JP4596786B2 - Photo-curable dental composite restorative material - Google Patents

Description

  The present invention relates to a photocurable dental composite restorative material, and more particularly to a composite restorative material excellent in physical properties of a cured body such as bending strength despite a low proportion of filler.

  In the field of dental treatment, especially as a material for repairing teeth lost due to caries, etc., composite restorative material (generally called composite resin), that is, curable composition mainly composed of polymerizable monomer and filler There is a thing.

  Such a photo-curable dental composite restorative material is widely used in dental treatment because it can provide a color tone equivalent to a natural tooth color and is easy to operate. Conventionally, such a photocurable dental composite restorative material has been mainly used for filling and repairing relatively large carious cavities such as a crown, and is based on 100 parts by weight of a polymerizable monomer. Most of them were blended with about 300 to 1000 parts by mass of filler. This is because the occlusal pressure associated with mastication or the like is applied in the oral cavity, so that if the blending ratio of the filler is small, the strength is inferior and breakage and wear are likely to occur. A composite restorative material with such a high blending ratio of the filler inevitably increases its viscosity. However, when treating the crown part as described above, dripping or flow due to its own weight due to the ease of form formation. It was more desirable to have less.

  However, unlike caries in the crown, in caries treatment or hypersensitivity treatment in the cervical and root parts, it is easy to reach the pulp when a deep cavity is formed, so a cavity cannot be formed or a cavity is formed. I have to make it shallow. Furthermore, since the crown is covered with a thick enamel, tooth pain is unlikely to occur, and it is difficult to detect or start treatment until it becomes a fairly large caries, whereas the dentine is exposed with slight caries. In the cervical region or the root portion, tooth pain that is likely to require active treatment is likely to occur at an early stage, which is a major factor in the treatment in a cavity or a shallow cavity. Therefore, in order not to adversely affect the masticatory function or create a feeling of strangeness in the oral cavity, it is necessary to reduce the coating thickness of the restoration in order to restore the shape close to the shape originally possessed by the tooth. There is.

  In general, in order to apply some composition thinly, the viscosity has a great influence, and the lower the viscosity, the thinner. For composite restorative materials composed of a polymerizable monomer and a filler, it is most effective to reduce the blending ratio of the filler in order to reduce the viscosity. Some composite restoration materials useful for coating of parts have a blending amount of filler of about 100 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer (for example, Patent Documents) 1-3).

  However, if the blending ratio of the filler in such a composite restorative material is reduced, the strength is inferior and problems such as breakage and wear may occur.

On the other hand, the dental composite restorative material is used by filling the composite restorative material into a tooth in an uncured paste state and molding it after being irradiated with light by a dental light irradiator or the like ( Hereinafter, the light irradiated for polymerization and curing is also referred to as “irradiation light.” In general, such irradiation has a light intensity in the wavelength range of about 360 to 500 nm, which is the main absorption range of the α-diketone compound, of 100 to 1500 mW / (Use a light source with an output of about cm ² from a distance of about 0 to 10 mm) (for example, Non-Patent Document 1).

  Such a composite restorative material is mixed with a photopolymerization initiator that generates radicals or ionic species by light irradiation and polymerizes a polymerizable unsaturated compound or cyclic compound. Proposals have been made. In general, a compound that absorbs light and decomposes itself to generate a polymerization active species, and a system in which an appropriate sensitizer is combined are widely studied and used.

  Acylphosphine oxide compounds and α-diketone compounds are known as the former examples, and combinations of α-diketone compounds and tertiary amine compounds are well known and usefully used as the latter examples. Yes.

  In addition to the above acylphosphine oxide compounds and α-diketone compounds, various photopolymerization initiators have been studied and proposed, and aryliodonium salts, sensitizers, and electron donors are used as polymerization initiator components. It is known (for example, see Patent Documents 4 and 5).

  The photopolymerization initiator comprising the aryl iodonium salt, the sensitizer and the electron donor can be used as a polymerization initiator of a curable composition containing a large amount of a filler, and has a curing rate and a curing rate as compared with other polymerization initiators. Although it is known that a composition excellent in depth, storage stability, and the like can be obtained, it is not known what effect it has on the strength of the cured body.

