JP2010208964A - Dental photocurable material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental photocurable material which is hardened with light irradiation for a short time by a light curing unit and exhibits a high breaking energy (toughness). <P>SOLUTION: The dental photocurable material includes: (A) a radically polymerizable monomer containing ≥70 wt.% of a monofunctional (meth)acrylate-based polymerizable monomer such as methyl methacrylate; (B) a non-crosslinked (meth)acrylate-based polymer such as polymethylmethacrylate and polyethylmethacrylate; and (C) a photoinitiator composed of (C1) an α-diketone compound, (C2) an amine compound, and (C3) a diaryl iodonium salt-based compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dental photocurable material suitable for a dental adhesive or a dental filling / restoring material.

  In the field of dental treatment, various curable materials are used as dental adhesives, dental filling restorative materials, denture base materials and the like. These materials are basically composed of a monomer (radical polymerizable monomer) component, a filler (filler) component, and a polymerization initiator, and those using a non-crosslinkable resin filler as a filler component are inorganic fillers. And the toughness of the cured product is higher than that using a crosslinkable resin filler. The material using such a non-crosslinkable resin filler is, for example, a tooth damaged by caries or an accident, and a prosthetic material (for example, composite resin, metal, ceramics, etc.) for repairing the tooth. It can be used for adhesion of dental restoration materials), adhesion of teeth and orthodontic brackets for the purpose of orthodontic treatment, and the method of adhering and fixing teeth that have been shaken due to periodontal disease, etc. (adjacent tooth fixation method). It is widely used, such as dental adhesive resin cements that can be made, and room temperature polymerization resins that are used to repair denture bases and make temporary crowns.

  The dental material for the above-described uses requires high toughness (hardness to break) that can withstand various external forces. Therefore, the monomer component is a liquid such as methyl methacrylate (hereinafter, methyl methacrylate may be abbreviated as “MMA”), which has a two-dimensionally polymerized and high toughness and has only one polymerizable functional group in the molecule. In general, a monofunctional (meth) acrylate polymerizable monomer is used. Furthermore, since liquid monomers such as methyl methacrylate are known to be difficult to polymerize due to low viscosity, non-crosslinkable polymethyl methacrylate (hereinafter referred to as “thin polymer”) that is dissolved and thickened in the monomer is known. It is preferable to blend a homopolymer or copolymer of a (meth) acrylate polymerizable monomer such as polymethyl methacrylate (sometimes abbreviated as “PMMA”).

  Dental materials containing the above monofunctional (meth) acrylate polymerizable monomers and non-crosslinkable (meth) acrylate polymers generally include a liquid material mainly composed of radically polymerizable monomers, Generally, it is divided into a powder material containing a crosslinkable (meth) acrylate polymer as a main component, and a chemical polymerization type polymerization initiator is divided into both materials and packaged. In this case, if the liquid material and the powder material are mixed at the time of use, the curing reaction starts, progresses and cures in the mixture (also called powder / liquid type). The chemical polymerization initiator is a type of initiator that generates radicals when two or more compounds come into contact with each other. Therefore, it is difficult for an operator to control the time until the composition is cured (curing time) (see Patent Documents 1 and 2).

  However, for example, in the case of bonding an orthodontic bracket, the bracket must be bonded to a large number of teeth, but in the case of the above-mentioned chemical polymerization type curable material, it is necessary to wait until it is cured. Treatment time (chair time) takes longer. Therefore, the operator can apply the composition at an arbitrary timing so that it is not cured while the bracket is mounted at the tooth bracket mounting position and fine adjustment is performed on the bracket of the adjacent tooth, and can be appropriately cured when fixing the bracket. There is a clinical need for photopolymerizable dental materials that can be cured. Although examination about such a photopolymerization type curable material is performed, the curability is still not clinically satisfactory (refer nonpatent literature 1, patent documents 3-5).

  Various studies have been conducted on photopolymerization initiators used for general photopolymerization-type dental materials, and compounds that absorb light and decompose themselves to generate polymerization active species, and more suitable A system combining various sensitizers has been widely studied and used. Examples of the former are acylphosphine oxide compounds and α-diketone compounds, and examples of the latter are well known combinations of α-diketone compounds and tertiary amine compounds, and aryl iodonium salts, A system in which a photoacid generator such as an s-triazine compound substituted with a trihalomethyl group is combined, or a system in which a dye / aryl borate compound / photoacid generator is combined has been proposed. However, in these proposals, a polyfunctional radical polymerizable monomer containing a plurality of polymerizable functional groups in one molecule is mainly used as the radical polymerizable monomer. A curable material having high toughness has not been obtained. On the other hand, in the case of the monofunctional (meth) acrylate polymerizable monomer, as described above, the viscosity is low and the polymerization does not proceed easily. Therefore, a (meth) acrylate polymer such as PMMA is added to increase the viscosity. Even so, many of these photopolymerization initiators have a long curing time and insufficient hardness, so that no clinically usable material has been obtained.

