Photopolymerizable dental surface coating material composition

Abstract

To provide a photopolymerizable dental surface coating material which can finish the applied part smoothly in a short time by exhibiting excellent surface curability regardless of the type of light irradiator, can protect the restoration from abrasion and discoloration for a long time by exhibiting excellent adhesiveness to various restorations including dental glass ionomer cement for filling and tooth substance, and has excellent storage stability capable of maintaining properties and characteristics for a long time.SOLUTION: A photopolymerizable dental surface coating material composition of the present invention comprises (a) a polyfunctional polymerizable monomer, (b) a volatile monofunctional polymerizable monomer, (c) an acidic group-containing polymerizable monomer, (d) an α-diketone compound, (e-1) an aromatic tertiary amine as (e) an amine compound, and (e-2) an aliphatic tertiary amine as (e) an amine compound, wherein the compounding ratio of (e-1) to (e-2) is in a mass ratio range of 1.0:99.0 to 70.0:30.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photopolymerizable dental surface coating material for forming a resin coating layer on the surface of a restoration. More specifically, the present invention relates to a photopolymerizable dental surface coating material capable of finishing the surface of a restoration into a smooth surface and protecting the restoration from wear and coloring by forming the resin coating layer.

Background Art

[0002] Restorations used in the oral cavity include filling restoration materials, inlays, onlays, crowns, prosthetic devices for dental crowns such as bridges, artificial teeth, denture bases, temporary restoration materials, and the like. These restorations are made of ceramic materials, resin materials, or organic-inorganic composite materials combining inorganic fillers and resin materials.

[0003] It is desired that the surface of these restorations exposed in the oral cavity be as smooth as possible. The reason is that the surface properties of the restoration affect aesthetics, tongue feeling, plaque adhesion, and wear of the opposing teeth. Therefore, the operation of polishing the surface of the restoration is generally performed.

[0004] The polishing of the restoration is generally performed in the order of rough polishing, medium polishing, and finish polishing using a plurality of abrasives with different grit sizes. However, such polishing work performed in a plurality of steps is very complicated and takes time to make the surface of the restoration smooth.

[0005] On the other hand, after rough polishing the surface of the restoration, a method has been proposed in which a photopolymerizable dental surface coating material mainly composed of a polymerizable monomer is applied and irradiated with light to form a thin resin coating layer, thereby obtaining a smooth surface in a short time.

[0006] For example, Patent Document 1 proposes a photopolymerizable dental surface coating material composition mainly composed of a tetrafunctional or higher dipentaerythritol acrylate-based polymerizable monomer, a volatile solvent, and a photopolymerization initiator.

[0007] Patent Document 2 discloses a technique for reducing the yellowness of a resin coating layer caused by a photoinitiator by using acylphosphine oxide as a photoinitiator in a photopolymerizable dental surface coating material composition containing a polyfunctional acrylate crosslinking agent in which three or more hydroxyl groups in one molecule of pentaerythritol or dipentaerythritol are modified with acrylate groups, a volatile (meth)acrylate compound, and a photoinitiator.

[0008] Patent Document 3 proposes a photopolymerizable dental surface coating material composition with improved wear resistance by incorporating inorganic fine particles with an average particle size of 1 to 100 nm and a surface modified with an alkoxysilane having an unsaturated double bond in a (meth)acrylate-based polymerizable monomer in a monodispersed state. Also, in this patent document, it is shown that by including a (meth)acrylate-based polymerizable monomer having an acidic group in the (meth)acrylate-based polymerizable monomer, the adhesiveness to dental filling glass ionomer cement and dentin is improved.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, although the photocurable dental surface coating material compositions of Patent Document 1 and Patent Document 2 have adhesiveness to resin-based materials, they do not have adhesiveness to glass ionomer cements for dental filling that do not contain a resin component. Therefore, when applied to such restorations, peeling of the resin coating layer occurred in a short period. Further, since these compositions do not have adhesiveness to dentin either, even when applied to restorations having adhesiveness, if the resin coating layer is formed not only on the restoration but also on the dentin beyond the interface between the restoration and the dentin, peeling and chipping occurred starting from there.

