Dental visible light curable composition

Abstract

This invention provides a dental visible light curable composition that achieves both ambient light stability and visible light curability, as well as a dual-cure dental visible light curable composition and a kit thereof. [Solution] The dental visible light curable composition of the present invention comprises one or more (meth)acrylic acid ester-based radical polymerizable monomers (A), a filler (B), a visible light polymerization initiator (C), and a hindered phenol compound (D). The visible light polymerization initiator (C) comprises a compound having an absorption peak wavelength in the range of 400 to 700 nm. The hindered phenol compound (D) is one of the compounds represented by formulas (1), (2), (3), (4), or (5).

Description

[Technical Field]

[0001] The present invention relates to a dental visible light curable composition, and more particularly to a dental visible light curable composition that can be suitably used as a dental composite resin. [Background technology]

[0002] Dental curable compositions are widely used as materials for restoring teeth because they can impart a color tone equivalent to that of natural teeth and are easy to handle during dental restoration work. These dental curable compositions mainly consist of polymerizable monomers, inorganic fillers, and polymerization initiators, and the components are optimized according to their application.

[0003] For example, when considering polymerization initiators, dental composite resins containing photopolymerization initiators are used for the restoration of shallow cavities where aesthetics are required, due to their ease of handling and rapid hardening, thus reducing the burden on the patient. In general-purpose curable compositions, photopolymerization initiators that react to highly active ultraviolet light are widely used. However, in dental curable compositions, combinations of α-diketone compounds, tertiary amine compounds, and other electron-donating compounds (sometimes called reducing agents) are often used because polymerization activity can be obtained by irradiation with visible light, which has little effect on the human body.

[0004] However, since the polymerization activity is triggered by visible light, the influence of ambient light, such as indoor lighting, is unavoidable. If the polymerization reaction proceeds due to unintended ambient light during use, the viscosity of the composition may change, potentially hindering its use. Therefore, polymerization inhibitors such as hindered phenols are often added to ensure stability against ambient light.

[0005] On the other hand, polymerization inhibitors work to inhibit polymerization, so naturally, adding them reduces photocurability. In other words, photocurability and ambient light stability are conflicting properties, and balancing them by adjusting the amount of polymerization inhibitor added is a common technique.

[0006] To achieve both ambient light stability and photocurability, which are often conflicting requirements, improvements to photoinitiators are being considered (Patent Documents 1-4). In these compositions, polymerization does not proceed easily with relatively weak light such as ambient light, but when irradiated with strong light such as dental curing lamps, polymerization proceeds rapidly, thus achieving a high level of both photocurability and ambient light stability. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-089729 [Patent Document 2] Japanese Patent Publication No. 2006-056844 [Patent Document 3] Japanese Patent Publication No. 2010-064998 [Patent Document 4] Japanese Patent Publication No. 2014-224072 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] To obtain the aforementioned excellent photocurability, Patent Documents 1 and 3 include aliphatic amine compounds as essential components. Patent Document 2 also includes aryl borate compounds as essential components. Aliphatic amine compounds and aryl borate compounds are highly reactive with acidic compounds. Therefore, when using the technologies of Patent Documents 1 to 3, the effect may be reduced by adding acidic raw materials. Since some fillers and monomers useful as raw materials for dental curable compositions are acidic, new technological development is necessary to use them in combination.

[0009] On the other hand, in Patent Document 4, an anthracene compound is included as an essential component. Anthracene compounds generally have strong fluorescence and have a great influence on the color tone. In dental curable compositions, it is desired that the treatment area is not conspicuous, and thus delicate control of the color tone including fluorescence is desired. When an anthracene compound is used as an essential component, it is necessary to pay attention to the control of the color tone.

[0010] Therefore, there is a need for a dental visible light curable composition that can achieve both excellent environmental light stability and visible light curability without relying on the improvement of photoinitiators.

[0011] The present invention has been made in view of the above circumstances, and an object thereof is to provide a dental visible light curable composition capable of achieving both excellent environmental light stability and visible light curability, as well as a dual cure type dental visible light curable composition and a kit thereof.

Means for Solving the Problems

[0012] The dental visible light curable composition according to one embodiment of the present invention includes one or more (meth)acrylic acid ester-based radically polymerizable monomers (A), a filler (B), a visible light polymerization initiator (C), and a hindered phenol compound (D). The above visible light polymerization initiator (C) includes a compound having an absorption peak wavelength in the range of 400 nm or more and 700 nm or less. The above hindered phenol compound (D) is at least one of the compounds represented by the following formulas (1), (2), (3), (4), or (5).

Chemical formula

Chemical formula

[0013] In the present invention, in a visible light curable composition of a specific polymerization system comprising the above-mentioned (meth)acrylic acid ester-based radical polymerizable monomer (A) and the above-mentioned visible light polymerization initiator (C) having an absorption wavelength in the visible light region, by using the above-mentioned specific hindered phenol compound (D) as a polymerization inhibitor, it is possible to achieve both excellent ambient light stability and visible light curability. Specifically, under the polymerization system described above, each of the multiple hindered phenol groups of the hindered phenol compound (D) effectively acts as a radical scavenging site for small amounts of radicals slowly generated by ambient light. On the other hand, for large amounts of radicals rapidly generated by visible light, only some of the hindered phenol groups can act as radical scavenging sites, making photocuring less likely to be inhibited. In the dental visible light-curable composition of the present invention, a simple composition that does not affect the composition itself can achieve a high level of both inhibition of photocuring by ambient light and progression of photocuring by visible light.

[0014] The above (meth)acrylic acid ester-based radical polymerizable monomer (A) may also include a polyfunctional (meth)acrylic acid ester-based radical polymerizable monomer.

[0015] The visible light polymerization initiator (C) described above may also contain an α-diketone compound.

[0016] The above hindered phenol compound (D) may be at least one of the compounds represented by the following formulas (1-1), (2), or (3-1). [ka] (In the formula, X is the base represented by formula (6) above.)

[0017] The above dental visible light curable composition may further contain a polymerization accelerator.