Dental Materials and Instruments Vol. 6 No. 6 p877-887 (1987) JP-A-9-67222 JP-A-11-71220 JP 2000-53727 A JP-A-8-169806 JP 2002-161013 A JP-A-2005-213231 JP 2005-89729 A JP 2000-16910 A JP-A-9-3109

  Therefore, an object of the present invention is to use a monofunctional (meth) acrylate polymerizable monomer and a non-crosslinkable (meth) acrylate polymer, so that the material has high toughness, and is a halogen lamp, xenon lamp, laser. It is an object of the present invention to provide a photocurable material containing a photopolymerization initiator capable of completing polymerization quickly in a short time by light irradiation with an irradiator such as a diode.

  The present inventors have intensively studied to achieve the above object. As a result, in the photopolymerizable curable material comprising the monofunctional (meth) acrylate polymerizable monomer, the non-crosslinkable (meth) acrylate polymer, and the photopolymerization initiator, the photopolymerization initiator In particular, by using a system composed of a combination of an α-diketone compound, an amine compound, and a diaryliodonium salt compound, it is a tough material and is based on an irradiator equipped with a halogen lamp, a xenon lamp, or a laser diode. The present inventors have found that a photocurable material that can be cured quickly in a short time by light irradiation is obtained, and the present invention has been completed.

That is, according to the present invention,
(A) a radical polymerizable monomer containing 70 wt% or more of a monofunctional (meth) acrylate polymerizable monomer,
And (B) a non-crosslinkable (meth) acrylate polymer, and a photopolymerization initiator comprising (C) a C1) α-diketone compound, C2) an amine compound, and C3) a diaryliodonium salt compound. A dental photocurable material is provided.

  The photocurable material of the present invention includes a monofunctional (meth) acrylate polymerizable monomer, a non-crosslinkable (meth) acrylate polymer, and a photopolymerization initiator, and α- By including the diketone, the amine compound, and the diaryl iodonium salt compound, the polymerization can be completed quickly in a short time by the light irradiation of the light irradiator. Moreover, since it is a material with high toughness, it can be suitably used for treatment of a site to which an external force is applied (fixation of a moving tooth, etc.). Furthermore, since it hardens | cures by light irradiation, it can be used conveniently for the treatment (adhesion of the bracket for correction, etc.) over many teeth.

  The dental photocurable material of the present invention comprises (A) a radical polymerizable monomer component having a specific composition, (B) a non-crosslinkable (meth) acrylate polymer component, and (C) a photopolymerization having a specific composition. Each initiator component is blended. Hereinafter, each of these components will be described.

[(A) radical polymerizable monomer]
In the dental photocurable material of the present invention, the (A) radical polymerizable monomer component has a monofunctional (meth) acrylate-based content of 70 wt% or more, more preferably 75 wt% or more in order to obtain a material having high toughness. It is occupied by polymerizable monomers. Here, the monofunctional (meth) acrylate polymerizable monomer refers to a (meth) acrylate polymerizable monomer containing one (meth) acryloyloxy group in one molecule.

  As such a monofunctional (meth) acrylate-based polymerizable monomer, those known as components of dental photocurable materials can be used without any limitation. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, Water-insoluble monofunctional (meth) acrylate monomers such as tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyethyl propionate, 2-methacryloxyethyl acetoacetate; 2-hydroxyethyl ( Water-soluble monofunctional (meth) acrylate monomers such as meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate are exemplified.

  Moreover, when using the photocurable material of this invention as a dental adhesive etc., what contains an acidic group is used suitably as this monofunctional (meth) acrylate type | system | group polymerizable monomer. . Examples of such monofunctional acidic group-containing (meth) acrylate 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, 4- (meth) acryloyloxyethyl trimellitate anhydride, N- (meta ) Monofunctional polymerizable monomers containing carboxylic acid acidic groups such as acryloylglycine and N- (meth) acryloylaspartic acid; 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, (meth) acryloyloxyethyldi Hydrogen phosphate, 10- (meth) acryloylo Monofunctional polymerizable monomers containing phosphoric acid groups such as sidecyl dihydrogen phosphate and 6- (meth) acryloyloxyhexyl dihydrogen phosphate; 3-containing sulfonic acid groups such as sulfopropane (meth) acrylate And radical polymerizable monomers. In the present invention, the monofunctional (meth) acrylate polymerizable monomer is a noble metal adhesive monomer described in JP-A-10-1409, JP-A-10-1473, JP-A-8-113763, or the like. Among these, monofunctional (meth) acrylate-based polymerizable monomers are also used for dental adhesives and dental materials that contact photocurable materials with dental materials made of precious metals such as gold alloys and gold-silver-palladium alloys. When used as a filling and repairing material, it can be preferably used.