[0011] Furthermore, the photocurable dental surface coating material composition of Patent Document 2 exhibits excellent surface curability and exhibits high lubricity and mechanical properties when irradiated with light using a dental polymerization light irradiator using a halogen lamp (hereinafter referred to as a halogen irradiator) as a light source. However, when irradiated with light using a dental polymerization light irradiator using an LED lamp (hereinafter referred to as an LED irradiator), which is widely used in actual clinical practice, as a light source, the surface curability is insufficient and a large amount of unpolymerized polymerizable monomers remains on the surface, and the lubricity and material strength of the cured product are significantly inferior.

[0012] In addition, as a result of the inventors' examination of the photocurable dental surface coating material composition of Patent Document 3, it was found that gelation occurred during storage when only an aromatic tertiary amine was included as a reducing agent for the photoinitiator in the composition. Further, when only an aliphatic tertiary amine was included as a reducing agent for the photoinitiator, it was found that the surface curability and the adhesiveness to glass ionomer cements for dental filling and dentin decreased over time.

[0013] As described above, the conventional photocurable dental surface coating material compositions had problems in either surface curability, adhesiveness, or storage stability. Therefore, there has been a demand for a photocurable dental surface coating material composition having these properties in a well-balanced manner.

[0014] Therefore, the present invention aims to solve the above-described problems of the prior art, exhibit excellent surface curability regardless of the type of light irradiator, and smoothly finish the application site in a short time. Also, by showing excellent adhesiveness to various restorations and tooth substances including glass ionomer cement for dental filling, it is possible to protect the restoration from wear and coloring for a long time. Furthermore, the present invention aims to provide a photocurable dental surface coating material having excellent storage stability capable of maintaining its properties and characteristics for a long time.

Means for Solving the Problems

[0015] As a result of intensive studies to solve the above problems, the inventors of the present invention found that in a photocurable dental surface coating material composition containing a polyfunctional polymerizable monomer, a volatile monofunctional polymerizable monomer, and an acidic group-containing polymerizable monomer, and an α-diketone compound and an amine compound, a composition in which an aromatic tertiary amine and an aliphatic tertiary amine are simultaneously blended as the amine compound and the blending ratio of the aromatic tertiary amine and the aliphatic tertiary amine is adjusted within a specific range exhibits good surface curability regardless of the type of light irradiator, and the formed resin coating layer shows excellent adhesiveness to various restorations including glass ionomer cement for dental filling and tooth substances, and further, even when stored for a long time, the composition does not gel and stably exhibits its properties. Also, in the above composition, by further blending an acylphosphine oxide compound and / or a polyfunctional acrylate-based polymerizable monomer, it was found that the surface curability is further improved and a smoother resin coating layer with less surface unpolymerized layer is formed, leading to the completion of the present invention.

[0016] That is, the present invention is (a) a polyfunctional polymerizable monomer, (b) a volatile monofunctional polymerizable monomer, (c) an acidic group-containing polymerizable monomer, (d) an α-diketone compound, (e) as an amine compound (e-1) an aromatic tertiary amine, and (e-2) an aliphatic tertiary amine A photopolymerizable dental surface coating material composition containing A photopolymerizable dental surface coating material composition characterized in that the blending ratio of (e-1) and (e-2) is 1.0:99.0 to 70.0:30.0 by mass ratio.

[0017] Further, in the photopolymerizable dental surface coating material composition, (a) Polyfunctional polymerizable monomer 20.0 to 90.0 wt%, (b) Volatile monofunctional polymerizable monomer 5.0 to 70.0 wt%, (c) Polymerizable monomer containing an acidic group 0.1 to 10.0 wt%, (d) α-diketone compound 0.1 to 10.0 wt%, (e-1) Aromatic tertiary amine 0.1 to 7.0 wt%, and (e-2) Aliphatic tertiary amine 0.1 to 10.0 wt%, Preferably contains.

[0018] Further, in the photopolymerizable dental surface coating material composition, it is preferable to contain (f) an acylphosphine oxide compound.

[0019] Further, in the photopolymerizable dental surface coating material composition, it is preferable that (a) the polyfunctional polymerizable monomer is a polyfunctional acrylate-based polymerizable monomer.

Effects of the Invention

[0020] The photocurable dental surface coating material composition of the present invention exhibits excellent surface curability regardless of the type of light irradiator, and can form a smooth resin coating layer on the restoration in a short time. Further, the photocurable dental surface coating material composition of the present invention exhibits excellent adhesiveness not only to restorations made of resin-based materials such as dental composite resins and hard resins for crowns, but also to restorations that do not contain a resin component such as glass ionomer cement for dental filling and tooth substance. Therefore, the risk of peeling and chipping can be reduced, and the restoration can be protected from wear and coloring for a long time in a wider range of cases. Furthermore, the photocurable dental surface coating material composition of the present invention is excellent in storage stability and can maintain its properties and characteristics for a long time.