[0018] The above-mentioned filler (B) may contain first particles (b1) having an average particle diameter of 0.05 μm or more and less than 1 μm, and second particles (b2) having an average particle diameter of 1 μm or more and less than 100 μm, and the amount of each of the first particles (b1) and the second particles (b2) added may be 50 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the above-mentioned (meth)acrylic acid ester-based radical polymerizable monomer (A).

[0019] A dual-cure dental visible light-curable composition according to one embodiment of the present invention may include the dental visible light-curable composition and a chemical polymerization initiator (E).

[0020] The hindered phenol group (D) used in the present invention can prevent the chemical polymerization initiator (E) from generating radicals due to heat or other factors during storage, thereby preventing polymerization from starting. Thus, the dual-cure type dental visible light-curable composition of the present invention has excellent not only ambient light stability and photocurability, but also storage stability.

[0021] The above-mentioned filler (B) may also contain inorganic particles having an average particle size of 0.05 μm or more and less than 100 μm.

[0022] The above-mentioned chemical polymerization initiator (E) may also include an organic peroxide (e1) and an aromatic amine compound (e2).

[0023] A kit according to one embodiment of the present invention may be a kit for preparing the dual-cure type dental visible light curable composition described above. The above kit consists of a combination of a first agent comprising a first partial composition and a second agent comprising a second partial composition, packaged in a manner that prevents physical contact between them, wherein the first agent comprises a portion of the (meth)acrylic acid ester-based radical polymerizable monomer (A), a portion of the filler (B), and the aromatic amine compound (e2), but does not contain the organic peroxide (e1); the second agent comprises the remainder of the (meth)acrylic acid ester-based radical polymerizable monomer (A), the remainder of the filler (B), and the organic peroxide (e1), but does not contain the aromatic amine compound (e2); the visible light polymerization initiator (C) is included in at least one of the first agent and the second agent; and the hindered phenol compound (D) may be included in at least one of the first agent and the second agent. [Effects of the Invention]

[0024] The dental visible light-curable composition of the present invention possesses excellent characteristics that combine ambient light stability and visible light curability. It is less susceptible to unwanted polymerization reactions due to ambient light, while efficiently polymerizing with short irradiation times using a dental light curing unit. Because its high ambient light stability allows for sufficient handling time and its high polymerization efficiency shortens the irradiation time, it is particularly suitable for use as a dental restorative material such as composite resin. [Modes for carrying out the invention]

[0025] 1. Overview of the dental visible light curable composition of the present invention The dental visible light curable composition of the present invention is a dental visible light curable composition comprising one or more (meth)acrylic acid ester-based radical polymerizable monomers (A), a filler (B), a visible light polymerization initiator (C), and a hindered phenol compound (D), wherein the visible light polymerization initiator (C) comprises a compound having an absorption peak wavelength in the range of 400 to 700 nm, and the hindered phenol compound (D) is at least one of the compounds represented by the following formulas (1), (2), (3), (4), and (5).

[0026] [ka] (In the formula, R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, Y 1 is an alkylene group having 1 to 6 carbon atoms, and X is a group represented by the following formula (6).) [Chemical Formula] (In the formula, R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, Y 2 is an alkylene group having 1 to 6 carbon atoms, and * represents a bonding site.)

[0027] The visible light-curable dental composition of the present invention achieves both high levels of photocurability and environmental light stability. This is due to the fact that a specific hindered phenol compound is blended in a specific polymerization system of a visible light-curable dental composition containing a (meth)acrylate-based radical polymerizable monomer (A) and a visible light polymerization initiator (C) that generates radicals upon exposure to visible light, resulting in this effect. The mechanism by which such excellent effects are obtained is not necessarily clear, but it is presumed that the use of a compound having a plurality of hindered phenol groups in the molecule is a major factor. As is widely known, hindered phenol groups have the effect of capturing radicals, so the higher the proportion of hindered phenol groups in the composition, the more difficult it is for radical polymerization to proceed. Here, when a compound having a plurality of hindered phenol groups in the molecule is used, the hindered phenol groups, which are radical capture sites, will be locally concentrated, and their movement is limited within the range of molecular motion. Therefore, when a large amount of radicals are rapidly generated by strong light irradiation, etc., in some cases, polymerization proceeds without some of the hindered phenol groups showing a radical capture action and is incorporated into the cured body. Therefore, the inhibitory effect on radical polymerization becomes relatively small. Therefore, when light irradiation is performed using a dental irradiator, it is considered that polymerization proceeds efficiently with short-time irradiation.

[0028] On the other hand, in cases where radicals are gradually generated by ambient light, even if the movement of hindered phenol groups is limited to within the molecule, it is thought that a relatively large number of hindered phenol groups can effectively function through diffusion or radical transfer. As a result, it is thought that the intended effect of ambient light stability was achieved even when using compounds with multiple hindered phenol groups within the molecule.

[0029] The dental visible light-curable composition of the present invention is a photopolymerization type that hardens by photopolymerization, but it may also be a dual-cure type that hardens by both photopolymerization and chemical polymerization, as described later.

[0030] The components of the dental visible light-curable composition of the present invention will be described below, followed by a description of the manufacturing method of the present invention.

[0031] In this specification, unless otherwise specified, the notation "x~y" using numerical values ​​x and y means "greater than or equal to x and less than or equal to y". If a unit is attached only to the numerical value y in such notation, that unit shall also apply to the numerical value x. Furthermore, in this specification, the term "(meth)acrylic acid ester" means both "acrylic acid ester" and "methacrylic acid ester".