  In the present invention, the above monofunctional (meth) acrylate polymerizable monomers may be used alone or in combination of two or more. Since the solubility of the (B) non-crosslinkable (meth) acrylate polymer described later is high, the monofunctional (meth) acrylate polymerizable monomer (A) is a lower monomer such as methyl methacrylate or ethyl methacrylate. It preferably contains an alkyl (meth) acrylate-based polymerizable monomer, and most preferably methyl methacrylate.

  In addition, when a hardened body with higher strength is desired, a polyfunctional (meth) acrylate-based compound containing two or more (meth) acryloyloxy groups is used if it is less than 30 wt%, more preferably less than 25 wt%. A combination of polymerizable monomers can also be used. Specific examples of such polyfunctional (meth) acrylate polymerizable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neo Aliphatic polyfunctional (meth) acrylates such as n-glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane (meth) acrylate Monomers: 2,2-bis ((meth) acryloxyphenyl) propane, 2,2-bis [4- (2-hydroxy-3- (meth) acryloxyphenyl)] propane, 2,2- Bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane Aromatic polyfunctional (meth) acrylate monomers and the like.

  Similarly to the case of the monofunctional (meth) acrylate polymerizable monomer, a polyfunctional (meth) acrylate polymerizable monomer is used when a photocurable material is used as a dental adhesive. As these, those containing an acidic group are preferably used. As such a polyfunctional acidic group-containing (meth) acrylate-based polymerizable monomer, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) ) Polyfunctional polymerizable monomers containing carboxylic acid groups of propyl succinate; Polyfunctional polymerizable monomers containing phosphoric acid groups such as bis ((meth) acryloyloxyethyl) hydrogen phosphate It is done.

  In addition, as the (A) radical polymerizable monomer, a monofunctional and / or polyfunctional polymerizable monomer other than the (meth) acrylate polymerizable monomer may be blended within a range of less than 30 wt%. Also good. Specific examples include vinylphosphonic acid, styrenesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, N, N′-methylene-bis (acrylamide) and the like.

[(B) Non-crosslinkable (meth) acrylate polymer]
In the dental photocurable material of the present invention, (B) non-crosslinkable (A) in order to dissolve and thicken in a radical polymerizable monomer to increase the polymerizability and to obtain a tough material (Meth) acrylate polymers are used. As such a non-crosslinkable (meth) acrylate polymer, known ones can be used without particular limitation, and those having high solubility in the above-mentioned (A) (meth) acrylate polymerizable monomer are preferable.

  Specific examples include polymers of alkyl (meth) acrylate monomers. Examples of the alkyl (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth). Preferred are alkyl groups having 1 to 4 carbon atoms such as acrylate, butyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. One or two are preferred.

  These non-crosslinkable (meth) acrylate polymers do not necessarily need to be homopolymers of (meth) acrylate polymerizable monomers, and two or more kinds of different (meth) acrylate monomers are different. It may be a polymer. Furthermore, it may be a copolymer with another copolymerizable monomer as long as it does not adversely affect the effect of the present invention (usually 10 mol% or less based on the monomer). Examples of the other copolymerizable monomer include styrene monomers such as styrene, α-methylstyrene, and para-methylstyrene.

  In the present invention, as the non-crosslinkable (meth) acrylate polymer most preferably used, the solubility with the (A) (meth) acrylate polymerizable monomer is particularly high. Examples of the (meth) acrylate polymer include polymethyl methacrylate and polyethyl methacrylate.

  Said non-crosslinkable (meth) acrylate type polymer can be used as a 1 type, or 2 or more types of mixture. The average molecular weight is not particularly limited, but generally an average weight molecular weight of 5,000 to 1,000,000, more preferably 100,000 to 300,000 is preferable.

  The shape of the non-crosslinkable (meth) acrylate polymer is not particularly limited, and may be irregular particles such as those obtained by normal pulverization, or may be spherical or nearly spherical particles. . The particle size is not particularly limited, but generally a particle size of 0.005 to 200 microns is preferable.

  The compounding quantity of (B) component in the dental photocurable material of this invention is 55-300 mass parts with respect to 100 mass parts of radically polymerizable monomers which are (A) components, Furthermore, 70-180 mass parts. In particular, the amount is preferably 80 to 150 parts by mass.

[(C) Photopolymerization initiator]
In the dental photocurable material of the present invention, a combination of C1) α-diketone compound, C2) amine compound, and C3) diaryliodonium salt compound is used as the photopolymerization initiator as component (C). To do. Since the photopolymerization initiator composed of each component has a high radical generation rate and high activity, the photocurable material of the present invention has a monofunctional main component as the radically polymerizable monomer (A). Nevertheless, sufficient curability can be obtained in a short light irradiation time. When a photopolymerization initiator other than this type is used, for example, an s-triazine compound substituted with a trihalomethyl group even if it is the same photoacid generator, instead of a C3) diaryliodonium salt type compound Is not preferable because it has a low polymerization activity and requires a long light irradiation time.

