JP5968128B2 - Dental photopolymerizable composition - Google Patents

Description

  The present invention relates to a dental photopolymerizable composition, and particularly to a dental photopolymerizable composition useful as a dental restorative material.

Various dental restorative materials are used in dental treatment. For example,
In the restoration of teeth damaged by caries, fractures, etc., a paste-like photocurable filling and restoration material generally called a composite resin is widely used because of its ease of operation and high aesthetics. Such a composite resin is usually composed of a polymerizable monomer, a filler, and a photopolymerization initiator.

In the field of dental treatment, it is difficult to use a photopolymerization initiator having activity in the ultraviolet region due to its harm to the living body, and therefore photopolymerization initiators having activity in the visible light region are mainly used. . The photopolymerization initiator may be a compound that absorbs light such as α-diketone or acylphosphine oxide and decomposes itself to produce a polymerization active species, and further a suitable sensitization such as a tertiary amine compound. Systems that combine agents are widely studied and used. The treatment method using a photo-curing type dental restoration material is filled with a photo-curing filling restoration material into the cavity of the tooth to be restored and shaped into a tooth shape, and then activated using a dedicated light irradiator. Teeth are repaired by irradiating and curing light (hereinafter, light irradiated for such polymerization and curing may be referred to as “active light”). In general, such actinic light uses a light source having an output power of about 100 to 1500 mW / cm ^{2 in} a wavelength range of about 380 to 500 nm (which is the main absorption range of the α-diketone compound), and is 0 to 10 mm. Irradiated from a certain distance.

  The dental restorative material is filled in the patient's mouth and then polymerized and cured by light irradiation. Therefore, if the irradiation time of the active light for polymerization is made long, there is a problem that not only the operation takes time but also a great burden is imposed on the patient, and the irradiation time (curing time) of the active light is shortened. It is requested. One technique for shortening the curing time is to increase the amount of photopolymerization initiator. However, a cured body of a dental restorative material with a large amount of photopolymerization initiator is greatly colored (discolored) in a relatively short time when exposed to ultraviolet light such as sunlight. When the hardened body changes color, it shifts from the color tone adjusted at the time of restoration, so that the initial aesthetics are lost and the demands required as a dental restoration material cannot be satisfied. For example, JIS T 6514 requires that even if the cured body is exposed to sunlight for 10 hours, the discoloration cannot be easily detected with the naked eye. Conventionally, in order to solve the above problems, an ultraviolet absorber is blended into a dental restorative material.

  In addition, restoration using a dental composite resin is indistinguishable from natural teeth and can be highly esthetically restored, but in an environment that emits ultraviolet light or short-wavelength visible light. In, the repaired site looked black, placing a mental burden. In order to improve this drawback, it has been proposed to further add a fluorescent agent in addition to the ultraviolet absorber. Among the fluorescent agents used at this time, phthalate ester-based ones are easy to obtain, emit fluorescent light similar to natural teeth, and have exceptional aesthetic features, so they are advantageously used. Yes. The use of a combination of a benzophenone ultraviolet absorber and a phthalate ester fluorescent agent is a typical example (for example, Patent Document 1).

  However, the present inventors have examined that a dental photopolymerizable composition in which a benzophenone ultraviolet absorber and a phthalate ester fluorescent agent are combined is difficult to achieve both stability to sunlight and fluorescence. I found out. Specifically, if the blending amount is increased in order to increase the stability to sunlight, sufficient fluorescence cannot be obtained, and conversely, the blending amount of the phthalate ester fluorescent agent to obtain sufficient fluorescence It has been found that sufficient stability against sunlight cannot be obtained when the amount is increased.

JP-T-2002-520347

  Under the circumstances described above, the present invention provides a cured product that does not discolor (excellent in sunlight stability) to an extent that affects aesthetics even when the cured product is exposed to sunlight for a long period of time. It aims at obtaining the dental photopolymerizable composition which shows the property.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by using a benzotriazole compound as an ultraviolet absorber and a phthalate ester fluorescent agent as a fluorescent agent, and have completed the present invention.