[0032] 2. Components of the dental visible light curable composition of the present invention 2-1. (Meth)acrylic acid ester-based radical polymerizable monomer (A) In the dental visible light-curable composition of the present invention, it is preferable to use only the (meth)acrylic acid ester-based radical polymerizable monomer (A) as the radical polymerizable monomer, and not to include radical polymerizable monomers of other polymerization systems. It is preferable not to include (meth)acrylamide-based polymerizable monomers or styrene-based polymerizable monomers as radical polymerizable monomers of other polymerization systems, and it is more preferable not to include (meth)acrylamide-based polymerizable monomers. The (meth)acrylic acid ester-based radical polymerizable monomer (A) polymerizes rapidly even at room temperature and has excellent photocurability, but mixing monomers of different polymerization systems may reduce the polymerization rate or cause phase separation, so it is preferable not to include radical polymerizable monomers of other polymerization systems. In particular, the (meth)acrylamide-based polymerizable monomer has a reactivity relatively similar to the (meth)acrylic acid ester-based radical polymerizable monomer (A), but due to hydrogen bonding in the amide portion, it may have high viscosity or be solid. Therefore, compared to (meth)acrylic acid ester-based radical polymerizable monomer (A), it is more difficult to create a paste suitable for dental visible light curable compositions, and the effects of the present invention are easily impaired. In addition, (meth)acrylic acid ester-based radical polymerizable monomer (A) is commercially available in various variations, making it easy to adjust the components according to the application and offering excellent handling properties.

[0033] As the (meth)acrylic acid ester-based radical polymerizable monomer (A), those used in conventional dental visible light curable compositions can be used without particular limitation. The polymerizable monomers that can be used in the present invention may include monofunctional (meth)acrylic acid ester-based radical polymerizable monomers and / or polyfunctional (meth)acrylic acid ester-based radical polymerizable monomers, and it is preferable that they include polyfunctional (meth)acrylic acid ester-based radical polymerizable monomers.

[0034] Examples of monofunctional (meth)acrylic acid ester-based radical polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glyceryl mono(meth)acrylate, 2-(meth)acryloxyethyl dihydrogen phosphate, 2-(meth)acryloxyethyl phenyl hydrogen phosphate, 10-(meth)acryloxydecyl dihydrogen phosphate, 4-(meth)acryloxyethyl trimellitic acid, and 11-(meth)acryloxy-1,1-undecanedicarboxylic acid. These monofunctional polymerizable monomers may be used individually or in combination with other types.

[0035] Examples of polyfunctional (meth)acrylic acid ester-based radical polymerizable monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 2,2'-bis[4-(meth)acryloyloxyethoxyphenyl]propane, 2,2'-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2'-bis[4-(meth)acryloyloxyethoxyethoxyethoxyphenyl]propane, 2,2'-bis{4-[2-hydroxy-3-(meth)acryloyloxypropoxy]phenyl}propane, and 1,4-buta Examples of polyfunctional polymerizable monomers include 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, bis[2-(meth)acryloxyethyl]hydrogen phosphate, 1,6-bis(methacrylateethyloxycarbonylamino)trimethylhexane, 1,6-bis(methacrylateethyloxycarbonylamino)-2,2,4-trimethylhexane, 1,6-bis(methacrylateethyloxycarbonylamino)-2,4,4-trimethylhexane, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and others. These polyfunctional polymerizable monomers may be used individually or in combination with other types.

[0036] Among the polyfunctional polymerizable monomers mentioned above, polymerizable monomers with two or more functions, and more preferably two to four functions, are preferred due to their high polymerizability and particularly high mechanical properties of the cured product.

[0037] 2-2. Filler (B) As the filler (B), any filler used in conventional visible light-curable dental compositions can be used without particular limitations. That is, any organic, inorganic, or organic-inorganic composite filler can be incorporated. Examples of organic fillers include particles made of organic polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer.

[0038] Specific examples of inorganic fillers include inorganic particles such as quartz, silica, alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, and strontium glass. It is preferable to use inorganic particles whose surfaces have been hydrophobicized to improve their dispersibility with polymerizable monomers. Examples of organic-inorganic composite fillers include amorphous organic-inorganic composite particles obtained by pre-mixing these inorganic particles with polymerizable monomers to form a paste, polymerizing it, and then grinding it, and substantially granular organic-inorganic composite particles obtained by mixing inorganic particles, polymerizable monomers, and a solvent, removing the solvent to form a powder, and then polymerizing it. Furthermore, X-ray contrast properties can be imparted by using inorganic fillers containing heavy metals such as zirconia.

[0039] The particle size and shape of these filling materials are not particularly limited, and spherical or irregularly shaped particles commonly used as dental materials may be used as appropriate depending on the purpose. These filling materials may be used individually, or multiple types with different materials, particle sizes, and shapes may be used in combination. However, when used as dental filling and restorative materials, it is preferable to include inorganic particles with an average particle size of 0.05 μm or more and less than 100 μm, from the viewpoint of strength and gloss. This condition is particularly suitable for dual-cure type dental composite resins, which will be described later. Furthermore, in light-curing type dental composite resins, it is particularly preferable to use a combination of first particles (b1) with an average particle size of 0.05 μm or more and less than 1 μm, and second particles (b2) with an average particle size of 1 μm or more and less than 100 μm.

[0040] The filler (B) of the present invention allows for the selection of the average particle size and the amount of filler added depending on the polymerization method (photopolymerization type, dual-cure type). Here, the average particle size is calculated by applying the optical model "Fraunhofer" to a laser diffraction particle size analyzer (Beckman Coulter, "LS230") to determine particles with a particle size of 0.05 μm or larger, and is the particle size at which the integrated distribution in the particle size-volume integrated distribution becomes 50%. However, since particles smaller than 0.05 μm are generally difficult to disperse, their particle size is measured using an electron microscope. That is, a photograph of the powder is taken at a magnification of 100,000 times using a scanning electron microscope (JEOL Ltd., "JSM-7800F Prime"), and 30 or more particles observed within the unit field of view of the photograph are randomly selected, and the primary particle size (maximum diameter) of each is measured, and the value is calculated based on the measured value using the following formula.

