Dental material composition, dental material and antibacterial composition

Abstract

The present invention provides a composition for a dental material containing a polymerizable compound (A) that includes a polymerizable group and two or more oxyalkylene groups.

Description

[Technical field]

[0001] The present disclosure relates to a dental material composition, a dental material, and an antibacterial composition. [Background technology]

[0002] Dental materials have long been known for use in dental treatment. When dental materials are used, bacteria may adhere to the surface of the dental material, and the adhered bacteria may cause plaque. In order to cope with such a situation, dental materials are sometimes required to have antibacterial properties. Antibacterial agents used in dental materials include silver ions, but antibacterial materials other than silver ions are also required. For example, Patent Document 1 describes an antibacterial dental polymerizable composition containing a (meth)acrylic acid ester compound (A) having a 10-undecenoxy group and an ethoxy group, represented by a specific structural formula, and a polymerization initiator (D).

[0003] Patent Document 1: JP 2004-189661 A Summary of the Invention [Problem to be solved by the invention]

[0004] The antibacterial properties of a dental material composition include antibacterial properties in the state of the dental material composition before hardening, and antibacterial properties in the state of a hardened product obtained by hardening the dental material composition. Here, from the viewpoint of inhibiting plaque formation when using a dental material, it is considered that the antibacterial properties of the hardened product obtained by hardening the dental material composition are particularly important. In this regard, the antibacterial dental polymerizable composition of Patent Document 1 leaves room for improvement in terms of antibacterial properties in the state of a cured product obtained by curing the composition.

[0005] An object of one embodiment of the present disclosure is to provide a dental composition capable of giving a cured product having excellent antibacterial properties, and a dental material and an antibacterial composition each including the cured product. [Means for solving the problem]

[0006] Means for solving the above problems include the following aspects. <1> A dental composition comprising a polymerizable compound (A) having one polymerizable group and two or more oxyalkylene groups. <2> The one polymerizable group is a (meth)acryloyl group. <1> The dental material composition according to claim 1. <3> The number average molecular weight Mn of the polymerizable compound (A) is 200 or more. <1> or <2> The dental material composition according to claim 1. <4> The polymerizable compound (A) contains a compound represented by the following formula (1): <1> ~ <3> 13. The dental material composition according to claim 12,

[0007] [ka]

[0008] In formula (1), R 1 is an organic group having 1 to 24 carbon atoms and not containing a polymerizable group, or a hydroxyl group, and R 2 is a hydrogen atom or a methyl group, X is a divalent hydrocarbon group having 2 to 6 carbon atoms, and n is an integer of 2 or greater. <5> R in the above formula (1) 1 is an alkoxy group having 1 to 24 carbon atoms or a hydroxyl group <4> The dental material composition according to claim 1. <6> the one polymerizable group in the polymerizable compound (A) is a (meth)acryloyl group, and the composition further contains a (meth)acrylate compound (B) other than the polymerizable compound (A); <1> ~ <5> 13. The dental material composition according to claim 12, <7> The total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is 15% by mass or more based on the total mass of the dental material composition. <6> The dental material composition according to claim 1. <8> The content of the polymerizable compound (A) is 1% by mass to 50% by mass based on the total content of the polymerizable compound (A) and the (meth)acrylate compound (B). <6> or <7> The dental material composition according to claim 1. <9> The (meth)acrylate compound (B) includes a (meth)acrylate compound containing an acidic group. <6> ~ <8> 13. The dental material composition according to claim 12, <10> A dental composition comprising a polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups. <11> The total content of pigments and dyes is 10% by mass or less <1> ~ <10> 13. The dental material composition according to claim 12, <12> Used as a bonding material or composite resin <1> ~ <11> 13. The dental material composition according to claim 12, <13> <1> ~ <12> 13. A dental material comprising a hardened product of the dental material composition according to claim 12. <14> An antibacterial composition comprising a polymerizable compound (A) having one polymerizable group and two or more oxyalkylene groups. <15> Used as a coating agent <14> The antibacterial composition according to claim 1. Effect of the Invention

[0009] According to one embodiment of the present disclosure, it is possible to provide a dental composition capable of giving a cured product having excellent antibacterial properties, and a dental material and an antibacterial composition including the cured product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In this disclosure, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate. In this disclosure, when referring to the amount of each component in a composition, if multiple substances corresponding to each component are present in the composition, it means the total amount of multiple substances present in the composition, unless otherwise specified.