Edited by Hiroyasu Hosoda, “Fundamental and Clinical Study of Photopolymerization Type Composite Restoration Materials”, Nippon Dental Press, February 10, 1986, p. 9-20 Japanese Patent Laid-Open No. 3-76702 JP 11-335220 A JP 2001-139411 A JP-A-63-273602 USP 5,545,676

  The present invention is a dental photo-curing type containing a filler of 100 to 300 parts by mass with respect to 100 parts by mass of a polymerizable monomer having an appropriate viscosity applicable to root caries and shallow cavities. The purpose of the composite restorative material is to solve the problem that the strength is significantly lower than those with a higher filler content, and to provide a photocurable dental composite restorative material that is less likely to break or wear. It is what.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors completed the present invention by finding that even a composite restoration material having a low blending ratio of the filler exhibits high strength by adopting a specific photopolymerization initiator system.

That is, the present invention relates to (A) light comprising 100 parts by mass of a radically polymerizable monomer and (B) 100 to 300 parts by mass of a filler and (C) an effective amount of a photopolymerization initiator. In curable dental composite restorative materials,
The (C) photopolymerization initiator is
(C-1) Diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-methoxyphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium , A cation selected from bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, and p-phenoxyphenylphenyliodonium, chloride, bromide Benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, Kisa fluorophosphate, hexafluoroarsenate, and aryl iodonium salt is a salt comprising a anion selected from hexafluoroantimonate,
(C-2) a compound for photosensitization comprising an α-diketone compound ,
(C-3) A photocurable dental composite restorative material comprising an amine compound.

  According to the present invention, even when it is necessary to reduce the thickness of the restorative material for the treatment of the tooth neck, root, etc., the blending ratio of the filler is relatively set in order to obtain good operability (low viscosity). Therefore, even if the composite restorative material is reduced in number, a photo-curing dental composite restorative material that exhibits good cured body strength with little possibility of breakage or wear is provided.

  The photocurable dental composite restorative material of the present invention comprises a radical polymerizable monomer, a filler and a photopolymerization initiator. As the radical polymerizable monomer, a known radical polymerizable monomer is used without any limitation as a component of the dental composite restorative material, but in general, from the viewpoint of curing speed and mechanical properties of the cured body. Therefore, a (meth) acrylate-based polymerizable monomer is preferably used, and a polyfunctional (meth) acrylate-based polymerizable monomer having a plurality of polymerizable functional groups is particularly preferable. As the polyfunctional (meth) acrylate polymerizable monomer, known ones can be used without particular limitation. Examples of those generally used preferably include those shown in the following (I) to (III).

(I) Bifunctional polymerizable monomer (i) Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxy Phenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (hereinafter referred to as D-2. 6E), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxy) Phenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propyl Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and diisocyanates Diaducts obtained from addition with a diisocyanate compound having an aromatic group such as methylbenzene and 4,4′-diphenylmethane diisocyanate.

(Ii) Aliphatic compound-based ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate Such as methacrylates or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and hexamethylene Diadducts obtained from adducts with diisocyanate compounds such as isocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2-hydroxy Propoxy) ethyl and the like.

(II) Trifunctional polymerizable monomer Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

(III) Tetrafunctional polymerizable monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4 Diadduct obtained from an adduct of a diisocyanate compound such as 1,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  These polyfunctional (meth) acrylate polymerizable monomers may be used in combination of a plurality of types as required.

  Further, if necessary, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. A polymerizable monomer other than the above-mentioned (meth) acrylate monomer may be used. Examples of these other polymerizable monomers include fumaric acid esters such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, or α -Methyl styrene derivatives; allyl compounds such as diallyl terephthalate, diallyl phthalate, diallyl diglycol carbonate, and the like. These monofunctional (meth) acrylate monomers and other polymerizable monomers can be used alone or in combination of two or more.

  Considering that the photocurable dental composite restorative material of the present invention is used in the oral cavity, in the total polymerizable monomer to be blended, in terms of excellent mechanical strength and water resistance of the obtained cured product, The polyfunctional (meth) acrylate polymerizable monomer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

  The second component in the photocurable dental composite restorative material of the present invention is (B) filler, and the addition amount thereof is 100 to 300 mass with respect to 100 mass parts of the radically polymerizable monomer of component (A). Part. In order to reduce the polymerization shrinkage, improve the strength of the cured product, and develop a certain degree of viscosity to improve the operability, 100 mass parts per 100 mass parts of the radical polymerizable monomer. Blend more than part of filler. On the other hand, if it exceeds 300 parts by mass, the viscosity of the composition becomes so high that it is difficult to apply the composition thinly, and operability at the time of restoration of the tooth neck portion or crown portion cannot be obtained. More preferably, it is 120-250 mass parts with respect to 100 mass parts of radically polymerizable monomers.