C1) α-Diketone Compound In the photopolymerization initiator of the present invention, any known compound can be used as the α-diketone compound as the component C1) without any limitation. Specific examples thereof include camphorquinones such as camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid; diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, Examples include acenaphthenequinone.

  The α-diketone compound to be used may be appropriately selected and used depending on the wavelength and intensity of light used for the polymerization, the time of light irradiation, or the type and amount of other components to be combined, alone or in combination of two or more. It can also be used. Among these, considering the use for dentistry, it is preferable to have a maximum absorption wavelength in the visible light region. Generally, camphorquinones are preferably used, and camphorquinone is particularly preferable.

  The compounding amount of the component C1) in the dental photocurable material of the present invention is 0.01 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass of the radical polymerizable monomer (A). 0.03 to 5 parts by mass.

C2) Amine Compound In the photopolymerization initiator of the present invention, any known compound can be used as the amine compound of component C2) without any limitation. Since the amine compound is a primary amine and a secondary amine compound, the volatility is high and there is a problem such as odor. Therefore, a tertiary amine compound is generally used when used for dentistry. Tertiary amine compounds generally tend to have higher polymerization activity than primary or secondary amine compounds, and tertiary aliphatic amine compounds in which three saturated aliphatic groups are attached to the nitrogen atom, or nitrogen atoms. And a tertiary aromatic amine compound in which at least one of the organic groups bonded to is an aromatic group. Further, as the tertiary aromatic amine compound, an amine compound in which one aromatic group and two aliphatic groups are bonded to the tertiary nitrogen atom in terms of higher polymerization activity and availability. It is preferable that

  Specific examples of the tertiary aliphatic amine compound include N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, triethanolamine, and tri (isopropanol). Examples include amine, tri (2-hydroxybutyl) amine, triallylamine, and tribenzylamine.

  Typical tertiary aromatic amine compounds include those represented by the following general formula (1).

(Wherein R ¹ and R ² are each independently an alkyl group which may have a substituent, and R ³ has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. An aryl group which may be substituted, an alkenyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkyloxycarbonyl group which may have a substituent.
Examples of the alkyl group which may have a substituent include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and n-hexyl group; Group, an alkyl group substituted with a halogen such as 2-chloroethyl group; an alkyl group substituted with a hydroxyl group such as 2-hydroxyethyl group and the like having 1 to 6 carbon atoms. Examples of the aryl group that may have a substituent include those having 6 to 12 carbon atoms such as a phenyl group, p-methoxyphenyl, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, Examples of the alkenyl group which may have a substituent include those having 2 to 12 carbon atoms such as vinyl group, allyl group and 2-phenylethenyl group, which may have a substituent. , A methoxy group, an ethoxy group, a butoxy group and the like having 1 to 10 carbon atoms are exemplified, and the alkyloxycarbonyl group which may have a substituent includes a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group And those having 1 to 10 carbon atoms in the alkyloxy group such as amyloxycarbonyl group and isoamyloxycarbonyl group.

R ¹ and R ² are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. Specific examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and a 2-hydroxyethyl group.

As the R ^3, more preferably the binding position is the para-position, and further preferably is alkyloxycarbonyl group.

Specific examples of such aromatic amine compounds in which R ³ is an alkyloxycarbonyl group bonded to the para-position include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid. Examples include propyl, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate, and the like.

  Specific examples of other aromatic amine compounds represented by the general formula (1) include 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.

  These amine compounds of component C2) can be used alone, but it is preferable to use a combination of a tertiary aliphatic amine compound and a tertiary aromatic amine compound. As the aliphatic amine compound and the aromatic amine compound, the above-exemplified compounds can be used singly or in combination of two or more, respectively, the mass ratio of both, aliphatic amine compound: aromatic amine It is most preferred to use both together so that the compound is in the range of 3:97 to 97: 3, preferably 25:75 to 90:10, particularly 40:60 to 80:20.

  The blending amount of the component C2) in the dental photocurable material of the present invention is 0.01 to 10 parts by mass, particularly 0.02 to 5 parts per 100 parts by mass of the polymerizable monomer (A). It is preferable that it is a mass part.

C3) Diaryliodonium Salt-Based Compound The diaryliodonium salt-based compound that is the component C3) of the present invention is a compound that functions as a photoacid generator that generates Bronsted acid or Lewis acid by light irradiation. Used without limitation.

  A typical diaryliodonium salt compound is represented by the following general formula (2).

(However, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a nitro group; ^- include those represented by an anion)..