Embodiments for Carrying Out the Invention

[0021] Hereinafter, each component in the photocurable dental surface coating material composition of the present invention will be described in detail.

[0022] The (a) polyfunctional polymerizable monomer that can be used in the photocurable dental surface coating material composition of the present invention can be used without any limitation as long as it has two or more radically polymerizable unsaturated groups, such as acryloyl groups and / or methacryloyl groups, in one molecule. That is, for example, polyfunctional (meth)acrylate-based polymerizable monomers and polyfunctional (meth)acrylamide-based polymerizable monomers can be mentioned. Hereinafter, the polyfunctional polymerizable monomer having a (meth)acrylate group as a polymerizable unsaturated group will be specifically shown as a representative example. In the present invention, (meth)acryloyl is used to comprehensively represent both acryloyl and methacryloyl, and (meth)acrylate is used to comprehensively represent both acrylate and methacrylate.

[0023] Examples of the aromatic difunctional polymerizable monomer include, but are not limited to, bisphenol A diglycidyl (meth)acrylate (Bis-GMA), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2(4-(meth)acryloyloxyethoxyphenyl)-2(4-(meth)acryloyloxydiethoxyphenyl)propane, 2(4-(meth)acryloyloxydiethoxyphenyl)-2(4-(meth)acryloyloxytriethoxyphenyl)propane, 2(4-(meth)acryloyloxydipropoxyphenyl)-2(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, etc.

[0024] Examples of aliphatic difunctional polymerizable monomers include, but are not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-hydroxypropyl-1,3-di(meth)acrylate (GDMA), 3-hydroxypropyl-1,2-di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate (GDA), neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethanol 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, 1,10-decanediol di(meth)acrylate, etc.

[0025] Examples of trifunctional polymerizable monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol triacrylate, etc.

[0026] Examples of tetrafunctional or higher functional polymerizable monomers include, but are not limited to, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc.

[0027] Examples of urethane polymerizable monomers include difunctional or polyfunctional (three or more functional groups) di(meth)acrylates having urethane bonds derived from the addition products of polymerizable monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, and diisocyanate compounds such as methylcyclohexane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylbenzene, and 4,4-diphenylmethane diisocyanate. However, the monomers are not limited thereto. These (a) polyfunctional polymerizable monomers can be used alone or as a mixture of two or more. Among them, it is preferable to use a polyfunctional acrylate-based polymerizable monomer as the (a) polyfunctional polymerizable monomer. Further, the (a) polyfunctional polymerizable monomer preferably does not contain an acidic group. Note that the (a) polyfunctional polymerizable monomer can be the same as the (c) acidic group-containing polymerizable monomer, but it is preferably different.

[0028] The (a) polyfunctional polymerizable monomer is preferably contained in the photocurable dental surface coating material composition in an amount of 20.0 to 90.0 wt%, and more preferably 30.0 to 80.0 wt%. When the content of the (a) polyfunctional polymerizable monomer is less than 20.0 wt% or exceeds 90.0 wt%, the surface curability may decrease.

[0029] The (b) volatile monofunctional polymerizable monomer that can be used in the photocurable dental surface coating material composition of the present invention can be used without any limitation as long as it is a monofunctional polymerizable monomer having a boiling point of 50 to 120°C at normal pressure. Specific examples of the (b) volatile monofunctional polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, and 2,2,2-trifluoroethyl (meth)acrylate. However, the monomers are not limited thereto. These can be used alone or as a mixture of two or more.

[0030] (b) The volatile monofunctional polymerizable monomer is preferably contained in the photocurable dental surface coating material composition in an amount of 5.0 to 70.0 wt%, more preferably 10.0 to 60.0 wt%. When the content of (b) the volatile monofunctional polymerizable monomer is less than 5.0 wt% or exceeds 70.0 wt%, the surface curability may decrease. Further, (b) the volatile monofunctional polymerizable monomer preferably does not contain an acidic group. Note that (b) the volatile monofunctional polymerizable monomer can be the same as (c) the acidic group-containing polymerizable monomer, but is preferably different.