  As the filler, known fillers can be used without any limitation as fillers for dental composite restorative materials. Examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, Examples thereof include metal oxides such as lanthanum glass, barium glass, and strontium glass. If necessary, a known cation-eluting inorganic filler such as silicate glass and fluoroaluminosilicate glass may be blended as a dental inorganic filler. These may be used alone or in combination of two or more.

  Moreover, you may use the granular organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers beforehand, making it paste-form, polymerizing, and grind | pulverizing.

  The particle size of these fillers is not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm (particularly preferably 0.01 to 5 μm) generally used as dental materials are used depending on the purpose. It can be used as appropriate. Further, the refractive index of the filler is not particularly limited, and those in the range of 1.4 to 1.7 which a general dental inorganic filler has can be used without limitation, and can be appropriately set according to the purpose. Good. You may use together several inorganic fillers from which a particle size range and refractive index differ.

  Furthermore, the use of spherical inorganic fillers among the above fillers improves the fluidity of the composite restorative material before curing, increases the surface smoothness of the resulting cured product, and improves the excellent dental composite restoration. Can be a material. Particularly preferred is the use of spherical inorganic particles having an average particle size in the range of 0.01 μm to 5 μm.

  It is desirable to treat the inorganic filler with a surface treating agent typified by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment method may be performed by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.

  The greatest feature of the photocurable dental composite restorative material of the present invention is that the photopolymerization initiator comprises (C-1) aryl iodonium salt, (C-2) photosensitizing compound, and (C-3) amine compound. The point is to use. As the photopolymerization initiator, those described in JP-A-63-273602 can be used, and specifically described as follows.

The first component in the photopolymerization initiator is (C-1) aryl iodonium salt. Examples of the aryliodonium salt include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-methoxyphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methyl. A cation selected from phenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, and p-phenoxyphenylphenyliodonium; , Bromide, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis Orofeniru) borate, hexafluorophosphate, hexafluoroarsenate, and salt composed of an anion selected from hexafluoroantimonate is used.

  Among these aryliodonium salts, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate are used from the viewpoint of solubility in radical polymerizable monomers. , Hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate salts are preferred, and tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) gallate and hexafluoroantimonate salts are particularly preferred from the viewpoint of storage stability. Is preferred. These aryl iodonium salts may be used alone or in combination of two or more.

  The amount of the aryliodonium salt used is not particularly limited as long as it can be polymerized by light irradiation depending on the type and amount of the photosensitizing compound or amine compound to be combined. It is preferable that it is 0.001-10 mass parts with respect to 100 mass parts, and it is more preferable that it is 0.05-5 mass parts.

The compound (C-2) for photosensitization in the present invention has a maximum absorption wavelength of 350 to 700 nm , preferably a maximum absorption wavelength of 400 to 650 nm, and a monomer (polymerizable monomer) or the like by irradiation with visible light. An α-diketone compound is used as a sensitizer that causes energy transfer or electron transfer with the substance and generates an active species effective for polymerization .

Specific examples of the α-diketone compound suitably used as the photosensitizing compound in the present invention include camphorquinone, 9,10-phenanthrenequinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2 , 3-octadione, 4,4-dimethoxybenzyl, acenaphthenequinone and the like .

  As the (C-3) amine compound in the present invention, any known amine compound can be used without any limitation, and examples thereof include primary amines, secondary amines and tertiary amines. In view of the above, a tertiary amine compound is 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, the following general formula (1) shows that it exhibits high polymerization activity, maintains stability to ambient light and polymerization curability in a short time by irradiation light, and can exhibit high cured product properties. It is more preferable to use the aromatic tertiary amine compound shown by these.

(In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
In general formula (1), R ₁ and R ₂ are each independently 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 (1), R ₃ 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 above formula include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine 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, The curing rate can be made faster than when only the amine compound is used.

  Most preferably, it is a combination of an aromatic tertiary amine compound represented by the general formula (1) and a tertiary aliphatic amine compound having a radical polymerizable functional group.

  The ratio of the amine compound in the photopolymerization initiator of the present invention is usually 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the polymerizable monomer. . Further, in the present invention, it is preferable to use both of the aromatic amine compound and the aliphatic amine compound, rather than using each independently, and the blending ratio is aromatic amine: aliphatic amine = 1: 99 to 99: 1. And more preferably in the range of 3:97 to 97: 3.