That is, the present invention provides dental light comprising (A) a radical polymerizable monomer, (B) a visible light polymerization initiator, (C) a phthalate ester fluorescent agent, and (D) a benzotriazole compound. It is a polymerizable composition (excluding those containing a cationic polymerizable monomer) .

  The dental photopolymerizable composition of the present invention can provide a dental restoration having little coloration of the cured product and sufficient fluorescence even when exposed to ultraviolet light such as sunlight. Therefore, it is extremely useful as a dental photopolymerizable composition for use in dental restorative materials such as dental composite resins and hard resins.

  Further, by controlling the (C) phthalate ester fluorescent agent and (D) benzotriazole compound contained in the dental photopolymerizable composition of the present invention to appropriate amounts, the balance between sunlight stability and fluorescence is achieved. In addition, the amount of surface unpolymerization when cured can be reduced.

Hereinafter, each component of the dental photopolymerizable composition of the present invention will be described.
[(A) radical polymerizable monomer]
As the radical 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 radical polymerizable monomer (i) Aromatic compound type bifunctional radical polymerizable monomer 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3- (Methacryloyloxy) -2-hydroxypropoxyphenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) Propane (hereinafter abbreviated as D-2.6E), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2- Bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloylo) Xydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxy) Phenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2 -Vinyl having an -OH group such as methacrylates such as hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates A monomer, a diisocyanate methyl benzene, diadduct and the like obtained from the addition of the diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate.

(Ii) Aliphatic compound-based bifunctional radically polymerizable monomer 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- Vinyl monomers having —OH groups such as methacrylates such as chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates Diadducts obtained from adducts of nomers and diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyl) Oxy-2-hydroxypropoxy) ethyl and the like.
(II) Trifunctional radically polymerizable monomer: Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.
(III) tetrafunctional radically polymerizable monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), Diaducts obtained by addition reaction of diisocyanate compounds such as 4,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate with 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.
[(B) Visible light polymerization initiator]
As the visible light polymerization initiator of the component (B) in the dental photopolymerizable composition of the present invention, known compounds can be used without any limitation.

  In the present invention, visible light means light in the wavelength region of 380 nm to 780 nm, and the visible light polymerization initiator means a compound having photosensitivity in the visible light region.

  As a visible light polymerization initiator, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, diaryl ketones such as benzophenone, anthraquinone and thioxanthone, Α-Diketones such as camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, acenaphthenequinone Bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, Su- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as can be used.

  Among these visible light polymerization initiators, α-diketones are preferably used in order to reduce the amount of surface unpolymerization. This is because (C) the phthalate ester fluorescent agent of the present invention has a relatively close fluorescence wavelength of 380 to 600 nm and the α-diketone absorption wavelength of 380 to 500 nm, and (C) phthalate ester fluorescence. However, it is presumed that the α-diketones are easily activated, and as a result, contribute to a reduction in the amount of surface unpolymerization.

  The amount of the visible light polymerization initiator used is more preferably 0.01 to 10 parts by mass, particularly 0.02 to 5 parts by mass, per 100 parts by mass of the (A) radical polymerizable monomer.

  The visible light polymerization initiator is preferably used in combination with a reducing compound. Examples of the reducing compound include amine compounds such as aromatic amine compounds and aliphatic amine compounds, sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and thiobenzoic acid, tetraphenylboric acid, tetrakis ( p-Fluorophenyl) boric acid, sodium salts such as butyltriphenylboric acid, tetraalkylborate compounds such as triethanolamine salt, N-phenylalanine and the like. The amine compound is preferably an amine compound from the viewpoints of high polymerization activity and excellent storage stability.

  As the aromatic amine compound in the present invention, an amine compound in which at least one of organic groups bonded to a nitrogen atom is an aromatic group is applicable, and known compounds satisfying this structure can be used without particular limitation. An amine compound (hereinafter referred to as the third compound) in which one aromatic group and two aliphatic groups are bonded to a nitrogen atom because it has higher polymerization activity and lower volatility due to lower volatility and is easily available. And a secondary aromatic amine compound). Typical tertiary aromatic amine compounds include those represented by the following general formula (3).