number

[0041] The amount of filler (B) to be added varies depending on the other components it is combined with and the desired properties, but usually it is sufficient to use 1 part by mass or more per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A). Generally, the more filler (B) added, the lower the fluidity of the composition and the higher the viscosity, so the amount should be adjusted according to the intended use. However, when used as a dental restorative material, from the viewpoint of strength and workability, it is preferable to use 50 to 1500 parts by mass, and particularly preferable to use 70 to 1000 parts by mass, per 100 parts by mass of the above-mentioned (meth)acrylic acid ester-based radical polymerizable monomer (A). However, when used as a dental composite resin, in order to achieve both strength and workability for dental restorative work, it is preferable to include a first particle (b1) with an average particle diameter of 0.05 μm or more and less than 1 μm, and a second particle (b2) with an average particle diameter of 1 μm or more and less than 100 μm, and the amount of each particle (b1) and (b2) added is preferably in the range of 50 to 400 parts by mass, and particularly preferably in the range of 100 to 300 parts by mass, per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A). Furthermore, from the viewpoint of pursuing aesthetics after restoration, if excellent gloss is required, it is particularly preferable that the second particle (b2) with an average particle diameter of 1 μm or more and less than 100 μm is an organic-inorganic composite filler. The above conditions are particularly suitable for light-curing type dental composite resins.

[0042] 2-3. Visible light polymerization initiator (C) As the visible light polymerization initiator (C), any known visible light polymerization initiator can be used without particular restriction. However, in order to utilize light energy in the visible light region, which has little effect on the human body, it is necessary to use at least one compound having an absorption peak wavelength in the range of 400 to 700 nm. The "absorption peak wavelength" refers to the wavelength at which the absorbance changes from increasing to decreasing when represented on a two-dimensional graph in a Cartesian coordinate system with wavelength as the X axis and absorbance as the Y axis. The compounds included in the visible light polymerization initiator (C) above only need to have at least one absorption peak wavelength in the range of 400 to 700 nm.

[0043] In the present invention, any compound having an absorption peak wavelength in the range of 400 to 700 nm that can be used as a visible light polymerization initiator can be used without particular limitations. However, since adjusting the rate of radical generation is important in the present invention, hydrogen abstraction initiators are preferred over intramolecular cleavage initiators. Examples of hydrogen abstraction type visible light polymerization initiators include α-diketone compounds such as camphorquinone, diacetyl, and 1-phenyl-1,2-propanedione; benzoquinone derivatives such as naphthoquinone and anthraquinone; and benzophenone derivatives such as p,p'-dimethylaminobenzophenone.

[0044] Among the visible light polymerization initiators mentioned above, α-diketone compounds are preferred from the viewpoint of high polymerizability and suppression of coloration of the cured product, and camphorquinone is particularly preferred. These visible light polymerization initiators may be used individually or in combination with other types.

[0045] The amount of visible light polymerization initiator (C) used varies depending on the other components and the type of polymerizable monomer used in combination, but usually 0.01 to 10 parts by mass is used per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A), preferably 0.05 to 5 parts by mass.

[0046] 2-4. Hindered phenol compounds (D) As the hindered phenol compound (D), any known compound represented by formulas (1) to (5) can be used without any particular restrictions. Examples of hindered phenol compounds that can be used in the present invention include 4,4',4''-[nitrilotris(methylene)]tris(2,6-di-t-butylphenol), pentaerythritol tetrakis[3-(3,5-di-t-di-butyl-4-hydroxyphenyl)propionate], pentaerythritol tris[3-(3,5-di-t-di-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)mesitylene, and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5,-triazinan-2,4,6-trione. These hindered phenol compounds may be used individually or in combination with other compounds.

[0047] Among the above hindered phenol compounds (D), it is preferable that at least one of the compounds represented by the following formulas (1-1), (2), or (3-1) is selected from the viewpoint of availability. [ka] (In the formula, X is the base represented by formula (6).) [ka] (In the formula, R 2 and R 3 Each of these is independently a linear or branched alkyl group having 1 to 12 carbon atoms, Y 2 (where * represents an alkylene group with 1 to 6 carbon atoms, and * represents a bonding site.)

[0048] In the hindered phenol group represented by formula (6), from the viewpoint of its ability to capture and stabilize radicals, it is preferable that the area around the hindered phenol group, which is the radical capture site, is sterically crowded. That is, R 2 and R 3Preferably, at least one of them is an alkyl group on a branched chain, R 2 and R 3 It is particularly preferable that it is a t-butyl group. 2 The longer the chain length, the greater the mobility of the hindered phenol group, and the less effective the present invention is, therefore, it is preferable that the compound is methylene or ethylene. For this reason, it is particularly preferable that the compound represented by formula (1-1), (2), or (3-1) is the compound represented by the following formula (HP1), the following formula (HP2), or the following formula (HP3), respectively. Specifically, it is preferable that HP1 is 2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)mesitylene, HP2 is 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5,-triazinan-2,4,6-trione, and HP3 is pentaerythritol tetrakis[3-(3,5-di-t-di-butyl-4-hydroxyphenyl)propionate].

[0049] [ka]

[0050] The amount of hindered phenol compound (D) used varies depending on the other components and the type of polymerizable monomer used in combination, but it is sufficient to use 0.01 to 10 parts by mass per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A), preferably 0.05 to 5 parts by mass, and more preferably 0.1 parts by mass or more and 1.0 part by mass or less.

[0051] 2-5. Other ingredients In the dental visible light curable composition of the present invention, in addition to the components (A) to (D) above, a polymerization accelerator may be further added as an optional component. The polymerization accelerator may include amine compounds that generate polymerization-active radicals by hydrogen abstraction and do not fall under the aromatic amine compound (e2) (reducing agent) described later, or electron-accepting compounds that promote radical generation by electron transfer, and any known compounds can be added without limitation. The combination of the polymerization accelerator and the visible light polymerization initiator promotes the generation of radicals, making it easier to obtain excellent visible light curability. Examples of usable polymerization accelerators include aromatic amine compounds such as p-dimethylaminoacetophenone and ethyl p-dimethylaminobenzoate; aliphatic amine compounds such as p-tolyldiethanolamine, triethanolamine, and N-methyldiethanolamine; iodonium salt compounds such as p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate and diphenyliodonium-2-carboxylate monohydrate; and s-triazine compounds such as 2,4,6-tris(trichloromethyl)-s-triazine. When a polymerization accelerator is included, the amount is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the (meth)acrylic acid ester-based radical polymerizable monomer (A).