[0031] The (c) acidic group-containing polymerizable monomer that can be used in the photocurable dental surface coating material composition of the present invention can be used without any limitation as long as it is a polymerizable monomer having one or more acidic groups such as a phosphate group, a phosphonic acid group, a carboxy group, and a sulfonic acid group, and one or more radically polymerizable unsaturated groups such as a (meth)acryloyl group in one molecule. That is, acidic group-containing (meth)acrylate-based polymerizable monomers and acidic group-containing (meth)acrylamide-based polymerizable monomers can be mentioned. Hereinafter, the acidic group-containing polymerizable monomer having a (meth)acrylate group as a polymerizable unsaturated group will be specifically shown as a representative example.

[0032] Examples of the polymerizable monomer having a phosphate group include, but are not limited to, (meth)acryloyloxymethyldihydrogen phosphate, 2-(meth)acryloyloxyethyldihydrogen phosphate, 3-(meth)acryloyloxypropyldihydrogen phosphate, 4-(meth)acryloyloxybutyldihydrogen phosphate, 5-(meth)acryloyloxypentyldihydrogen phosphate, 6-(meth)acryloyloxyhexyldihydrogen phosphate, 7-(meth)acryloyloxyheptyldihydrogen phosphate, 8-(meth)acryloyloxyoctyldihydrogen phosphate, 9-(meth)acryloyloxynonyldihydrogen phosphate, 10-(meth)acryloyloxydecyldihydrogen phosphate, 11-(meth)acryloyloxyundecyldihydrogen phosphate, 12-(meth)acryloyloxydodecyldihydrogen phosphate, 16-(meth)acryloyloxyhexadecyldihydrogen phosphate, 20-(meth)acryloyloxyeicosyldihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[3-(meth)acryloyloxypropyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenylhydrogen phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethylhydrogen phosphate, and the like.

[0033] Examples of the polymerizable monomer having a phosphonic acid group include, but are not limited to, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate, (meth)acryloyloxyethylphenylphosphonate, and the like.

[0034] Examples of the polymerizable monomer having a carboxy group include (meth)acrylic acid, 2-chloroacrylic acid, 3-chloro(meth)acrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, 1,4-di(meth)acryloyloxyethyl pyromellitic acid, 6-(meth)acryloyloxynaphthalene-1,2,6-tricarboxylic acid, 1-butene-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, 4-(meth)acryloyloxyethyl trimellitic acid and its anhydride, 4-(meth)acryloyloxybutyl trimellitic acid and its anhydride, 2-(meth)acryloyloxybenzoic acid, β-(meth)acryloyloxyethyl hydrogen succinate, β-(meth)acryloyloxyethyl hydrogen maleate, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, p-vinylbenzoic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyoctyloxycarbonyl phthalic acid, 4-(meth)acryloyloxydecyloxycarbonyl phthalic acid and their acid anhydrides, 5-(meth)acryloylaminopentyl carboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, etc., but are not limited thereto.

[0035] Examples of the polymerizable monomer having a sulfonic acid group include, but are not limited to, 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth)acrylate, 4-(meth)acryloyloxybenzenesulfonic acid, 3-(meth)acryloyloxypropanesulfonic acid, etc. These (c) acidic group-containing polymerizable monomers can be used alone or in admixture of two or more.

[0036] (c) The acidic group-containing polymerizable monomer is preferably contained in the photopolymerizable dental surface coating material composition in an amount of 0.1 to 10.0 wt%, more preferably 1.0 to 7.0 wt%. When the content of the (c) acidic group-containing polymerizable monomer is less than 0.1 wt%, the adhesiveness to dental filling glass ionomer cement or the dentin around the restoration may decrease. Further, when the content of the (c) acidic group-containing polymerizable monomer exceeds 10.0 wt%, the surface curability decreases, and the storage stability deteriorates, and gelation may occur over time.

[0037] The (d) α-diketone compound that can be used in the photopolymerizable dental surface coating material composition of the present invention acts as a photosensitizer and can be used without any limitation as long as it is generally used in dental curable compositions. Specific examples of the α-diketone compound include, but are not limited to, benzil, camphorquinone, α-naphthyl, acetonaphthacene, p,p'-dimethoxybenzil, p,p'-dichlorobenzilacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone, etc. These can be used alone or in admixture of two or more. Among them, it is preferable to use camphorquinone as the (d) α-diketone compound.