(In the formula, R ⁸ and R ⁹ are each independently an alkyl group, and R ¹⁰ is a hydrogen atom, a hydrocarbon group, an alkoxy group, or an alkyloxycarbonyl group.)
Examples of the alkyl group of R ⁸ and R ⁹ include those having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and n-hexyl group. . These alkyl groups may be substituted products such as those substituted with halogen such as chloromethyl group and 2-chloroethyl group, and those substituted with hydroxyl group such as 2-hydroxyethyl group.

Examples of the hydrocarbon group for R ¹⁰ include an aryl group, an alkenyl group, an aralkenyl group, and the like in addition to the above alkyl group, and these may also have a substituent. Specifically, aryl groups such as phenyl group, p-methoxyphenyl, p-methylthiophenyl group, p-chlorophenyl group and 4-biphenylyl group, alkenyl groups such as vinyl group and 2-propenyl group, 2-phenylethenyl And those having 1 to 12 carbon atoms such as an aralkenyl group such as a group.

  Examples of the alkoxy group include those having 1 to 10 carbon atoms such as methoxy group, ethoxy group, butoxy group and pentoxy group, and more preferably those having 1 to 5 carbon atoms, which also have a substituent. May be. In addition, as the alkyloxycarbonyl group, the alkyloxy group moiety such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, etc. has 1 to 10 carbon atoms, more preferably carbon. The thing of number 1-5 is illustrated and these may also have a substituent.

Incidentally, R ¹⁰ is more preferably the binding position is the para position.

  Specific examples of the aromatic amine compound represented by the general formula (3) include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, and pentyl p-dimethylaminobenzoate. , Isopentyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate, N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine and the like can be mentioned.

  In the present invention, if the content of the above-mentioned aromatic amine compound is too small, a sufficient effect of improving the polymerization activity cannot be obtained, and if it is too large, coloring may be darkened. It is preferably in the range of 10 to 1000 parts by mass, particularly 50 to 500 parts by mass per 100 parts by mass of the photopolymerization initiator. Moreover, if it shows per 100 mass parts of (A) radically polymerizable monomers, it is more preferable to use in the range of 0.01-10 mass parts, especially 0.02-5 mass parts.

  As the aliphatic amine compound, known compounds can be used without limitation, and any of primary amine, secondary amine and tertiary amine may be used. Since there are few problems, such as an odor, when using it for dentistry, a tertiary amine compound is generally used. In addition, the said aliphatic amine compound is a compound whose organic group couple | bonded with the nitrogen atom is all aliphatic groups (however, you may have a substituent).

  Specific examples of such an aliphatic group bonded to a nitrogen atom include linear or branched carbon numbers such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and an i-butyl group. 1-6 alkyl groups; alkenyl groups such as ethenyl group (vinyl group) and allyl group. In addition, examples of the substituent bonded to the aliphatic group include hydroxyl groups such as a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, and a 2,3-dihydroxypropyl group; an ethenyl group (vinyl group). Unsaturated aliphatic groups such as 1-propenyl group and ethynyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; acyloxy groups such as acetyloxy group, acryloyloxy group and methacryloyloxy group; phenyl group and naphthyl group An aryl group such as an alkoxyl group, a carbonyl group, a carbonyloxy group, or a cyano group.

  Specific examples of the aliphatic amine compound suitably used in the present invention include aliphatic primary amine compounds such as 2-ethylhexylamine, n-butylamine, n-hexylamine and n-octylamine; Aliphatic secondary amine compounds such as butylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, di-n-octylamine; triethylamine, tributylamine, triallylamine, N, N-dimethylaminoethyl methacrylate, N, N -Diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine Tertiary amine compounds such as dipropylethanolamine, triethanolamine, tri (isopropanol) amine, tri (2-hydroxybutyl) amine, tribenzylamine, more preferably N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, triethylamine, tri Butylamine is mentioned.