  The photocurable dental composite restorative material of the present invention may contain pigments, fluorescent pigments, dyes, ultraviolet absorbers to prevent discoloration to ultraviolet rays in order to match the color tone of the teeth, and other dental use You may mix | blend a well-known additive as a component of a composite restoration material in the range which does not affect the effect of this invention.

  Furthermore, you may mix | blend other well-known polymerization initiator components in the photocurable dental composite restorative material of this invention in the range which does not impair the effect of this invention. Examples of the other polymerization initiator components include amine compounds such as aliphatic amine compounds and aromatic amine compounds; organic peroxides such as benzoyl peroxide and cumene hydroperoxide; vanadium oxide (IV) acetylacetonate; + IV or + V vanadium compounds such as bis (maltolate) oxovanadium (IV); tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) ) Aryl borate compounds such as sodium boron and butyltri (p-fluorophenyl) boron sodium; coumarin dyes such as 3,3′-carbonylbis (7-diethylamino) coumarin and 7-hydroxy-4-methyl-coumarin; Screw (2, 4, 6 Acylphosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, etc. Benzoin alkyl ethers; thioxanthone derivatives such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone; benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone, etc. Examples include benzophenone derivatives. However, in order to obtain high ambient light stability, it is preferable that the aryl borate compounds and the organic peroxide be as small as possible. In addition, when the pigments such as coumarin-based pigments are blended in such an amount that they act as polymerization initiators, they greatly affect the color tone of the photopolymerizable composition, and a dental composite restorative material that requires high aesthetics. Tends to have a color tone different from that of teeth.

  In addition, the photocurable dental composite restorative material of the present invention can be blended with other components known as blending components for dental composite restorative materials within a range in which the performance is not lowered depending on the purpose. Examples of such components include coloring components such as pigments and dyes, polymerization inhibitors, polymerization inhibitors, and ultraviolet absorbers.

  The method for producing such a photopolymerizable composite restorative material is not particularly limited, and any known method for producing a photopolymerizable composite restorative material may be followed. In general, a predetermined amount of each component to be blended may be weighed out under light shielding and kneaded until uniform.

  When the photocurable dental composite restorative material of the present invention is cured, a visible light irradiator generally used for dentistry may be used in accordance with a common method. Examples of the light source of the light irradiator include a light source such as a halogen lamp, a xenon lamp, a laser diode, a metal halide lamp, a helium cadmium laser, and an argon laser, preferably a halogen lamp, a xenon lamp, and a laser diode. Since the irradiation time varies depending on the wavelength and intensity of the light source and the shape and material of the cured body, it may be determined in advance through preliminary experiments.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the abbreviations (in parentheses) of the compounds used in the following Examples and Comparative Examples are shown below.

(1) Abbreviations and abbreviations (A) Radical polymerizable monomers, 2,2-bis [(3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane (bis-GMA)
2,2-bis (4- (methacryloyloxypolyethoxyphenyl) propane (D2.6E)
・ Triethylene glycol dimethacrylate (3G)
1,6-bis (methacrylethyloxycarbonylamino) trimethylhexane (UDMA)
(B) Filler / spherical silica-zirconia, γ-methacryloyloxytrimethoxysilane surface-treated product; average particle size: 0.5 μm (E-1)
Spherical silica-titania, γ-methacryloyloxytrimethoxysilane surface-treated product; average particle size: 0.08 μm (E-2)
(C) Photopolymerization initiator (C-1) aryl iodonium salt / diphenyl iodonium hexafluorophosphate (Ph2IPF6)
(C-2) Photosensitizing compound / camphorquinone (CQ)
(C-3) Amine compound / triethanolamine (TEOA)
N, N-dimethyl p-ethyl benzoate (DMBE)
・ N, N-dimethyl p-toluidine (DMPT)
(D) Other components ・ Hydroquinone monomethyl ether (HQME)
Moreover, the following methods were used for the measurement of the preparation method of photocurable composite restorative material, curing characteristics (environmental light stability, curing time, hardness), mechanical strength and storage stability of the cured product.

(1) Preparation method of photocurable composite restoration material A predetermined amount of a photopolymerization initiator and an inorganic filler were added to a polymerizable monomer, and the mixture was uniformly stirred and degassed under red light.

