in Table 1.

Comparative Examples 1-13
In accordance with the method of Example 1, adhesives having different compositions were prepared. The obtained adhesive for composite resin was subjected to bending strength measurement and adhesion test. The composition and results of the adhesive are shown in Table 2.

  Comparative Example 9 is an adhesive using, as a polymerization initiator, POH, which is a chemical polymerization initiator alone, without being combined with a photopolymerization initiator, and an adhesion test was performed in the dental adhesion in a simulated cavity. The material was applied, allowed to stand for 20 seconds, dried by blowing compressed air for about 10 seconds, and then allowed to harden by standing at 37 ° C. for 10 minutes. Moreover, since Comparative Examples 11-13 did not contain an acidic group-containing polymerizable monomer and was not an adhesive composition, no adhesion test was performed.

  Examples 1-8 are those in which an iron arene complex and an organic peroxide are blended as a photopolymerization initiator composition, but the cured body has good bending strength, and the result of the adhesion test is It was good for both enamel and dentin.

  On the other hand, Comparative Examples 1 to 4 are those in which camphorquinone and tertiary amine are blended as the photopolymerization initiator composition, but the result of the adhesion test is either enamel or dentin. On the other hand, it was inferior to the case where an iron arene complex and an organic peroxide were used. Moreover, also in bending strength, it was inferior compared with the adhesive composition using an iron arene complex and an organic peroxide.

  Comparative Examples 5 and 6 are those in which a phosphorus polymerization initiator is blended as a photopolymerization initiator composition. In the LED irradiator used in this test, the results of the adhesion test are enamel and dentin. Both of these were inferior to the case of using an iron arene complex and an organic peroxide. Moreover, also in bending strength, it was inferior compared with the adhesive composition using an iron arene complex and an organic peroxide.

  In Comparative Example 7, a phosphoric polymerization initiator and an organic peroxide were blended as a photopolymerization initiator composition. In the LED irradiator used in this test, the result of the adhesion test was enamel. , And dentin were inferior to those using iron arene complex and organic peroxide. Moreover, also in bending strength, it was inferior compared with the adhesive composition using an iron arene complex and an organic peroxide.

  In Comparative Example 8, a titanocene polymerization initiator was blended as a photopolymerization initiator composition. The results of the adhesion test showed that the iron arene complex and the organic peroxidation were obtained for both enamel and dentin. It was inferior compared with the case where a thing was used. Moreover, also in bending strength, it was inferior compared with the adhesive composition using an iron arene complex and an organic peroxide.

  In Comparative Example 9, a photopolymerization initiator was not used and only an organic peroxide was blended. The result of the adhesion test was that the iron arene complex was used for both enamel and dentin. It was inferior compared with the case where it was used in combination. Moreover, since the cured product was not obtained, the bending strength could not be measured.

  In Comparative Example 10, only the iron arene complex was blended as the photopolymerization initiator composition, but the result of the adhesion test was that the organic peroxide was used for both enamel and dentin. It was inferior to. Moreover, since the cured product was not obtained, the bending strength could not be measured.

  In Comparative Example 11, an acidic group-containing polymerizable monomer was not blended as a polymerizable monomer, and camphorquinone and a tertiary amine were blended as a photopolymerization initiator composition. The bending strength was higher than when the acidic group-containing polymerizable monomer was blended (Comparative Example 3), but was still significantly inferior to each of the Examples.

  In Comparative Example 12, an acidic group-containing polymerizable monomer was not blended as a polymerizable monomer, and a phosphorus polymerization initiator was blended as a photopolymerization initiator composition, but the bending strength of the cured product was It was only the same as the case where the acidic group-containing polymerizable monomer was blended.

  In Comparative Example 13, an acidic group-containing polymerizable monomer was not blended as a polymerizable monomer, and an iron arene complex and an organic peroxide were blended as a photopolymerization initiator composition. It was greatly inferior to each Example which mix | blended the polymerizable monomer.

Claims (4)

A dental adhesive composition comprising a) an acidic group-containing polymerizable monomer, b) an iron arene complex, and c) an organic peroxide. The dental adhesive composition according to claim 1, wherein b) the iron arene complex is a compound represented by the following formula 1).

(R ³ is a hydrogen atom or a hydrocarbon group, n is an integer of 0-6, and when n is 2 or more, each R ³ may be the same or different, and a plurality of R ³ Together may form a condensed aromatic hydrocarbon ring group, and X ⁻ represents a halide ion, a sulfonate ion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B ( C ₆ F ₅ ) ₄ ⁻ or an anion selected from Ga (C ₆ F ₅ ) ₄ ^— . The dental adhesive composition according to claim 1 or 2, wherein c) the organic peroxide is a compound represented by the following formula 2).

(R ¹ is an alkyl group, and R ² is a hydrogen atom or a trialkylsilyl group.) The dental adhesive composition according to any one of claims 1 to 3, further comprising d) water.