[0052] Furthermore, polymerization inhibitors that do not fall under the category of hindered phenol compounds (D) may be used in combination. Examples of known polymerization inhibitors that do not fall under the category of hindered phenol compounds (D) include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, hydroquinone monomethyl ether, and phenothiazine. However, using other polymerization inhibitors in large quantities may reduce the effectiveness of the present invention. Therefore, the polymerization inhibitor that does not fall under the category of hindered phenol compounds (D) is preferably blended in an amount of 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and particularly preferably not used at all, per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A).

[0053] The visible light-curable dental composition of the present invention may contain known additives used in dental restorative materials. Examples of such additives include ultraviolet absorbers, organic solvents, pigments, fragrances, thickeners, and antistatic agents.

[0054] 3. Method for producing the dental visible light-curable composition of the present invention and its uses The method for producing the dental visible light-curable composition of the present invention is not particularly limited, and any known method for producing dental visible light-curable compositions may be used as appropriate. Specifically, in the dark, predetermined amounts of the (meth)acrylic acid ester-based radical polymerizable monomer (A), filler (B), visible light polymerization initiator (C), hindered phenol compound (D), and other components such as polymerization accelerators, which constitute the dental visible light-curable composition of the present invention, may be weighed out and mixed to form a paste. The dental visible light-curable composition of the present invention produced in this manner is stored in a light-shielded place until use.

[0055] The dental visible light curable composition of the present invention is not particularly limited to dental applications, but due to its excellent ambient light stability and ability to cure with short light exposure times, it is preferably used as a dental restorative material (especially dental composite resin).

[0056] As a means of curing the dental visible light-curable composition of the present invention, any known polymerization method may be employed. Specifically, methods such as light irradiation using light sources such as LEDs, halogen lamps, fluorescent lamps, sunlight, or laser light, or a combination of these methods and a heating polymerization apparatus, can be used. However, the irradiation light must include visible light with a wavelength in the range of 400 to 700 nm. The irradiation time of the light varies depending on the wavelength and intensity of the light source, as well as the shape and material of the cured body. This can be determined in advance through preliminary experiments, but generally, it is preferable to adjust the mixing ratio of the various components so that the irradiation time is in the range of 5 to 60 seconds.

[0057] 4. Dual-cure type dental visible light curable composition The dual-cure dental visible light-curable composition according to one embodiment of the present invention undergoes curing by photopolymerization and chemical polymerization. Therefore, the dual-cure dental visible light-curable composition according to one embodiment of the present invention further comprises a chemical polymerization initiator (E) in addition to the dental visible light-curable composition of the present invention described above.

[0058] The chemical polymerization initiator (E) of the present invention comprises an organic peroxide (e1) and an aromatic amine compound (e2). The organic peroxide (e1) acts as an oxidizing agent, and the aromatic amine compound (e2) acts as a reducing agent, generating radicals through a redox reaction and promoting chemical polymerization. In this dual-cure type dental visible light curable composition, chemical polymerization curing proceeds at the moment the oxidizing agent and reducing agent are mixed. However, polymerization may proceed due to heat applied during storage. In contrast, the hindered phenol compound (D) used in the present invention can inhibit polymerization that proceeds due to heat applied during storage, and also acts to inhibit photocuring in response to ambient light that enters at the stage before preparation. For this reason, the dual-cure type dental visible light curable composition used in the present invention is excellent not only in ambient light stability and photocurability, but also in storage stability.

[0059] The following describes the components of a chemical polymerization initiator (E) suitable for dual-cure dental visible light-curable compositions.

[0060] 5. Components of the dual-cure type dental visible light curable composition of the present invention 5-1.Organic peroxide (e1) The organic peroxide (e1) is not particularly limited and any known one can be used. Typical organic peroxides (e1) include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates.

[0061] Examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

[0062] Examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

[0063] Examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0064] Examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3.

[0065] Examples of peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)valeric acid-n-butyl ester.

[0066] Examples of peroxyesters include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate and t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxyisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate and t-butyl peroxymalelic acid.

[0067] Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

[0068] Among these, diacyl peroxide is preferred in terms of stability, toxicity, and catalytic activity, and benzoyl peroxide is particularly preferred.

[0069] The above organic peroxide (e1) can be used alone or in a mixture of two or more types.

[0070] From the viewpoint of achieving both curability and storage stability, the amount of organic peroxide (e1) added is preferably 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A), and more preferably 0.1 parts by mass or more and 3 parts by mass or less.

[0071] 3-2. Aromatic amine compounds (e2) The aromatic amine compound (e2) can be any known compound that acts as a reducing agent for the oxidizing agent of the organic peroxide (e1) above, and is not particularly limited. Typically, however, it is an amine compound in which at least one of the organic groups bonded to the nitrogen atom is an aromatic group, and the aromatic group does not have an electron-withdrawing group. The aromatic amine compound (e2) is preferably an amine compound in which one aromatic group and two aliphatic groups (typically alkyl groups) are bonded to a tertiary nitrogen atom (hereinafter also referred to as a "tertiary aromatic amine compound"), as it has higher polymerization activity, lower volatility and therefore less odor, and is also readily available. The aromatic group may have substituents of a hydrogen atom, alkyl group, aryl group, alkenyl group, or alkoxy group. A typical tertiary aromatic amine compound is one represented by the following general formula (7).

[0072] [ka] (In the formula, R a and R b Each of them is an alkyl group, and R c (This is a hydrogen atom, a hydrocarbon group, or an alkoxy group.)

[0073] The above R a and R b Examples of alkyl groups include those having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, and n-hexyl groups. These alkyl groups may also be substituted, such as those substituted with halogens like chloromethyl or 2-chloroethyl groups, or those substituted with hydroxyl groups like 2-hydroxyethyl groups.