[0011] <Dental material composition> The dental material composition of the present disclosure includes a first embodiment and a second embodiment. Each embodiment will be described below.

[0012] [First embodiment] The dental composition of the first embodiment contains a polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups. The dental composition of the first embodiment contains the polymerizable compound (A), and thus a cured product having excellent antibacterial properties can be obtained. The reason for this is presumed to be as follows. This is presumably because the two or more oxyalkylene groups in the polymerizable compound (A) have antibacterial activity, and further, because there is one polymerizable group, it is more likely that two or more oxyalkylene groups will be present on the surface of the cured product upon curing.

[0013] Moreover, one embodiment of the dental composition of the first embodiment can also give a cured product with excellent adhesive strength.

[0014] <Polymerizable compound (A)> The polymerizable compound (A) contains one polymerizable group and two or more oxyalkylene groups. There are no particular limitations on the type of polymerizable group, and examples thereof include a (meth)acryloyl group and a vinyl group. Of the above, from the viewpoint of obtaining a cured product with excellent antibacterial properties, one of the polymerizable groups is preferably a (meth)acryloyl group.

[0015] The two or more oxyalkylene groups are not particularly limited as long as they contain two or more oxyalkylene groups. The oxyalkylene group preferably has 2 to 6 carbon atoms, more preferably has 2 to 5 carbon atoms, and further preferably has 2 to 4 carbon atoms. The two or more oxyalkylene groups may or may not be consecutive, but are preferably consecutive.

[0016] In the dental composition of the first embodiment, the polymerizable compound (A) preferably contains a compound represented by the following formula (1).

[0017] [ka]

[0018] In formula (1), R 1 is an organic group having 1 to 24 carbon atoms and not containing a polymerizable group, or a hydroxyl group, R 2 is a hydrogen atom or a methyl group, X is a divalent hydrocarbon group having 2 to 6 carbon atoms; n is an integer of 2 or greater.

[0019] R in formula (1) 1 R is preferably an alkoxy group having 1 to 24 carbon atoms or a hydroxyl group. 1 Preferably, the alkyl group has 1 to 18 carbon atoms, and more preferably has 1 to 12 carbon atoms. X is preferably a divalent hydrocarbon group having 2 to 6 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and even more preferably a divalent hydrocarbon group having 2 carbon atoms. It is preferable that n is an integer of 3 or more.

[0020] The number average molecular weight of the polymerizable compound (A) is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more, from the viewpoint of obtaining a cured product with excellent antibacterial properties. The number average molecular weight of the polymerizable compound (A) may be 2000 or less, 1500 or less, or 1000 or less.

[0021] As the polymerizable compound (A), polyethylene glycol methyl ether (meth)acrylate, polyethylene glycol dodecyl ether (meth)acrylate, and polyethylene glycol (meth)acrylate are preferred.

[0022] <(Meth)acrylate compound (B)> The dental composition of the first embodiment preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A). Moreover, it is more preferable that the dental material composition of the first embodiment has one polymerizable group in the polymerizable compound (A) that is a (meth)acryloyl group, and further contains a (meth)acrylate compound (B) other than the polymerizable compound (A).

[0023] The (meth)acrylate compound (B) can be used without any particular limitation so long as it is a (meth)acrylate compound other than the polymerizable compound (A). Specifically, the (meth)acrylate compound (B) includes a (meth)acrylate compound containing two or more polymerizable groups, a (meth)acrylate compound containing no oxyalkylene group or only one oxyalkylene group, and the like. Specific examples of the (meth)acrylate compound (B) will be described below.

[0024] ((Meth)acrylate compound containing two or more (meth)acryloyloxy groups) The (meth)acrylate compound (B) may include a (meth)acrylate compound containing two or more (meth)acryloyloxy groups.

[0025] Examples of the (meth)acrylate compound containing two or more (meth)acryloyloxy groups include difunctional (meth)acrylate compounds and trifunctional or higher (meth)acrylate compounds. Examples of the difunctional (meth)acrylate compound include aromatic compound-based difunctional (meth)acrylate compounds, aliphatic compound-based difunctional (meth)acrylate compounds, (meth)acrylate compounds containing two or more urethane bonds, and (meth)acrylate compounds containing two or more thiourethane bonds.