  These aliphatic amine compounds may be used alone or in combination of two or more. Moreover, the general compounding quantity is 0.005-5 weight part with respect to 100 weight part of (A) radically polymerizable monomers, More preferably, it is 0.01-3 weight part.

It is also a preferred embodiment to add a photoacid generator in order to further increase the activity of the visible light polymerization initiator. Examples of the photoacid generator include diaryliodonium salt compounds, sulfonium salt compounds, sulfonate ester compounds, halomethyl-substituted S-triazine conductors, pyridinium salt compounds, and the like. When a photoacid generator is used, the visible light polymerization initiator is preferably an α-diketone such as camphorquinone, and more preferably a reducing compound such as 4-dimethylaminobenzoic acid is used in combination.
[(C) Phthalate ester fluorescent agent]
As the phthalate ester fluorescent agent to be blended in the dental photopolymerizable composition of the present invention, known phthalate fluorescent agents can be used without any limitation. A particularly preferred phthalate ester fluorescent agent is represented by the following general formula (1).

(In the formula, R ¹ and R ² are each independently an alkyl group, R ³ is a hydrogen atom, an amino group, or a hydroxyl group, and R ⁴ is an amino group or a hydroxyl group.)
As said alkyl group, a C1-C3 thing, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, is preferable, and a C1-C2 thing is especially more preferable.

  Specific examples of the phthalate ester fluorescent agent include dimethyl 2,5-dihydroxyterephthalate, diethyl 2,5-dihydroxyterephthalate, dimethylaminoterephthalate, diethylaminoterephthalate, and the like, and diethyl 2,5-dihydroxyterephthalate. A phthalate ester fluorescent agent substituted with a hydroxyl group such as is more preferred. These phthalate ester fluorescent agents may be used alone or in admixture of two or more.

  When α-diketone is used as the visible light polymerization initiator, it is preferable to use diethyl 2,5-dihydroxyterephthalate as the phthalate ester fluorescent agent from the viewpoint of reducing surface unpolymerization. This is probably because there are many overlapping portions between the absorption wavelength of α-diketone and the fluorescence wavelength of diethyl 2,5-dihydroxyterephthalate, and α-diketone is easily activated.

The blending amount of the phthalate ester-based fluorescent agent with respect to 100 parts by mass of the radically polymerizable monomer (A) is not particularly limited, but a certain amount is necessary to ensure fluorescence, and conversely the blending amount is When the amount is too large, it is difficult to ensure a certain degree of sunlight stability. For a good balance between sunlight stability and fluorescence, 0.005 to 0.5 parts by mass is preferable, and 0.01 to 0.1 parts by mass is more preferable. .
[(D) Benzotriazole compound]
In the system containing the above (A) radical polymerizable monomer, (B) visible light polymerization initiator, and (C) phthalate ester fluorescent agent, the greatest feature of the present invention is (D) The use of a benzotriazole compound.

  UV absorbers other than benzotriazole compounds, for example, UV absorbers such as benzophenone-based, cyanoacrylate-based, hindered amine-based, etc. are known, but these are difficult to dissolve in the polymerizable monomer or even if dissolved. (C) In a system containing a phthalate ester fluorescent agent, it is difficult to obtain a sufficient discoloration (coloring) prevention effect.

  The benzotriazole compound is generally known as an ultraviolet absorber and is used to prevent the cured body of the dental restorative material from being discolored by ultraviolet rays such as sunlight. As the benzotriazole compound, a known compound can be used without particular limitation as long as the hydroxyl group is bonded to the position of the 2-position of the aromatic ring bonded to the nitrogen atom of the triazole structure.

  Representative benzotriazole compounds include those represented by the following general formula (2).