Here, examples of the halogen atom for R ⁴ , R ⁵ , R ⁶ , and R ⁷ include a fluoro group, a chloro group, a bromo group, and an iodo group. Moreover, as an alkyl group, a C1-C20 thing, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group, is preferable. Moreover, as an aryl group, a C6-C14 thing, such as a phenyl group, p-methylphenyl group, p-chlorophenyl group, a naphthyl group, is preferable. As the alkenyl group, those having 2 to 14 carbon atoms such as vinyl group, allyl group, isopropenyl group, butenyl group, 2-phenylethenyl group, 2- (substituted phenyl) ethenyl group and the like are preferable. Moreover, as an alkoxy group, a C1-C6 thing of a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is preferable. Furthermore, as the aryloxy group, those having 6 to 14 carbon atoms such as phenoxy, p-methoxyphenyl and p-octyloxyphenyl are preferable.

  Specific examples of the diaryliodonium salt include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis ( cations such as m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium, chloride, bromide, p- Toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, Kisa fluorophosphate, can be mentioned hexafluoroarsenate, diaryliodonium salt comprising anions such as hexafluoroantimonate.

  Among these diaryl iodonium salts, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphine are preferable from the viewpoint of solubility in radical polymerizable monomers. Fate, hexafluoroarsenate, and hexafluoroantimonate salt are preferable, and tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, and hexafluoroantimonate salt are particularly preferable from the viewpoint of storage stability.

  The blending amount of the component C3) in the dental photocurable material of the present invention is preferably 0.005 to 10 parts by mass, most preferably 0, per 100 parts by mass of the polymerizable monomer of component (A). 0.03 to 5 parts by mass.

  In the dental photocurable material of the present invention, the total amount of C) photopolymerization initiator comprising the above components C1) to C3) is such that (A) (meth) acrylate polymerizable monomer is polymerized. In general, the amount is preferably in the range of 0.03 to 30 parts by mass, more preferably 0.08 to 15 parts by mass with respect to 100 parts by mass of the component (A). is there. In the (C) photopolymerization initiator, the compounding ratio of C1) α-diketone compound, C2) amine compound, and C3) diaryliodonium salt compound is 10 to 1000 per 100 parts by mass of C1) α-diketone compound. Preference is given to C2) amine compounds, 5 to 1000 parts C3) diaryliodonium salt compounds, particularly 50 to 500 parts C2) amine compounds, 30 to 500 parts C3) diaryl iodonium salt compounds. Is preferred.

  The dental photocurable material of the present invention uses (A) (meth) acrylate-based polymerizable monomer and (B) non-crosslinkable (meth) acrylate-based polymer dissolved therein, and its packaging In view of storage stability, the form is preferably divided into (A) a liquid material containing a (meth) acrylate polymerizable monomer and (B) a powder material containing non-crosslinked PMMA. . At that time, each component of the photopolymerization initiator (C) may be added to either the liquid material or the powder material, but in consideration of reactivity, all components are dissolved in the liquid material in advance. Is preferred. In some cases, considering the storage stability, all or some of the components (C) of the photopolymerization initiator can be packaged separately from the liquid material and the powder material.

  Thus, when the packaging form is a powder / liquid type, the mixing ratio of the liquid material and the powder material is not particularly limited, but in the mixture, each of the components constituting the photocurable material of the present invention. However, it is preferable to carry out so as to be maintained within the range of the respective preferable blending amounts. Usually, the ratio of liquid material: powder material is in the range of 1: 0.1 to 1:10, more preferably in the range of 1: 0.5 to 1: 4, and more preferably in the range of 1: 0.75 to 1: 2. Is good to do.

  The dental photocurable material of the present invention can use a known chemical polymerization initiator in addition to the above-described (C) photopolymerization initiator, and initiates polymerization by either photopolymerization or chemical polymerization. It is also possible to use a dual cure type.

  Typical chemical polymerization initiators include combinations of organic peroxides and amines, organic peroxides, combinations of amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acids, Examples include chemical polymerization initiators such as combinations of copper ions and halogen compounds.

  Examples of compounds suitable for use in the chemical polymerization initiator include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, Organized oxides such as benzoyl peroxide; sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p Sulfinates such as sodium fluorobenzenesulfinate; (thio) barbituric acid derivatives include 5-butyl (thio) barbituric acid, 1,3,5-trimethyl (thio) barbituric acid, 1-benzyl-5-phenyl (Thio) barbituric acid, -Barbituric acids such as cyclohexyl-5-methyl (thio) barbituric acid and 1-cyclohexyl-5-butyl (thio) barbituric acid; dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium And halogen compounds such as chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide. Moreover, as amines, (C2) amine compound illustrated by the said photoinitiator can be used similarly. These chemical polymerization initiators can be used alone or in combination of two or more.

  In the above liquid material and powder material, in addition to the (B) non-crosslinkable (meth) acrylate polymer, an inorganic filler is used for operability of the dental photocurable material and adjustment of the strength of the cured product. And a crosslinkable filler can be added within a range that does not adversely affect physical properties such as toughness. As the filler, generally used are inorganic fillers and crosslinkable fillers without any limitation.