[0026] Examples of aromatic bifunctional (meth)acrylate compounds include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxypolypropoxyphenyl)propane. Among these, at least one selected from the group consisting of 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl)propane (also referred to as Bis-GMA) and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane is preferred.

[0027] Examples of the aliphatic compound-based bifunctional (meth)acrylate compound include an aliphatic compound-based bifunctional (meth)acrylate that does not contain a urethane bond or a thiourethane bond, a (meth)acrylate compound that contains two or more urethane bonds, and a (meth)acrylate compound that contains two or more thiourethane bonds.

[0028] Examples of aliphatic compound-based bifunctional (meth)acrylates not containing a urethane bond or a thiourethane bond include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, Examples of suitable acrylates include butyl di(meth)acrylate, butyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane. Among these, at least one selected from the group consisting of glycerol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate (also referred to as HexDMA), neopentyl glycol dimethacrylate (also referred to as NPG), and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane is preferred.

[0029] A (meth)acrylate compound containing two or more urethane bonds can be produced, for example, as a reaction product of an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups and a (meth)acrylate compound containing a hydroxy group described below. In a (meth)acrylate compound containing two or more urethane bonds, the number of urethane bonds is preferably two. The (meth)acrylate compound containing two or more urethane bonds is not particularly limited, and examples thereof include 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (also referred to as UDMA).

[0030] A (meth)acrylate compound containing two or more thiourethane bonds can be produced, for example, as a reaction product of a thiol compound containing two or more thiol groups (such as pentaerythritol tetrakis(3-mercaptopropionate)), an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group.

[0031] In the first embodiment, the "(meth)acrylate compound containing two or more urethane bonds" does not contain two or more thiourethane bonds. In the first embodiment, the "(meth)acrylate compound containing two or more thiourethane bonds" may have two or more urethane bonds.

[0032] Examples of trifunctional or higher (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0033] (Iso(thio)cyanate compounds) Examples of iso(thio)cyanate compounds containing two or more iso(thio)cyanate groups that can be used as a raw material for a (meth)acrylate compound containing two or more urethane bonds or thiourethane bonds include the following isocyanate compounds and isothiocyanate compounds.

[0034] Examples of the isocyanate compound include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. The isocyanate compound may be used alone or in combination of two or more kinds.

[0035] Examples of the isothiocyanate compound include alicyclic polyisothiocyanate compounds such as hexamethylene diisothiocyanate; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate; and sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanate thiophene. The isothiocyanate compound may be used alone or in combination of two or more kinds.

[0036] Among the above, it is preferable that the iso(thio)cyanate compound includes at least one selected from the group consisting of hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0037] ((Meth)acrylate compounds containing hydroxy groups) Examples of (meth)acrylate compounds containing a hydroxy group that can be used as a raw material for a (meth)acrylate compound containing two or more urethane bonds or thiourethane bonds include 2-hydroxyethyl (meth)acrylate (also known as HEMA), 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Among the above, the (meth)acrylate compound containing a hydroxy group preferably includes at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0038] ((Meth)acrylate compounds containing no oxyalkylene group or only one oxyalkylene group) In the (meth)acrylate compound (B) of the first embodiment, the (meth)acrylate compound that does not contain an oxyalkylene group or contains only one oxyalkylene group may, for example, be a (meth)acrylate compound that contains one polymerizable group and has one or less oxyalkylene groups. Examples of the (meth)acrylate compound containing one polymerizable group and one or less oxyalkylene group include a (meth)acrylate compound containing a hydroxy group and a (meth)acrylate compound not containing a hydroxy group. Examples of (meth)acrylate compounds containing a hydroxy group include 2-hydroxyethyl (meth)acrylate (also known as HEMA), 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Among the above, the (meth)acrylate compound containing a hydroxy group preferably includes at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of (meth)acrylate compounds that do not contain a hydroxy group include alkyl (meth)acrylates such as dodecyl (meth)acrylate (DMA).