[0038] (d) The α-diketone compound is preferably contained in the photocurable dental surface coating composition in an amount of 0.1 to 10.0 wt%, more preferably 0.5 to 5.0 wt%. When the content of the (d) α-diketone compound is less than 0.1 wt%, the surface curability may decrease. Further, when the content of the (d) α-diketone compound exceeds 10.0 wt%, the cured body may become significantly yellow or brown and may be inferior in aesthetics.

[0039] The (e) amine compound that can be used in the photocurable dental surface coating composition of the present invention acts as a photopolymerization accelerator and can be used without any limitation as long as it is generally used in dental curable compositions. However, in the present invention, two types, namely, (e-1) an aromatic tertiary amine and (e-2) an aliphatic tertiary amine, must be blended simultaneously. The (e) amine compound is specifically exemplified below.

[0040] Specific examples of the (e-1) aromatic tertiary amine include, but are not limited to, N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, p-N,N-dimethyl-toluidine, m-N,N-dimethyl-toluidine, p-N,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic acid methyl ester, N,N-dihydroxyethylaniline, p-N,N-dihydroxyethyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, etc. These can be used alone or in combination of several types. Among them, it is preferable to use p-dimethylaminobenzoic acid ethyl ester as the (e-1) aromatic tertiary amine.

[0041] The (e-1) aromatic tertiary amine is preferably contained in the photocurable dental surface coating material composition in an amount of 0.1 to 7.0 wt%, and more preferably in an amount of 0.5 to 5.0 wt%. When the content of the (e-1) aromatic tertiary amine is less than 0.1 wt%, the surface curability may decrease over time. Further, when the content of the (e-1) aromatic tertiary amine exceeds 7.0 wt%, the storage stability deteriorates and gelation may occur over time.

[0042] (e-2)Specific examples of the aliphatic tertiary amine include, but are not limited to, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-ethyldiallylamine, N-ethyldibenzylamine, triethanolamine, tri(isopropanol)amine, tri(2-hydroxybutyl)amine, triallylamine, tribenzylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N-[3-(dimethylamino)propyl]acrylamide, 2,2'-(n-butylimino)diethanol, etc. These can be used alone or in combination of two or more. Among them, as the (e-2) aliphatic tertiary amine, it is preferable to use triethanolamine, N,N-dimethylaminoethyl methacrylate, and N-[3-(dimethylamino)propyl]acrylamide.

[0043] The (e-2) aliphatic tertiary amine is preferably contained in the photocurable dental surface coating material composition in an amount of 0.1 to 10.0 wt%, and more preferably 1.0 to 7.0 wt%. When the content of the (e-2) aliphatic tertiary amine is less than 0.1 wt%, the surface curability decreases, and the storage stability deteriorates, and gelation may occur over time. Further, when the content of the (e-2) aliphatic tertiary amine exceeds 10.0 wt%, a salt is formed with the (c) acidic group-containing polymerizable monomer contained in the composition, and the adhesiveness to dental filling glass ionomer cement or the dentin around the restoration may decrease.

[0044] In the present invention, the mass ratio of (e-1) an aromatic tertiary amine to (e-2) an aliphatic tertiary amine must be 1.0:99.0 to 70.0:30.0. Further preferably, the mass ratio of (e-1) an aromatic tertiary amine to (e-2) an aliphatic tertiary amine is 10.0:90.0 to 50.0:50.0. At this ratio, when the blending ratio of (e-1) an aromatic tertiary amine is smaller than 1.0:99.0, the storage stability deteriorates, and the surface curability decreases over time. Also, when the (e-2) aliphatic tertiary amine with a higher blending ratio is contained, it forms a salt with the (c) acidic group-containing polymerizable monomer in the composition, and the adhesiveness to the dental filling glass ionomer cement or the dentin around the restoration decreases. On the other hand, at this ratio, when the blending ratio of (e-1) an aromatic tertiary amine is larger than 70.0:30.0, the surface curability decreases. Also, the storage stability deteriorates and it gels over time.

[0045] In the photopolymerizable dental surface coating material composition of the present invention, it is preferable to contain (f) an acylphosphine oxide compound because the surface curability is further improved. The (f) acylphosphine oxide compound acts as a photosensitizer and can be used without any limitation as long as it is generally used in dental curable compositions. Specific examples of the (f) acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, etc. These can be used alone or in combination of two or more.

[0046] The (f) acylphosphine oxide compound is preferably contained in the photopolymerizable dental surface coating material composition in an amount of 0.1 to 10.0 wt%.