(In the formula, R ⁵ is a hydrogen atom or an alkyl group, R ⁶ is an alkyl group, R ⁷ is an alkyl group or a halogen atom, and m is an integer of 0 to 4.)
The alkyl group in R ⁵ , R ⁶ and R ⁷ may have a substituent, and specific examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i- Unsubstituted alkyl groups such as propyl group, n-butyl group, t-butyl group, n-hexyl group, amyl group and octyl group; alkyl groups substituted by halogen such as chloromethyl group and 2-chloroethyl group; dimethyl An alkyl group substituted with an aryl group such as a benzyl group; an alkyl group substituted with a hydroxyl group such as a 2-hydroxyethyl group and the like having 1 to 12 carbon atoms.

Examples of the halogen atom for R ⁷ include fluorine, chlorine, iodine and bromine.

As the R ⁵ and R ^6, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 8 carbon atoms. Specific examples of such an alkyl group again include a methyl group, an ethyl group, an n-propyl group, a t-butyl group, and the like. The bonding positions of R ⁵ and R ⁶ are generally the 3-position and 5-position when both are alkyl groups, and when R ⁵ is a hydrogen atom, R ⁶ is the 5-position. It is common that

m is an integer of 0 to 4, that is, 0 to 4 R ⁷ are bonded to the benzene ring of the benzotriazole ring. m is more preferably 0 or 1, and still more preferably 0. When m is other than 0, R ⁷ is preferably a halogen atom, and more preferably a chlorine atom.

  Hereinafter, specific examples of the benzotriazole compound include 2- (2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, and 2- (2-hydroxy-5-ethylphenyl). Benzotriazole, 2- (2-hydroxy-5-propylphenyl) benzotriazole, 2- (2-hydroxy-5-butylphenyl) benzotriazole, 2- (2-hydroxy-5-pentylphenyl) benzotriazole, 2- (2-hydroxy-5-hexylphenyl) benzotriazole, 2- (2-hydroxy-5-heptylphenyl) benzotriazole, 2- (2-hydroxy-5-octylphenyl) benzotriazole, 2- (2-hydroxy- 5-tert-butylphenyl) benzo Riazole, 2- (2-hydroxy-5-tert-pentylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-hexylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-heptylphenyl) Benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-pentylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-hexylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-heptylphenyl) ) Benzotriazole, 2- (2-hydroxy-) , 5-di-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-tert-pentyl-2-hydroxy-5-methyl) Phenyl) benzotriazole, 2- (3-tert-hexyl-2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-tert-heptyl-2-hydroxy-5-methylphenyl) benzotriazole, 2- ( 3-tert-octyl-2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-ethylphenyl) benzotriazole, 2- (3-tert-butyl-2- Hydroxy-5-propylphenyl) benzotriazole, 2- (3 -Tert-butyl-2-hydroxy-5-ethylphenyl) benzotriazole, 2- (3-tert-pentyl-2-hydroxy-5-ethylphenyl) benzotriazole, 2- (3-tert-hexyl-2-hydroxy) -5-ethylphenyl) benzotriazole, 2- (3-tert-heptyl-2-hydroxy-5-ethylphenyl) benzotriazole, 2- (3-tert-octyl-2-hydroxy-5-ethylphenyl) benzotriazole 2- (3-tert-butyl-2-hydroxy-5-propylphenyl) benzotriazole, 2- (3-tert-pentyl-2-hydroxy-5-propylphenyl) benzotriazole, 2- (3-tert- (Hexyl-2-hydroxy-5-propylphenyl) ben Triazole, 2- (3-tert- heptyl-2-hydroxy-5-propylphenyl) benzotriazole, 2- (3-tert- octyl-2-hydroxy-5-propylphenyl) benzotriazole.

  These benzotriazole compounds may be used alone or in combination of two or more. The blending amount of the benzotriazole compound is not particularly limited as long as the effects of the present invention can be obtained, but if it is too large, the strength and color tone of the cured product may be affected. (A) It is 0.01-10 mass parts with respect to 100 mass parts of radically polymerizable monomers, More preferably, it is 0.02-5 mass parts.