[0039] Examples of compounds that do not contain an oxyalkylene group or that contain only one oxyalkylene group and have two or more polymerizable groups include (meth)acrylate compounds that contain one or more (meth)acryloyloxy groups and one or more vinyl groups (such as ω-undecienylethylene oxide 4-mol adduct methacrylate (also referred to as ML-4G)).

[0040] ((Meth)acrylate Compound Containing Acidic Group) The (meth)acrylate compound (B) preferably includes a (meth)acrylate compound containing an acidic group. The (meth)acrylate compound containing an acidic group has affinity for the adherend and also has a demineralizing effect on tooth structure.

[0041] Examples of the acidic group include a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonic acid group, and a carboxylate group. Among the above, the acidic group is preferably at least one selected from the group consisting of a phosphoric acid group and a carboxylic acid group, and is more preferably a phosphoric acid group.

[0042] Examples of the (meth)acrylate compound containing a phosphoric acid group include (meth)acryloyloxyalkyl dihydrogen phosphates such as 10-(phosphonooxy)decyl-(meth)acrylate (also referred to as PDM), bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxyethyl]hydrogen phosphate, bis[10-(meth)acryloyloxyethyl]hydrogen phosphate, bis[11-(meth)acryloyloxyethyl]hydrogen phosphate, bis[12-(meth)acryloyloxyethyl]hydrogen phosphate, bis[13-(meth)acryloyloxyethyl]hydrogen phosphate, bis[14-(meth)acryloyloxyethyl]hydrogen phosphate, bis[15-(meth)acryloyloxyethyl]hydrogen phosphate, bis[16-(meth)acryloyloxyethyl]hydrogen phosphate, bis[17-(meth)acryloyloxyethyl]hydrogen phosphate, bis[18-(meth)acryloyloxyethyl]hydrogen phosphate, bis[19-(meth)acryloyloxyethyl]hydrogen phosphate, bis[20-(meth)acryloyloxyethyl]hydrogen phosphate, bis[21-(meth)acryloyloxyethyl]hydrogen phosphate, bis[22-(meth)acryloyloxyethyl]hydrogen phosphate, bis[23-(meth)acryloyloxyethyl]hydrogen phosphate, bis[24-(meth)acryloyloxyethyl]hydrogen phosphate, bis[25-(meth)acryloyloxyethyl]hydrogen phosphate, bis[26-(meth)acryloyloxyethyl Examples of suitable hydrogen phosphates include 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate, bis[10-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. Examples of the (meth)acrylate compound containing a carboxylic acid group include 4-methacryloyloxyethyltrimellitic acid (also referred to as 4-MET) and its anhydride.

[0043] From the viewpoint of obtaining a cured product having excellent antibacterial properties, the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is preferably 15 mass % or more, more preferably 20 mass % or more, and even more preferably 25 mass % or more, based on the total mass of the dental material composition. The total content of the polymerizable compound (A) and the (meth)acrylate compound (B) may be 99 mass % or less, or 80 mass % or less, based on the total mass of the dental composition.

[0044] From the viewpoint of obtaining a cured product having excellent antibacterial properties, the content of the polymerizable compound (A) is preferably 1% by mass to 50% by mass, more preferably 10% by mass to 45% by mass, and even more preferably 20% by mass to 45% by mass, based on the total content of the polymerizable compound (A) and the (meth)acrylate compound (B).

[0045] <Other ingredients> The dental material composition of the first embodiment may contain other components than the above-mentioned components as appropriate depending on the purpose. The components that may be contained in the dental material composition of the first embodiment are not particularly limited as long as they are known components. For example, the dental composition of the first embodiment may contain a polymerization initiator, a filler, a solvent, and the like.

[0046] <Polymerization initiator> The dental composition of the first embodiment may further contain a polymerization initiator. The dental composition of the first embodiment contains a polymerization initiator, and thus has chemical, thermal or photopolymerizability, making it possible to more satisfactorily obtain a cured product. As the polymerization initiator, a general polymerization initiator used in the dental field can be used.

[0047] In the case of carrying out chemical polymerization, the polymerization initiator is preferably, for example, a redox-based polymerization initiator in which an oxidizing agent and a reducing agent are combined. When using a redox-based polymerization initiator, the oxidizing agent and the reducing agent are packaged separately, and the two are mixed just before use. The polymerization initiator can be any known polymerization initiator that is generally used, and is usually selected in consideration of the polymerizability of the polymerizable compound and the polymerization conditions.