[0047] For the purpose of adjusting the properties, workability, or mechanical properties of the photocurable dental surface coating composition of the present invention, in addition to the above-mentioned (b) volatile monofunctional polymerizable monomers, non-volatile monofunctional polymerizable monomers can be further included. In this case, it is preferable that the non-volatile monofunctional polymerizable monomer does not contain an acidic group-containing polymerizable monomer.

[0048] Examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, etc., but are not limited thereto. These can be used alone or in combination of two or more.

[0049] The photocurable dental surface coating composition of the present invention can further contain a photosensitizer and / or a photopolymerization accelerator other than those described above.

[0050] Examples of the photosensitizer include benzoin alkyl ethers such as benzoin ethyl ether, thioxanthones such as thioxanthone, benzophenones such as benzophenone, α-aminoacetophenones such as 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ketals such as benzyldimethyl ketal, coumarins such as 3-(4-methoxybenzoyl)coumarin, titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, etc., but are not limited thereto. These can be used alone or in combination of two or more.

[0051] Examples of the photopolymerization accelerator include, but are not limited to, amine compounds such as primary amines and secondary amines, barbituric acids such as 1,3,5-trimethylbarbituric acid, tin compounds such as dibutyltin dilaurate, aldehyde compounds such as lauryl aldehyde, and sulfur-containing compounds such as dodecyl mercaptan. These can be used alone or in combination of two or more.

[0052] Furthermore, for the purpose of adjusting the properties or workability of the photopolymerizable dental surface coating material composition of the present invention, a thickener can be included within a range that does not adversely affect various properties. As the thickener that can be used in the photopolymerizable dental surface coating material composition of the present invention, either an inorganic thickener or an organic thickener can be used.

[0053] Examples of the inorganic thickener include, but are not limited to, fumed silica, calcium carbonate, calcium silicate, magnesium silicate, and clay minerals such as saponite, montmorillonite, beidellite, vermiculite, sauconite, stibnite, hectorite, smectite, nontronite, and sepiolite.

[0054] Examples of the organic thickener include, but are not limited to, methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, carboxypolymethylene, sodium alginate, propylene glycol alginate, sodium polyacrylate, starch, sodium starch glycolate, starch phosphate ester, polyvinyl pyrrolidone, carboxyvinyl polymer, carrageenan, gum arabic, karaya gum, and guar gum. These thickeners can be used alone or in combination of two or more.

[0055] The tackifier is preferably contained in the photocurable dental surface coating composition in the range of 0.001 to 10.0% by mass.

[0056] Furthermore, the photocurable dental surface coating composition of the present invention can contain a non-acid-reactive powder within a range that does not adversely affect various properties for the purpose of adjusting its operability, mechanical properties, or curing properties.

[0057] The non-acid-reactive powder that can be used in the photocurable dental surface coating composition of the present invention is not particularly limited as long as it does not contain an element that reacts with the acidic group of the (c) acidic group-containing polymerizable monomer, and can be used without particular limitation. Examples of the non-acid-reactive powder include those known as dental fillers, such as inorganic fillers, organic fillers, and organic-inorganic composite fillers, etc. These can be used alone or in combination of several kinds without any limitation. Among them, it is particularly preferable to use an inorganic filler. Also, the shape of these non-acid-reactive powders is not particularly limited, and they may be of any particle shape such as spherical, needle-like, plate-like, crushed, scaly, etc., or aggregates thereof, and are not limited thereto. The average particle diameter of these non-acid-reactive powders is not particularly limited, but is preferably in the range of 0.001 to 30 μm.

[0058] Specific examples of the inorganic filler include quartz, amorphous silica, ultrafine silica, various glasses that do not contain an element that reacts with the acidic group (including glass by the melting method, synthetic glass by the sol-gel method, glass produced by gas-phase reaction, etc.), silicon nitride, silicon carbide, boron carbide, etc., but are not limited thereto.

[0059] The non-acid-reactive powder is preferably contained in the photocurable dental surface coating composition in the range of 0.001 to 30% by mass.

[0060] The photocurable dental surface coating composition of the present invention can optionally contain components such as preservatives, antibacterial agents, coloring pigments, and other conventionally known additives as necessary.

Examples

[0061] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The components (a) to (f) and their abbreviations used in the preparation of the photopolymerizable dental surface coating material compositions of the examples and comparative examples are as follows.