  Specific examples of the inorganic filler that can be used in the present invention include quartz, silica, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-barium oxide, silica-strontium oxide, silica- Examples include titania-sodium oxide, silica-titania-potassium oxide, silica-zirconia-sodium oxide, silica-zirconia-potassium oxide, titania, zirconia, and alumina.

  An ion-eluting filler that elutes cations under an acidic solution is also preferably used. Specific examples of the ion-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, zinc oxide, silicate glass, fluoroaluminosilicate glass, barium glass, and strontium glass.

  These inorganic fillers are preferably coated with a polymer such as a methacrylate polymer such as PMMA or polyethyl methacrylate, a silane coupling agent, or the like in order to improve the familiarity with the polymerizable monomer.

  As the crosslinkable filler, a crosslinkable filler such as crosslinkable polymethyl methacrylate can be used.

  An inorganic organic composite filler obtained by pulverizing a composite of an inorganic oxide and a polymer can also be used.

  The shape of these fillers is not particularly limited, and may be pulverized particles or spherical particles obtained by ordinary pulverization.

  The particle size of these fillers is not particularly limited, but is preferably 50 μm or less, more preferably 30 μm or less in terms of the film thickness for obtaining good compatibility of the prosthesis. Is done.

  In order to improve storage stability and environmental light stability, a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiary butylphenol is added to the dental photocurable material of the present invention as necessary. It is preferable to do. Moreover, various thickeners, such as an organic solvent and a polymer, can also be added in order to adjust a viscosity. As the organic solvent, those having a less harmful effect on the living body are desirable, and ethanol, propanol, ethylene glycol, propanediol, acetone and the like are preferably used. A plurality of these organic solvents and thickeners can be used as needed. Furthermore, a colorant such as a pigment can be blended in an appropriate amount as necessary.

  Since the dental curable material of the present invention has high toughness by using a monofunctional (meth) acrylate-based polymerizable monomer and a non-crosslinkable (meth) acrylate-based polymer, it is durable against various external forces. It is preferable to use as a material for which is required. Moreover, since it is a photopolymerization type curable material, it is preferably used as a material for which a long operation margin time and a short curing time are required. Dentals that bond teeth and other materials, or teeth, such as bonding of orthodontic brackets that bond multiple teeth in a single treatment, or fixed tooth movements that bond adjacent teeth with adjacent teeth. For example, a dental restorative material, which is often cured in the oral cavity such as an adhesive for use in the preparation of a temporary crown and a short curing time is preferable.

  The polymerizable monomer component in the dental adhesive using the dental curable material of the present invention contains at least one acidic group-containing (meth) acrylate in order to obtain better adhesive strength and adhesion durability. It is preferable to contain a system polymerizable monomer. Here, the acidic group-containing (meth) acrylate polymerizable monomer is not particularly limited as long as it is a compound having at least one acidic group and one (meth) acryloyloxy group in one molecule. These compounds can be used. Examples of the acidic group include a carboxyl group, a sulfo group, a phosphone group, a phosphoric acid monoester group, and a phosphoric acid diester group. Among them, a carboxyl group, a phosphoric acid monoester group, or a phosphoric acid diester group is more preferable as the acidic group having high adhesiveness to the tooth. Specific examples of such an acidic group-containing (meth) acrylate polymerizable monomer are as already shown in the above-mentioned (A) radical polymerizable monomer.

  Thus, when using as a dental adhesive, the (A) radical polymerizable monomer contains an acidic group-containing (meth) acrylate-based polymerizable monomer in an amount of 3 to 50 wt%, particularly 5 to 30 wt%. (It is preferable that the acidic group-containing (meth) acrylate-based polymerizable monomer is not only a monofunctional one but also a polyfunctional one.) ).

  On the other hand, when the dental curable material of the present invention is used as a dental restorative material, in order to obtain a material having high cured body strength while maintaining toughness, (A) a polyfunctional radical polymerizable monomer as a radical polymerizable monomer It is preferable to contain a body. Specific examples of the polyfunctional radical polymerizable monomer are as already shown in (A) Radical polymerizable monomer. Thus, when using as a dental restoration material, it is also a suitable aspect to add a pigment in order to adjust a color tone in restoration of a denture base.