[0048] As the polymerization initiator, for example, redox polymerization initiators such as organic peroxide / aromatic amine system such as diacyl peroxides such as benzoyl peroxide and decanoyl peroxide, cumene hydroperoxide / thiourea system, ascorbic acid / copper salt system, organic peroxide / amine compound / sulfinic acid (or its salt) system, etc. Also preferably used as the polymerization initiator are trialkylboranes and partial oxides thereof such as tributylborane and partial oxides thereof, 5-butylbarbituric acid, 5-butyl-2-thiobarbituric acid catalysts, etc.

[0049] When thermal polymerization is carried out by heating, a polymerization initiator such as a peroxide or an azo compound is preferred. The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. The azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile, etc.

[0050] In the case of photopolymerization by irradiation with visible light, examples of photopolymerization catalysts include α-diketones such as camphorquinone (also referred to as CQ) and acetylbenzoyl; benzoyl alkyl ethers such as benzoyl ethyl ether; thioxanthone derivatives such as 2-chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone and p,p'-methoxybenzophenone; and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide. In addition to these polymerization initiators, it is preferable to use in combination a co-catalyst component such as an amine compound such as dimethylaminoethyl methacrylate, N,N-dimethyl-p-toluidine, ethyl p-dimethylaminobenzoate (also referred to as EDB), or 2-butoxyethyl 4-(dimethylamino)benzoate (also referred to as BEDB), an aldehyde compound such as citronellal or dimethylaminobenzaldehyde, or a compound having a thiol group such as 2-mercaptobenzoxazole or decanethiol. The polymerization initiator may be used alone or in combination of two or more kinds. The content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 5% by mass, based on 100% by mass of the dental material composition.

[0051] <Filler> The dental composition of the first embodiment may contain a filler. The filler is not particularly limited and may be any filler commonly used in the dental field. Fillers are generally broadly classified into organic fillers and inorganic fillers. Examples of the organic filler include fine powders of polymethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.

[0052] Examples of inorganic fillers include fine powders of various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, and hydroxyapatite. Specific examples of such inorganic fillers include barium borosilicate glass (Schott 8235, Schott GM27884, Schott G018-053, etc.), strontium boroaluminosilicate glass (Schott G018-163, etc.), lanthanum glass (Schott GM31684, etc.), fluoroaluminosilicate glass (Schott G018-117, etc.), and boroaluminosilicate glass containing zirconium, cesium, etc. (Schott G018-307, etc.).

[0053] The filler in the present disclosure is preferably a filler other than a pigment. Examples of fillers other than pigments include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, boroaluminosilicate glass, silica, zirconia, and composites thereof (e.g., silica-zirconia composite oxide).

[0054] These fillers may be used alone or in combination of two or more. The content of the filler may be appropriately determined in consideration of the operability (viscosity) of the dental material composition (e.g., composite resin composition) and the bending strength of the cured product thereof, and is preferably 10 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 100 to 600 parts by mass, relative to 100 parts by mass of all components other than the filler contained in the dental material composition. In particular, when the filler in the present disclosure is a filler other than a pigment, the content of the filler other than the pigment is preferably within the above-mentioned range.

[0055] The dental material composition of the present disclosure preferably contains a filler other than a pigment, or a composite of a filler other than a pigment and titania. That is, the filler in the present disclosure is preferably a filler other than a pigment, or a composite of a filler other than a pigment and titania. Examples of composites of titania and fillers other than pigments include composite oxides such as silica-titania and silica-titania-zirconia.

[0056] Even when the filler in the present disclosure is a composite of a filler other than a pigment and titania, the content of the composite of a filler other than a pigment and titania is preferably within the above-mentioned range. That is, the content of the composite of the filler other than the pigment and titania is preferably 10 parts by mass to 2000 parts by mass, more preferably 50 parts by mass to 1000 parts by mass, and even more preferably 100 parts by mass to 600 parts by mass, relative to 100 parts by mass of all components other than the filler contained in the dental material composition. In addition, in the composite of titania and a filler other than a pigment, the content of titania is preferably, for example, 5 mol % to 30 mol %.