  As described above, the greatest feature of the present invention is that in the system containing the above (A) radical polymerizable monomer, (B) visible light polymerization initiator, and (C) phthalate ester fluorescent agent, an ultraviolet absorber. (D) To use a benzotriazole compound, and to have a good balance between sunlight stability and fluorescence. From the viewpoint of achieving a higher degree of compatibility between fluorescence and sunlight stability, the blending ratio of (C) phthalate-based fluorescent agent and (D) benzotriazole compound is 1 part by weight of (C) phthalate-based fluorescent agent. The (D) benzotriazole compound is preferably 1 to 50 parts by mass, (C) the phthalate ester fluorescent agent is 1 part by mass, and (D) the benzotriazole compound is 2 to 30 parts by mass. It is more preferable that (C) the phthalate ester fluorescent agent is 1 part by mass, and (D) the benzotriazole compound is particularly preferably 3 to 20 parts by mass.

  In addition to the blending ratio of the above-mentioned (C) phthalate ester fluorescent agent and (D) benzotriazole compound, from the viewpoint of making fluorescence and sunlight stability more compatible and further reducing the amount of unpolymerized surface, (D) It is preferable that the mixture ratio of a benzotriazole compound is 0.01-3 mass parts with respect to 100 mass parts of (A) radically polymerizable monomers, and it is 0.1-2 mass parts or less. More preferably, it is 0.2-1 mass part or less especially.

  In addition to the above components, the dental photopolymerizable composition of the present invention may contain other compounding components known as compounding components for the dental photopolymerizable composition.

  The dental photopolymerizable composition of the present invention has a high mechanical strength and can reduce filler shrinkage and thermal expansion, preferably an inorganic filler or an organic-inorganic filler, in particular. It is preferable to blend an inorganic filler.

  As the inorganic filler, known inorganic fillers can be used without limitation as fillers for dental restoration materials. Examples of typical inorganic fillers include quartz, silica, alumina, zirconia, titania, and lanthanoids. Silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass and the like. 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. A plurality of inorganic fillers having different particle size ranges, average particle sizes, refractive indexes, and materials may be used in combination.

  Furthermore, when a spherical inorganic filler is used among the above fillers, the surface smoothness of the resulting cured product is increased, and an excellent dental restoration material can be obtained.

  It is desirable that the inorganic filler is treated with a surface treatment agent typified by a silane coupling agent in order to improve the compatibility with the radical 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 proportion of these fillers may be appropriately determined in consideration of the viscosity (operability) when mixed with the radical polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. Is used in an amount of 50 to 1500 parts by weight, preferably 70 to 1000 parts by weight, based on 100 parts by weight of the radical polymerizable monomer.

  In addition, pigments and dyes may be added to match the color tone of the tooth, and other additives known as components of dental restorative materials may be blended within a range that does not affect the effects of the present invention. .

  Furthermore, you may mix | blend another well-known polymerization initiator with the dental photopolymerizable composition of this invention in the range which does not impair the effect of this invention. Other polymerization initiator components include: organic peroxides such as benzoyl peroxide and cumene hydroperoxide; + IV value or + V such as vanadium (IV) acetylacetonate, bis (maltolate) oxovanadium (IV) Valent vanadium compounds; tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) boron sodium, butyltri (p-fluorophenyl) boron sodium, etc. Aryl borate compounds; coumarin dyes such as 3,3′-carbonylbis (7-diethylamino) coumarin, 7-hydroxy-4-methyl-coumarin; benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether Benzoin alkyl ethers such as 2, thioxanthone derivatives such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone; benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxy And benzophenone derivatives such as benzophenone. 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, if the pigments such as coumarin-based pigments are mixed in an amount that acts as a polymerization initiator, the color tone of the dental photopolymerizable composition is greatly affected, and dental restoration that requires high aesthetics is required. The material tends to have a different color tone than the teeth.

  The method for producing the visible light polymerizable dental photopolymerizable composition of the present invention is not particularly limited, and any known visible light polymerizable composition producing method may be used. In general, a predetermined amount of each component to be blended is weighed out under light shielding, kneaded until uniform, and bubbles mixed during kneading may be removed as necessary. The obtained paste of the composition is divided into light-shielding containers and supplied to a dental clinic or a dental laboratory in that state.