[0074] Also, R cExamples of hydrocarbon groups include the alkyl groups mentioned above, as well as aryl groups, alkenyl groups, and aralkenyl groups, which may also have substituents. Specifically, examples include aryl groups such as phenyl groups, p-methoxyphenyl, p-methylthiophenyl groups, p-chlorophenyl groups, and 4-biphenylyl groups, alkenyl groups such as vinyl groups and 2-propenyl groups, and aralkenyl groups such as 2-phenylethenyl groups, which have 1 to 12 carbon atoms.

[0075] Examples of alkoxy groups include methoxy, ethoxy, butoxy, and pentoxy groups, which have 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. These groups may also have substituents.

[0076] Note, R c It is more preferable that the bond position be in the para position.

[0077] Specific examples of aromatic amine compounds represented by general formula (7) include N,N-dimethylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-di(β-hydroxyethyl)-p-toluidine, 4-t-butyl-N,N-dimethylaniline, 2-[4-(dimethylamino)phenyl]methanol, and 2-[4-(dimethylamino)phenyl]ethanol.

[0078] The above aromatic amine compound (e2) can be used alone or as a mixture of two or more types.

[0079] From the viewpoint of curability and color stability of the cured product, the amount of aromatic amine compound (e2) added is preferably 0.01 parts by mass or more and 3 parts by mass or less per 100 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A), and more preferably 0.1 parts by mass or more and 2 parts by mass or less.

[0080] 6. Kit for preparing dental visible light curable compositions A kit for preparing a dental visible light-curable composition according to one embodiment of the present invention may consist of a combination of a first component, comprising a first partial composition, and a second component, comprising a second partial composition, which are packaged in a manner that prevents physical contact between them in order to prevent hardening from progressing during storage and distribution. That is, in the kit according to this embodiment, the first component and the second component are separated by an inhibitory member that inhibits molecular diffusion between them, thereby making physical contact impossible. Typically, the first component and the second component are held individually in various containers such as syringes, bags, or bottles that serve as the inhibitory member. The containers or bags containing the first and second components are preferably capable of blocking outside air and external light, and can be made of, for example, resin, glass, metal, or ceramics. However, the inhibitory member only needs to be capable of separating the first component and the second component, and is not limited to the above configuration.

[0081] In the kit according to this embodiment, from the viewpoint of storage stability, the components contained in the first agent and the components contained in the second agent are combinations of components that do not react with each other. From this viewpoint, it is preferable that the first agent contains the aromatic amine compound (e2) and does not contain the organic peroxide (e1), and the second agent contains the organic peroxide (e1) and does not contain the aromatic amine compound (e2), so that the oxidizing agent, the organic peroxide (e1), and the reducing agent, the aromatic amine compound (e2), do not react with each other. Furthermore, the (meth)acrylic acid ester-based radical polymerizable monomer (A) and the filler (B) may be contained in either the first agent or the second agent, but typically, it is preferable that the first agent and the second agent each contain a portion of the (meth)acrylic acid ester-based radical polymerizable monomer (A) and a portion of the filler (B).

[0082] The visible light polymerization initiator (C) may be included in at least one of the first and second components. Similarly, the hindered phenol compound (D) may also be included in at least one of the first and second components. In other words, the visible light polymerization initiator (C) and the hindered phenol compound (D) may be included in either the first or second component, or in both the first and second components. In particular, since the organic peroxide (e1) is prone to generating radicals due to the heat applied during storage, it is preferable to add the hindered phenol compound (D) to the second component containing the organic peroxide (e1) from the viewpoint of storage stability. Furthermore, from the viewpoint of uniformly dispersing the hindered phenol compound (D) in the dual-cure type dental visible light curable composition, it is even more preferable that it be included in both the first and second components. This allows for uniform photocuring and makes it easier to obtain a cured body with uniform hardness.

[0083] In the kit according to this embodiment, from the viewpoint of storage stability and photocurability, the first component preferably contains 0.01 parts by mass or more and 1 part by mass or less of a hindered phenol compound (D) per 50 parts by mass of a (meth)acrylic acid ester-based radical polymerizable monomer (A). Furthermore, in the kit according to this embodiment, from the viewpoint of storage stability and photocurability, the second agent preferably contains 0.1 parts by mass or more and 2 parts by mass or less of hindered phenol compound (D) per 50 parts by mass of (meth)acrylic acid ester-based radical polymerizable monomer (A), and more preferably 0.2 parts by mass or more and 1 part by mass or less. In a dual-cure type dental visible light curable composition, it is preferable that the hindered phenol compound (D) is present in an amount of 0.1 parts by mass to 3 parts by mass, and more preferably 0.2 parts by mass to 1 part by mass, per 100 parts by mass of the (meth)acrylic acid ester-based radical polymerizable monomer (A). [Examples]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] 1. Abbreviation of a compound [(Meth)acrylic acid ester-based radical polymerizable monomer (A)] • Bis-GMA: 2,2'-Bis[4-(2-hydroxy-3-methacrylateoxypropoxy)phenyl]propane • 3G: Triethylene glycol dimethacrylate · D-2.6E; 2,2-bis(methacryloyloxypolyethoxyphenyl)propane

[0086] [Filler (B)] F1: Spherical silica-zirconia, average particle size; 0.2 μm, treated with γ-methacryloyloxypropyltrimethoxysilane. F2: Organic-inorganic composite filler, average particle size: 30 μm, manufactured by the method described below. F3: Amorphous silica-zirconia, average particle size: 5 μm Furthermore, F2 is prepared by mixing 100 parts by mass of F1, 25 parts by mass of urethane dimethacrylate as a polymerizable monomer, 0.5 parts by mass of azobisisobutyronitrile as a thermal polymerization initiator, and ethanol as a solvent, then removing the solvent to obtain a powder, and then thermal polymerization (100°C, 1 hour).