[0062] [(a) Polyfunctional polymerizable monomer] PTA: Pentaerythritol triacrylate UDMA: Di(methacryloxyethyl)-2,2,4-trimethylhexane methylene diurethane DPH: Dipentaerythritol hexaacrylate [(b) Volatile monofunctional polymerizable monomer] MMA: Methyl methacrylate EMA: Ethyl methacrylate [(c) Polymerizable monomer containing an acidic group] MDP: 10-Methacryloyloxydecyl dihydrogen phosphate 6-MHPA: 6-Methacryloxyhexyl-3-phosphonoacetate [(d) α-Diketone compound] CQ: dl-Camphorquinone [(e-1) Aromatic tertiary amine] DMBE: p-Dimethylaminobenzoic acid ethyl ester [(e-2) Aliphatic tertiary amine] TEOA: Triethanolamine DMEM: N,N-Dimethylaminoethyl methacrylate [(f) Acylphosphine oxide compound] APO: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide

[0063] The photopolymerizable dental surface coating material compositions of Examples 1 to 34 and Comparative Examples 1 to 8 were prepared by mixing the respective components in the proportions shown in Tables 1 and 2.

[0064]

Table 1

[0065]

Table 2

[0066] For these photocurable dental surface coating compositions (Examples 1 to 34, Comparative Examples 1 to 8), surface curability, adhesiveness, and storage stability were evaluated. The test results are shown in Tables 3 and 4. The evaluation methods are as follows.

[0067] 〔Surface curability〕 In an environment of 23°C and 50% humidity, each photocurable dental surface coating composition was thinly applied using a brush onto a disk-shaped hardened body (φ15, thickness = 1.0 mm) of a commercially available glass ionomer cement for dental filling (Glass Ionomer FX Ultra (shade: A2) / manufactured by Shofu Inc.). After that, light irradiation was performed using a dental polymerization light irradiator to form a resin coating layer. The dental polymerization light irradiator used was of two types: Shofu Grip Light II with a halogen lamp as the light source or Pen Bright with an LED lamp as the light source (both manufactured by Shofu Inc.), and the light irradiation time was set to two conditions of 10 seconds or 20 seconds. The surface state of the resin coating layer was visually and instrumentally confirmed, and the surface curability was evaluated in the following five grades. In addition, the test was carried out three times for each composition and light irradiation condition. 5···Shows high gloss, and no surface unpolymerized layer is observed at all. 4···Shows relatively high gloss, but a slight surface unpolymerized layer is observed. 3···Shows gloss, but a slight surface unpolymerized layer is observed. 2···Somewhat inferior in gloss, and many surface unpolymerized layers are observed. 1···Has no gloss, and many surface unpolymerized layers are observed.

[0068] 〔Adhesiveness〕 In an environment of 23°C and 50% humidity, bovine tooth enamel polished on the surface with #600 silicon carbide abrasive paper, or a disc-shaped hardened body (φ15, thickness = 1.0 mm) of a commercially available glass ionomer cement for dental filling (Glass Ionomer FX Ultra (shade: A2) / manufactured by Kuraray Noritake Dental Inc.), each photocurable dental surface coating material composition was thinly applied using a brush. After that, light irradiation was performed for 20 seconds using a Penlight (manufactured by Kuraray Noritake Dental Inc.) with an LED lamp as the light source to form a resin coating layer. After applying a load of 5,000 thermal cycles (5°C ⇔ 60°C, immersion time at each temperature: 1 minute) to each test piece, the adhesion state of the resin coating layer to the adherend was visually confirmed, and the adhesiveness was evaluated in the following 5 grades. In addition, the test was carried out 5 times for each composition and adherend. 5... No peeling is observed in all samples. 4... Peeling is observed in 1 sample out of 5. 3... Peeling is observed in 2 samples out of 5. 2... Peeling is observed in 3 or 4 samples out of 5. 1... Peeling is observed in all samples.