(2) Hardness of cured body (Vickers hardness)
The hardness of the cured product was measured by the following method using the following three types of dental light irradiators. That is, a polytetrafluoroethylene mold having a hole of 6 mmφ × 1.0 mm is filled with a paste and pressed with a polypropylene film, a Toxo power light is used as a dental light irradiator, and the irradiator is applied to the polypropylene film. It adhered and irradiated for the predetermined time, and the hardening body was prepared. The obtained cured product was obtained from the diagonal length of the indentation formed in the test piece with a load of 100 gf and a load holding time of 30 seconds using a Vickers indenter with a micro hardness tester (MHT-1 type manufactured by Matsuzawa Seiki Co., Ltd.). {Tokuso Power Light: light output density 700 mW / cm 2, light intensity 640 to 650 mW / cm 2 on irradiated surface, light source is halogen lamp, 30 seconds irradiation, Tokuyama Dental Co., Ltd.}
(3) Bending strength Tosso Powerlite is filled with a curable composition in a stainless steel formwork and pressed with polypropylene for 30 seconds x 3 times from one side, changing the location so that the entire surface is exposed to light. And was irradiated with light in close contact with polypropylene. Subsequently, the opposite surface was similarly adhered to polypropylene 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). The 3-point bending fracture strength was measured at 1 mm / min.

Example 1
Bis-GMA (60 parts by mass) and 3G (40 parts by mass), Ph2IPF6 (0.5 parts by mass), amine (0.5 parts by mass), CQ (0.3 parts by mass) and polymerization inhibition as polymerization initiators 0.15 parts by mass of HQME was added as an agent and dissolved in the dark to obtain a uniform solution. This solution 100 and the inorganic fillers E-1 and E-2 are mixed so that the polymerizable monomer has a ratio of 100 parts by mass, E-1 has 140 parts by mass, and E-2 has a ratio of 60 parts by mass. The mixture was mixed using a mortar to obtain a paste-like photocurable composition. This paste was polymerized and cured under predetermined conditions, and the Vickers hardness and bending strength of the obtained cured product were measured. The results are shown in Table 1.

Examples 2 to 5, Comparative Examples 1 to 5, Reference Examples 1 to 4
A photocurable composition was prepared and evaluated using the polymerizable monomer, filler, and polymerization initiator composition described in Table 1 in the same manner as in Example 1, and the results are shown in Table 1. Further, FIG. 1 shows the relationship between the filler blending ratio and the cured product bending strength in each of Examples 1 to 3, Comparative Examples 1, 3, 5 and Reference Examples 1 to 4, and FIG. 2 shows the relationship with Vickers hardness. (Except for Examples 4 and 5 having different polymerizable monomer compositions).

  As shown in Table 1 and FIGS. 1 and 2, when the blending ratio of the filler is as large as 350 to 400 parts by mass with respect to 100 parts by mass of the polymerizable monomer (out of the scope of the present invention), Initiation of α-diketone / tertiary amine photopolymerization which has been conventionally used as a polymerization initiator for dental composite restorative materials even in the case of aryliodonium salt / photosensitizer / amine compound photoinitiators in the present invention There is no difference in bending strength and Vickers hardness even with the agent. However, when the amount is less than 300 parts by mass, there is a sharp difference, and the aryliodonium salt / photosensitizing compound / amine compound-based photopolymerization initiator exhibits a remarkable effect when the blending ratio of the filler is small. It is clear.

The graph which shows the compounding ratio of a filler, and the relationship of bending strength in an Example, a comparative example, and a reference example. The graph which shows the relationship of the mixture ratio of a filler in a Example, a comparative example, and a reference example, and Vickers hardness.

Claims (2)

(A) A photocurable dental composite restoration comprising (B) 100 to 300 parts by mass of a filler and (C) an effective amount of a photopolymerization initiator with respect to 100 parts by mass of a radically polymerizable monomer. In the material,
The (C) photopolymerization initiator is
(C-1) Diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-methoxyphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium , A cation selected from bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, and p-phenoxyphenylphenyliodonium, chloride, bromide Benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, Kisa fluorophosphate, hexafluoroarsenate, and aryl iodonium salt is a salt comprising a anion selected from hexafluoroantimonate,
(C-2) a compound for photosensitization comprising an α-diketone compound ,
(C-3) A photocurable dental composite restorative material comprising an amine compound. (B) The photocurable dental composite restorative material according to claim 1, wherein the filler is spherical inorganic particles having an average particle diameter in the range of 0.01 μm to 5 μm.

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