[0087] In the production of a light-curable dental visible light-curable composition, F1 is used as a first particle (b1) with an average particle diameter of 0.05 μm or more and less than 1 μm, and F2 is used as a second particle (b2) with an average particle diameter of 1 μm or more and less than 100 μm. In the manufacture of a dual-cure type dental visible light curable composition, F1 and F3 are used as inorganic particles with an average particle size of 0.05 μm or more and less than 100 μm.

[0088] The average particle size of the filler was calculated using the measurement method described above.

[0089] [Visible light polymerization initiator (C)] • CQ: Camphorquinone

[0090] [Hindered phenolic compounds (D)] HP1: 2,4,6-Tris(3',5'-di-t-butyl-4'-hydroxybenzyl)mesicylene HP2: 1,3,5-Tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5,-triazinan-2,4,6-trione HP3: Pentaerythritol tetrakis[3-(3,5-di-t-di-butyl-4-hydroxyphenyl)propionate]

[0091] [Chemical polymerization initiator (E)] (Oxidizing agent: Organic peroxide (e1)) BPO: Benzoyl peroxide (Reducing agent: Aromatic amine compound (e2)) DEPT: N,N-di(2-hydroxyethyl)-p-toluidine • DMPT: N,N-dimethyl-p-toluidine

[0092] [Other compounds] (Polymerization accelerator) • DMBE: p-dimethylaminobenzoate ethyl • DPIC: Diphenyliodonium-2-carboxylate monohydrate (General polymerization inhibitors) BHT: 2,6-di-t-butyl-4-methylphenol

[0093] 2. Examples 1-7 and Comparative Examples 1 and 2 In Examples 1-7 and Comparative Examples 1 and 2, photopolymerizable dental visible light curable compositions were prepared and evaluated as follows.

[0094] [Example 1] Under red light, a polymerizable monomer composition was prepared by mixing 100 parts by mass of a (meth)acrylic acid ester-based radical polymerizable monomer (A), consisting of a mixture of Bis-GMA: 60 parts by mass and 3G: 40 parts by mass, with 0.2 parts by mass of CQ as a photopolymerization initiator (C), 0.5 parts by mass of HP1 as a hindered phenol compound (D), and 0.5 parts by mass of DMBE. Next, the obtained polymerizable monomer composition and 150 parts by mass of F1 as a filler (B) were mixed using a mortar and pestle until homogeneous to prepare a paste-like dental visible light curable composition. The obtained paste was filled into the barrel of a syringe for dental flowable composite resin (manufactured by Tokuyama Dental Co., Ltd., the same container used for product name: Esterite FlowQuick). After attaching a needle tip (inner diameter φ0.75 mm) to the syringe nozzle, the paste was dispensed by manually pressing the plunger, and the ambient light stability and polymerization rate (visible light curability) of the cured material were evaluated as follows. The ambient light stability and polymerization rate of the cured product were evaluated as follows.

[0095] (1) Environmental light stability The distance between the light source and the sample was set so that the surface of the dental visible light curable composition paste to be evaluated was 10,000 lux. A dental light (light source: halogen light, manufactured by Takara Belmont Co., Ltd.) was used as the light source, and the distance between the sample and the light source was set so that the illuminance measured by an illuminance meter (Tokyo Glass Instruments Co., Ltd., "Digital Lux Meter FLX-1330") was the above illuminance. The light intensity at this irradiated surface was 0.3 mW / cm². 2 The following procedure was performed: 0.03 g of the prepared dental visible light-curable composition was weighed onto a polypropylene film, irradiated with the above-mentioned dental light for a predetermined time, and then the sample was crushed and its state was observed. A sample was deemed acceptable if it spread uniformly and thinly when crushed, and unacceptable if gelation occurred and it could not be spread uniformly and thinly. The above procedure was repeated with irradiation times at 5-second intervals, and the longest irradiation time among the acceptable samples was used as the value of ambient light stability. A longer value indicates better ambient light stability and ensures a good margin of error for handling. The illuminometer used had a sensitivity of 400 nm to 700 nm.

[0096] For evaluating ambient light stability, a time of 90 seconds or more until curing begins was considered good, while any other case was considered poor.

[0097] (2) Polymerization rate of the cured product The prepared dental visible light-curable composition was applied to a polyethylene IR card to a thickness of 1 mm, and the initial near-infrared absorption spectrum was measured by transmission using an infrared spectrometer (Perkin Elmer, "Spectrum One"). Subsequently, the dental visible light-curable composition was irradiated with light for 5 or 10 seconds using a dental light curing unit (Tokuyama Dental, "Tokuso Power Light") (light output density 700 mW / cm²). 2 After curing using the method described above, the near-infrared absorption spectrum was measured in the same manner. From the initial and post-light irradiation near-infrared absorption spectra, 6160 cm⁻¹ was obtained. -1 The area of ​​the absorption peak originating from the C=CH bond, with a peak in the vicinity, was determined, and the polymerization rate was calculated using the following formula.

[0098] Polymerization rate [%]=(1-A1 / A0)×100 In the equation, A0 is the peak area derived from the initial C=CH bond. A1 represents the peak area originating from the C=CH bond after light irradiation.

[0099] For the evaluation of visible light curability, a polymerization rate of 60% or more after 5 seconds of irradiation and 65% or more after 10 seconds of irradiation was considered good, while all other cases were considered poor.

[0100] [Examples 2-7 and Comparative Examples 1 and 2] The paste was prepared in the same manner as in Example 1, except that the paste composition was changed to that shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. In Table 1, the numbers in parentheses indicate the amount added (parts by mass).

[0101] [Table 1]

[0102] As shown in Examples 1 to 7 of Table 1 above, when hindered phenol compound (D) was incorporated, the ambient light stability was 90 seconds or more, and when a dental light curing unit was used, the polymerization rate was 60% or more even with 5 seconds of light irradiation, indicating good ambient light stability and polymerizability. On the other hand, when hindered phenol compound (D) was not incorporated (Comparative Examples 1 and 2), either the ambient light stability or the polymerization rate was inferior to that of the above examples, indicating that it is difficult to achieve both ambient light stability and polymerizability.