[0069] 〔Storage stability〕 Each photocurable dental surface coating material composition was filled into a plastic bottle container, and after tightly closing the cap, it was left standing in an environment of 50°C for 3 months (hereinafter referred to as 50°C stored product). After leaving the 50°C stored product standing in an environment of 23°C for 24 hours, the surface curability was evaluated by the method described above. In addition, a dental polymerization light irradiator used a Penlight with an LED lamp as the light source, and the light irradiation time was 20 seconds. Further, the content of each 50°C stored product was taken out of the container, and its properties were confirmed visually and with an instrument. The confirmation of the properties was performed for 3 bottle containers of each composition and evaluated in the following 5 grades. 5... No gelation is observed in all samples. 4... A slight increase in viscosity is observed in at least 1 or more samples out of 3. Among 3 ··· 3 samples, an obvious increase in viscosity is observed in at least 1 or more samples. Among 2 ··· 3 samples, partial curing is observed in at least 1 or more samples. Among 1 ··· 3 samples, complete curing is observed in at least 1 or more samples. - ··· Evaluation was impossible because the sample had gelled.

[0070] 〔Aesthetic property〕 In an environment of 23°C and 50% humidity, each photopolymerizable dental surface coating material composition was thinly applied onto a disk-shaped cured body (φ15, thickness = 1.0 mm) of a commercially available glass ionomer cement for dental filling (glass ionomer FX Ultra (shade: A2) / manufactured by Kuraray Noritake Dental Inc.) using a brush, and then light irradiation was performed using a dental polymerization light irradiator to form a resin coating layer with a thickness of 30 μm or 10 μm. Note that a Penbright (manufactured by Kuraray Noritake Dental Inc.) using an LED lamp as a light source was used as the dental polymerization light irradiator, and the light irradiation time was set to 10 seconds. The shade of the prepared sample was visually compared with the shade of a disk-shaped test body to which the photopolymerizable dental surface coating material composition was not applied, and the aesthetic property was evaluated in the following 5 grades. 5 ··· When the thickness of the resin coating layer is 30 μm, no shade difference is observed. 4 ··· When the thickness of the resin coating layer is 30 μm, a slight shade difference is observed, but when the thickness is 10 μm, no shade difference is observed. 3 ··· When the thickness of the resin coating layer is 10 μm, a slight shade difference is observed. 2 ··· When the thickness of the resin coating layer is 10 μm, a shade difference is observed. 1 ··· When the thickness of the resin coating layer is 10 μm, an obvious shade difference is observed.

[0071]

Table 3

[0072]

Table 4

[0073] As shown in Table 3, the photopolymerizable dental surface coating material compositions of Examples 1 to 34 were excellent in surface curability regardless of the type of light irradiator, and exhibited good adhesiveness and storage stability. On the other hand, as shown in Table 4, the photopolymerizable dental surface coating material compositions of Comparative Examples 1 to 8 were inferior in any one of the properties of surface curability, adhesiveness, and storage stability as compared with Examples 1 to 34.

Industrial Applicability

[0074] According to the present invention, by exhibiting excellent surface curability regardless of the type of light irradiator, the application site can be smoothly finished in a short time, and excellent adhesiveness to various restorations and dentin including glass ionomer cement for dental filling can be shown to protect the restoration from wear and coloring for a long time. Furthermore, it is possible to provide a photopolymerizable dental surface coating material composition having excellent storage stability capable of maintaining its properties and characteristics for a long time.

Claims

1. (a) a polyfunctional polymerizable monomer, (b) a volatile monofunctional polymerizable monomer; (c) acidic group-containing polymerizable monomer, (d) an α-diketone compound, (e) As an amine compound (e-1) aromatic tertiary amines, and (e-2) Aliphatic tertiary amine A photopolymerizable dental surface coating composition comprising: A photopolymerizable dental surface coating material composition, characterized in that the blending ratio of (e-1) and (e-2) is 1.0:99.0 to 70.0:30.0 by mass ratio.

2. (a) 20.0 to 90.0 wt % of a polyfunctional polymerizable monomer, (b) 5.0 to 70.0 wt % of a volatile monofunctional polymerizable monomer, (c) 0.1 to 10.0 wt % of an acidic group-containing polymerizable monomer, (d) 0.1 to 10.0 wt % of an α-diketone compound, (e-1) 0.1 to 7.0 wt % of an aromatic tertiary amine, and (e-2) aliphatic tertiary amine 0.1 to 10.0 wt%, The photopolymerizable dental surface coating composition according to claim 1 ,

3. 3. The photopolymerizable dental surface coating material composition according to claim 1, further comprising (f) an acylphosphine oxide compound.

4. 4. The photopolymerizable dental surface coating material composition according to claim 1, wherein the polyfunctional polymerizable monomer (a) is a polyfunctional acrylate-based polymerizable monomer.

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