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)
・ Triethylene glycol dimethacrylate (3G)
(B) Visible light polymerization initiator, camphorquinone (CQ), maximum absorption wavelength of 460 to 480 nm
(C) Fluorescent agent [phthalate ester fluorescent agent]
・ Diethyl 2,5-dihydroxyterephthalate (DHTP)
..Maximum fluorescence wavelength 433 to 453 nm
(Light source: Maximum absorption wavelength is 360 to 380 nm)
・ Dimethylaminoterephthalate (DATP)
..Maximum fluorescence wavelength 430 to 450 nm
(Light source: Maximum absorption wavelength is 360 to 380 nm)
[Other fluorescent agents]
-2,5 bis (5'-tert-butylbenzoxazolyl) thiophene (BOTh)
..Maximum fluorescence wavelength 405 to 425, 428 to 448 nm
(Light source: Maximum absorption wavelength is 360 to 380 nm)

(D) UV absorber [benzotriazole UV absorber]
2- (2-hydroxy-5-methylphenyl) benzotriazole (BT1)
2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (BT2 )
[ Other UV absorbers]
・ 2-Hydroxy-4-methoxybenzophenone (BP)
(E) Other components · N, N-dimethyl p-ethyl benzoate (DMBE)
・ Hydroquinone monomethyl ether (HQME)
(F) Inorganic filler, spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product; average particle size: 0.5 μm (E-1)
Spherical silica-titania, γ-methacryloyloxypropyltrimethoxysilane surface-treated product; average particle size: 0.08 μm (E-2)

Moreover, the following method was used for the preparation method of a dental restoration material, and the physical-property measurement of a hardening body.

(1) Preparation method of dental restorative material A polymerizable monomer is mixed in a predetermined quantity ratio, and under a red light, a predetermined amount of a visible light polymerization initiator and a filler are added thereto, and uniform. The mixture was well mixed and stirred in an agate mortar until the paste became a paste. Further, this was vacuum degassed to obtain a dental composite resin paste having a predetermined composition.

(2) Evaluation of Fluorescence Teflon (registered trademark) mold having a 7 mmφ × 3.0 mm hole is filled with paste and pressed with a polypropylene film, and a dental light irradiator (Tokuso Power Light, Tokuyama Dental Co., Ltd.) A light output density of 600 mW / cm ² , an irradiation wavelength of 400 to 525 nm) was closely adhered to the polypropylene film and irradiated for 30 seconds to prepare a cured product. The obtained cured product was observed for its fluorescence emission state using an ultraviolet light irradiator (MINERALIGHT LAMP, Funakoshi Chemical Co., Ltd .; maximum absorption wavelength 366 nm). In particular, the case where excellent fluorescence was confirmed was evaluated as ◎, the case where good fluorescence was confirmed as ○, the case where fluorescence was confirmed but insufficient, as Δ, and the case where fluorescence could not be confirmed as ×.

(3) Color tone change (sunlight stability)
A 1 mm thick polyacetal mold with a 15 mm diameter through hole was filled with a paste of a dental restorative material, pressed with a polypropylene film, and a dental light irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; 5 sites were irradiated with light for 10 seconds each so that the entire dental restorative material of the present invention was exposed to light at an optical output density of 700 mW / cm ² and an irradiation wavelength of 400 to 525 nm. Half of the test piece was covered with aluminum foil and exposed to direct sunlight for 10 hours. The color tone of the part covered with aluminum foil (unexposed part) and the part exposed to direct sunlight (exposed part) was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd .: TC-1800MKII), and the difference ΔE ^* Expressed in

ΔE ^* = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
ΔL ^* = L1 ^* −L2 ^*
Δa ^* = a1 ^* −a2 ^*
Δb ^* = b1 ^* −b2 ^*
L1 ^* : Lightness index of unexposed area, a1 ^* , b1 ^* : Color quality index of unexposed area, L2 ^* : Lightness index of exposed area, a2 ^* , b2 ^* : Color quality index of exposed area, ΔE ^* : Color tone change amount.