[0103] 3. Examples 8-15 and Comparative Examples 3 and 4 In Examples 8-15 and Comparative Examples 3 and 4, dual-cure dental visible light-curable compositions were prepared and evaluated.

[0104] Specifically, Composition I (Part 1), containing a reducing agent, and Composition II (Part 2), containing an oxidizing agent, were prepared using the additive amounts (parts by mass) shown in Table 2, corresponding to (I-1) to (I-4). The (meth)acrylic acid ester-based radical polymerizable monomer (A) (50 parts by mass) contained in Composition I and Composition II both consist of D-2.6E (22 parts by mass), 3G (22 parts by mass), and Bis-GMA (6 parts by mass). The filler (B) contained in Composition I and Composition II both consist of F3 (160 parts by mass) and F1 (140 parts by mass). Then, dual-cure type dental visible light curable compositions corresponding to Examples 8 to 15 and Comparative Examples 3 and 4 were prepared using the combinations of Composition I and Composition II shown in Table 3.

[0105] The polymerization rate (visible light curability) and storage stability of the cured bodies of the obtained dual-cure dental visible light curable compositions were evaluated. Visible light curability was evaluated in the same manner as described above. Storage stability was confirmed starting with composition II, which contains an organic peroxide (e1) that is prone to generating radicals when heated. Specifically, the state of composition II was observed after storage at 45°C for 10 days and 15 days. Compositions that showed gelation after the above period were evaluated as B (poor), and those that did not show gelation were evaluated as A (good). The results are shown in Table 3.

[0106] [Table 2] [Table 3]

[0107] (Evaluation results) In Examples 8-14, where the hindered phenol compound (D) of the present invention was used as a polymerization inhibitor, the polymerization rate was high both after 5 seconds of visible light irradiation and after 10 seconds of visible light irradiation, and good or better results were obtained in the evaluation of photocurability. Furthermore, in Composition II (second agent) containing the organic peroxide (e1) in Examples 8-14, no gelation was observed even after 10 days of storage at 45°C. This confirmed that the composition exhibited excellent storage stability and photocurability. In particular, in Example 12, a large amount of hindered phenol compound (D) was added, and no gelation occurred even after 15 days of storage, demonstrating superior storage stability and good photocurability.

[0108] In contrast, Comparative Examples 3 and 4, which did not contain the hindered phenol compound (D) of the present invention and used a general polymerization inhibitor (BHT) having one hindered phenol group, resulted in poor storage stability or poor photocurability. Specifically, in Comparative Example 3, increasing the amount of BHT added suppressed gelation after storage, but resulted in a low polymerization rate and poor photocurability. In Comparative Example 4, reducing the amount of BHT added improved photocurability, but resulted in gelation and poor storage stability.

Claims

1. It comprises one or more (meth)acrylic acid ester-based radical polymerizable monomers (A), a filler (B), a visible light polymerization initiator (C), and a hindered phenol compound (D), The visible light polymerization initiator (C) comprises a compound having an absorption peak wavelength in the range of 400 nm to 700 nm. A dental visible light curable composition wherein the hindered phenol compound (D) is at least one of the compounds represented by the following formulas (1), (2), (3), (4), and (5). 【Chemistry 1】 (In the formula, R １ Y is a linear or branched alkyl group having 1 to 6 carbon atoms. １ (where X is an alkylene group having 1 to 6 carbon atoms, and X is the group represented by the following formula (6).) 【Chemistry 2】 (In the formula, R ２ and R ３ Each is independently a linear or branched alkyl group having 1 to 12 carbon atoms, Y ２ (where * represents an alkylene group with 1 to 6 carbon atoms, and * represents a bonding site.)

2. The dental visible light curable composition according to claim 1, wherein the (meth)acrylic acid ester-based radical polymerizable monomer (A) comprises a polyfunctional (meth)acrylic acid ester-based radical polymerizable monomer.

3. The dental visible light curable composition according to claim 1, wherein the visible light polymerization initiator (C) comprises an α-diketone compound.

4. The dental visible light curable composition according to claim 1, wherein the hindered phenol compound (D) is at least one compound represented by the following formulas (1-1), (2), or (3-1). 【Transformation 3】 (In the formula, X is the base represented by formula (6) above.)

5. The dental visible light curable composition according to claim 1, further comprising a polymerization accelerator.

6. The dental visible light curable composition according to claim 1, wherein the filler (B) comprises first particles (b1) having an average particle diameter of 0.05 μm or more and less than 1 μm, and second particles (b2) having an average particle diameter of 1 μm or more and less than 100 μm, and the amount of each of the first particles (b1) and the second particles (b2) added is 50 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the (meth)acrylic acid ester-based radical polymerizable monomer (A).

7. A dual-cure dental visible light-curable composition comprising a dental visible light-curable composition according to any one of claims 1 to 5 and a chemical polymerization initiator (E).

8. The dual-cure type dental visible light curable composition according to claim 7, wherein the filler (B) contains inorganic particles having an average particle diameter of 0.05 μm or more and less than 100 μm.

9. The dual-cure type dental visible light curable composition according to claim 7, wherein the chemical polymerization initiator (E) comprises an organic peroxide (e1) and an aromatic amine compound (e2).

10. A kit for preparing a dual-cure type dental visible light curable composition according to claim 9, It consists of a combination of a first component, comprising a first subcomposition, and a second component, comprising a second subcomposition, which are packaged in a manner that prevents them from physically coming into contact with each other. The first agent comprises a portion of the (meth)acrylic acid ester-based radical polymerizable monomer (A), a portion of the filler (B), and the aromatic amine compound (e2), but does not contain the organic peroxide (e1). The second agent comprises the remainder of the (meth)acrylic acid ester-based radical polymerizable monomer (A), the remainder of the filler (B), and the organic peroxide (e1), but does not contain the aromatic amine compound (e2). The visible light polymerization initiator (C) is included in at least one of the first agent and the second agent. The kit wherein the hindered phenol compound (D) is contained in at least one of the first agent and the second agent.

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