EXAMPLES Hereinafter, although an Example shows this invention concretely, this invention is not limited at all by these Examples. In addition, the abbreviations of the compounds used in the following Examples and Comparative Examples are shown below.
(1) Abbreviations / Abbreviations (A) (Meth) acrylate polymerizable monomers [monofunctional]
-MMA: methyl methacrylate-HEMA: 2-hydroxyethyl methacrylate-MAC10: 11-methacryloyloxy-1, 1-undecanedicarboxylic acid-4-MET: 4-methacryloxyethyl trimellit [polyfunctional]
UDMA: 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane and 1,6-bis (methacrylethyloxycarbonylamino) 2,4,4-trimethylhexane mixture bis-GMA : 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane, 3G: triethylene glycol dimethacrylate, D2.6E; 2,2-bis [(4-methacryloyloxypolyethoxy) Phenyl) propane]
(B) Non-crosslinkable (meth) acrylate polymer / PMMA: polymethyl methacrylate (weight average molecular weight 250,000, average particle size 30 μm)
PEMA: polyethyl methacrylate (weight average molecular weight 250,000, average particle size 30 μm)
(C) Photopolymerization initiator C1) α-diketone compound • CQ: camphorquinone C2) amine compound • MDEOA: methyldiethanolamine • TEOA: triethanolamine • DMBE: ethyl p-dimethylaminobenzoate • DEPT: diethylamino-p- Toluidine C3) Diaryliodonium salt compounds DPI: Diphenyliodonium hexafluorophosphate IPDPI: p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate C4) Other photopolymerization initiator components TCT: 2, 4, 6-tris (trichloromethyl) -s-triazine, BSNa: sodium benzenesulfinate, PhBTEOA: tetraphenylboron triethanolamine salt, CM: 3,3′-carboni Bis (7-diethylamino) coumarin (D) Additive Components · HQME: Hydroquinone monomethyl ether · BHT: 2,6-di -t- butyl-4-methylphenol Further, following the light irradiation device using.

TP: Tokuso Power Light manufactured by Tokuyama Dental Co., Ltd., light output density 700 mW / cm ² , light intensity on irradiation surface 640-650 mW / cm ² , light source: halogen lamp, irradiation aperture 8 mm.

  Moreover, the following methods were used for the preparation method of a dental photocurable material, the evaluation method of a cure rate, and the evaluation method of toughness.

(1) Preparation method of dental photocurable material A predetermined amount of photopolymerization initiator, 0.15 parts by mass of HQME, and 0.02 parts by mass of BHT are added to the (meth) acrylate-based polymerizable monomer. The mixture was used as a liquid material, a non-crosslinkable (meth) acrylate polymer was used as a powder material, and the liquid material: powder material ratio was measured at a mixing ratio of 1: 1.3 and kneaded for 30 seconds.

(2) Curing time evaluation method A polytetrafluoroethylene mold having a 6 mmφ × 1.0 mm hole is filled with a paste and pressed with a polypropylene film, and a dental light irradiator (TP) is adhered to the polypropylene film. Then, light irradiation was performed at intervals of 10 seconds, and the hardness of the cured body was touched by hand at each irradiation time, and the light irradiation time when a force was required to sufficiently cure and break was evaluated as the curing speed.

(3) Evaluation method of toughness Cement paste was poured into a 35 mm × 1 mm × 1 mm high polytetrafluoroethylene mold, and light was irradiated for 5 minutes with a dental light irradiator (α light, manufactured by Morita) to be fully cured. . The obtained cured body was immersed in water and allowed to stand at 37 ° C. for 24 hours. A shape such as deburring of the obtained cured body was prepared, and a three-point bending test was performed using an autograph (manufactured by Shimadzu Corporation), and a fracture energy value (mJ) until the cured body was broken or bent was examined. The breaking energy value was used as an index of toughness.

(4) Measurement of enamel and dentin bond strength The bovine anterior teeth were extracted within 24 hours after slaughter, and the enamel plane was cut out with water through # 800 emery paper so as to be parallel to the lip. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then a double-sided tape with a hole having a diameter of 3 mm was fixed on this plane to form a simulated cavity. In this simulated cavity, a dental primer prepared from 1.7 g PM, 0.5 g UDMA, 0.1 g PhBTEOA, 0.2 g PTSNa, 4.2 g acetone, and 3.3 g water was used. After coating on the surface and leaving for 30 seconds, compressed air was blown for about 5 seconds. Then, after mixing the powder material and liquid material of the dental photocurable material of an Example or a comparative example, and filling this mixture in a simulated cavity, the hardened | cured material of the hard resin of diameter 8mmphi and thickness 2mm from it. (Pearl esthetic manufactured by Tokuyama Dental Co., Ltd.) was pressed and cured from above the hard resin by light irradiation with a dental light irradiator (TP) for 60 seconds. Furthermore, a stainless steel attachment having a diameter of 8 mmφ was pressed against the adhesive surface onto which a synthetic instant adhesive (“Aron Alpha” (registered trademark) manufactured by Toagosei Co., Ltd.) was dropped to produce an adhesion test piece.

  Immediately after producing the above-mentioned adhesion test piece (after 10 minutes), the adhesion strength with the tooth was measured at a crosshead speed of 1 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation).

Examples 1-14
A liquid material was prepared by stirring and mixing the (meth) acrylate polymerizable monomer and photopolymerization initiator shown in Table 1 in the dark. The liquid material and the powder material comprising the non-crosslinkable (meth) acrylate polymer shown in Table 1 were weighed in a mixing dish at a weight ratio of 1: 1.3 and mixed for 30 seconds to be pasted and cured. The curing time and breaking energy of the paste were evaluated. The results are shown in Table 1.