(4) Surface unpolymerized amount A paste of dental restorative material was filled in a 1.5 mm thick polyacetal mold with a 7 mm diameter through hole, and the top surface was exposed to air. Irradiated with light for 10 seconds. After completion of irradiation, the cured product was taken out of the mold and weighed. Thereafter, the cured product was immersed in ethanol, subjected to ultrasonic cleaning for 3 minutes, dried, and then weighed again to determine the amount of weight loss per unit area as the surface unpolymerized amount (μg / mm ³ ).

Examples 1 to 12 , Comparative Examples 1 to 5, Reference Example 1
Bis-GMA (60 parts by mass), 3G (40 parts by mass) of polymerizable monomer 100 parts by mass, inorganic filler E-1 is 147 parts by mass, E-2 is 63 parts by mass, polymerization is prohibited 0.15 parts by mass of HQME as an agent, 0.3 part by mass of CQ as a visible light polymerization initiator, 1.0 part by mass of DMBE, and a predetermined amount of UV absorber and fluorescent agent as shown in Table 1. A paste of dental restorative material was prepared.

  Table 1 also shows the results of measuring various physical properties of the obtained dental restorative material.

  As understood from Table 1 above, as the blending amount of the ultraviolet absorber is increased, the sunlight stability is improved (the color change amount is reduced). On the other hand, the sunlight stability decreases as the blending amount of the fluorescent agent is increased.

  It can be seen that the composition using the benzotriazole compound exhibits good fluorescence and sunlight stability.

Further, when the blending amount of the ultraviolet absorber is increased, the surface unpolymerized amount increases at the same time. As can be seen from Example 9 and Comparative Example 4, for example , (C) phthalate ester fluorescent agent and (D) By using a benzotriazole compound, good solar stability and good fluorescence can be obtained in a well-balanced manner with a smaller amount of each, so the increase in the amount of surface unpolymerization has adopted a benzophenone UV absorber. The solar stability of Example 9 and Comparative Example 4 is comparable, but the Comparative Example has low fluorescence and a large amount of surface unpolymerization.

  In addition, the fluorescence confirmed in Reference Example 1 emits fluorescence different from that of the teeth, and is relatively inferior in aesthetics compared to that used in the Examples, and also has a large amount of surface unpolymerization. .

Claims (6)

(A) a radical polymerizable monomer,
(B) a visible light polymerization initiator,
(C) Dental photopolymerizable composition containing a phthalate ester fluorescent agent and (D) a benzotriazole compound (excluding those containing a cationic polymerizable monomer) . The dental photopolymerizable composition according to claim 1, wherein (C) the phthalate ester-based fluorescent agent is a compound represented by the following general formula (1).

(In the formula, R ¹ and R ² are each independently an alkyl group, R ³ is a hydrogen atom, an amino group, or a hydroxyl group, and R ⁴ is an amino group or a hydroxyl group.) (D) The dental photopolymerizable composition according to claim 1 or 2, wherein the benzotriazole compound is a compound represented by the following general formula (2).

(In the formula, R ⁵ is a hydrogen atom or an alkyl group, R ⁶ is an alkyl group, R ⁷ is an alkyl group or a halogen atom, and m is an integer of 0 to 4.) (B) The dental photopolymerizable composition according to any one of claims 1 to 3, wherein the visible light polymerization initiator is an α-diketone. A dental restorative material comprising the dental photopolymerizable composition according to any one of claims 1 to 4. (A) per 100 parts by mass of radically polymerizable monomer,
(B) 0.01 to 10 parts by mass of a visible light polymerization initiator,
(C) 0.005 to 0.5 parts by mass of a phthalate ester fluorescent agent, and
(D) 0.01 to 10 parts by mass of a benzotriazole compound
The dental photopolymerizable composition according to claim 1, wherein the proportion of (D) the benzotriazole compound is 1 to 50 parts by mass with respect to 1 part by mass of (C) the phthalate ester fluorescent agent.