Comparative Examples 1-13
Similarly to Examples 1-14, the liquid material and powder material which consist of each composition shown in Table 2 were adjusted, and the hardening time and breaking energy at the time of making into a paste were evaluated. The results are shown in Table 2.

  As understood from the results of Examples 1 to 14 shown in Tables 1 and 2, in the case of the dental curable material of the present invention, a short (60 seconds or less) curing time and a sufficiently high (40 mJ or more) ) Breaking energy was obtained, and both curing time and toughness were compatible.

  On the other hand, as in Comparative Examples 1 to 5, the composition containing no diaryl iodonium salt as a photoacid generator or the composition containing sulfinates or aryl borates has a sufficiently high toughness, but has a curing time. Became longer (over 60 seconds). In particular, in a system in which the radical polymerizable monomer is composed of a polyfunctional monomer, the same photoacid generator can be used even if a diaryliodonium salt is used as the photoacid generator component of the photopolymerization initiator (Comparative Example 9). 2,4,6-tris (trichloromethyl) -s-triazine was used (Comparative Example 8), while the curing time was equal to 10 seconds, whereas the radical polymerizable monomer In the case of a monofunctional system, when 2,4,6-tris (trichloromethyl) -s-triazine is used as the photoacid generator component instead of the diaryl iodonium salt, the former can achieve 40 seconds. As a result, the time (Example 2) was greatly reduced to 80 seconds (Comparative Example 3). Thus, diaryl was used as the photoacid generator component of the monofunctional (meth) acrylate polymerizable monomer and the photopolymerization initiator. With iodonium salt compounds Specific effect on the curing time reduction when using together could be confirmed.

  Further, as in Comparative Examples 6 to 13, when a large amount of polyfunctional monomers are added as the (meth) acrylate polymerizable monomer, the curing time can be shortened, but the fracture energy is small (30 mJ or less) and toughness. Became a low material.

  As described above, when the photopolymerization initiator of the comparative example is used, if the (meth) acrylate polymerizable monomer is polyfunctional, the curing time is short but the material has low toughness. When a monofunctional monomer is used as the acrylate polymerizable monomer, the toughness is increased, but the curing time is prolonged, and it is difficult to achieve both the curing time and the toughness.

Examples 15-19
A liquid material was prepared by stirring and mixing the (meth) acrylate polymerizable monomer and photopolymerization initiator shown in Table 3 in the dark. The liquid material and the non-crosslinkable (meth) acrylate polymer were weighed in a mixing dish at a weight ratio of 1: 1.3 and mixed for 30 seconds to form a paste to obtain a dental adhesive. Each dental adhesive was evaluated for adhesion strength to enamel and dentin. The results are shown in Table 3.

Comparative Examples 14-18
Similarly to Examples 15 to 19, dental adhesives were prepared using liquid materials and powder materials having the respective compositions shown in Table 3, and the adhesion strength to enamel and dentin was evaluated. The results are shown in Table 3.

  As understood from the results of Examples 15 to 19 shown in Table 3, in the case of the dental adhesive made of the dental photocurable material of the present invention, both enamel and dentin are very high (20 MPa). The above (adhesive strength) was obtained.

  On the other hand, in the case of the composition containing no diaryl iodonium salt compound or the composition containing sulfinates or aryl borates as the photoacid generator of Comparative Examples 14 to 18, the adhesive strength is low (less than 12 MPa). there were.

Claims (5)

(A) a radical polymerizable monomer containing 70 wt% or more of a monofunctional (meth) acrylate polymerizable monomer,
And (B) a non-crosslinkable (meth) acrylate polymer, and a photopolymerization initiator comprising (C) a C1) α-diketone compound, C2) an amine compound, and C3) a diaryliodonium salt compound. Dental photocurable material.   (A) (B) Non-crosslinkable (meth) acrylate polymer 55 to 300 parts by mass, (C) C1) α-diketone compound 0.01 to 10 with respect to 100 parts by mass of the radically polymerizable monomer. 2. The dental photocurable material according to claim 1, comprising 0.01 to 10 parts by mass of C2) amine compound and 0.005 to 10 parts by mass of C3) diaryliodonium salt compound.   Divided into (A) a radically polymerizable monomer and (C) a liquid material containing a photopolymerization initiator and (B) a powder material containing a non-crosslinkable (meth) acrylate polymer. The dental photocurable material according to claim 1 or 2, wherein the dental photocurable material is a packaging form in which both materials are mixed and used at the time of use.   It is a dental adhesive, The dental photocurable material as described in any one of Claims 1-3.   It is a dental filling restorative material, The dental photocurable material as described in any one of Claims 1-3.