[0057] <Solvent> The dental composition of the first embodiment preferably contains a solvent. Examples of the solvent include organic solvents and water. The dental composition of the first embodiment preferably contains an organic solvent and water.

[0058] As the organic solvent, ethanol, isopropyl alcohol, acetone, etc. can be used. The water includes distilled water, ultrapure water, and the like.

[0059] In the dental material composition of the first embodiment, the total content of pigment and dye is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 1.0% by mass or less, and more preferably contains no pigment or dye. Examples of pigments include fillers other than those mentioned above (such as barium borosilicate glass), such as titanium dioxide, iron oxide, and carbon black. Alternatively, when titania, among the pigments of the present disclosure, is used as a complex with a filler other than a pigment, the dental material composition of the first embodiment preferably contains the pigment and dye other than titania in a total content of 10 mass % or less, more preferably 5.0 mass % or less, even more preferably 1.0 mass % or less, and more preferably contains no pigment or dye. In the dental composition of the first embodiment, the total content of the pigment and dye may be 0% by mass or more, or 0.01% by mass or more.

[0060] The dental material composition of the first embodiment may contain, for example, a polymerization inhibitor to improve storage stability. In addition, it may contain a colorant such as a known pigment or dye to adjust the color tone. Furthermore, it may contain a reinforcing material such as a known fiber to improve the strength of the cured product. In addition, the dental material composition of the first embodiment may contain additives such as a bactericide, disinfectant, stabilizer, and preservative as necessary as long as the effects of the present disclosure are achieved.

[0061] ≪Applications≫ The dental composition of the first embodiment is suitably used for applications relating to dental materials. Among the above, the dental composition of the first embodiment is particularly preferably used as a bonding material or a composite resin. When the dental material composition of the first embodiment is used as a bonding material, for example, the dental material composition preferably contains 10 parts by mass to 250 parts by mass of water and 10 parts by mass to 250 parts by mass of an organic solvent relative to 100 parts by mass of a polymerizable compound. When the dental composition of the first embodiment is used as a bonding material, the dental composition preferably has a total content of water and organic solvent of 20 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound. The organic solvent is not particularly limited, but ethanol, acetone and isopropyl alcohol are preferred, and ethanol is more preferred.

[0062] When the dental material composition of the first embodiment is used as a composite resin, for example, it is preferable that the dental material composition contains water and an organic solvent in total amount of 1 mass % or less based on the total mass of the dental material composition, or contains no water or organic solvent.

[0063] [Second embodiment] The dental composition of the second embodiment contains a polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups. The dental composition of the second embodiment contains the polymerizable compound (C), and thus a cured product having excellent antibacterial properties can be obtained. The reason for this is presumed to be as follows. The polymerizable compound (C) contains an oxypropylene structure, which is more likely to cause steric hindrance than an oxyethylene structure. This is presumably because it makes it difficult for the polymerizable compound (C) to be incorporated into the cured product, and makes it easier for the oxypropylene structure, which has antibacterial activity, to exist on the surface.

[0064] Moreover, one embodiment of the dental composition of the second embodiment can also give a cured product with excellent adhesive strength.

[0065] <Polymerizable compound (C)> The polymerizable compound (C) contains one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups. The polymerizable compound (C) contains two or more polymerizable groups. The alkenyloxy group preferably has 8 to 18 carbon atoms, more preferably 9 to 16 carbon atoms, and even more preferably 10 to 14 carbon atoms. The number of oxypropylene groups may be 4-35, and preferably 8-16. From the viewpoint of antibacterial activity, one (meth)acryloyl group is preferably one acryloyl group.

[0066] The dental material composition of the second embodiment can have the same configuration as the dental material composition of the first embodiment, except that the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups is changed to a polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups. In other words, except that the polymerizable compound (A) is changed to the polymerizable compound (C), the preferred aspects including specific examples, preferred specific examples, contents, etc. of each component described in the section of the first embodiment can also be applied to the dental material composition of the second embodiment.

[0067] The dental composition of the second embodiment preferably further contains a (meth)acrylate compound (B') other than the polymerizable compound (C). Details of specific examples, preferred specific examples, and preferred aspects including the content of the (meth)acrylate compound (B') are the same as the details of specific examples, preferred specific examples, and preferred aspects including the content of the (meth)acrylate compound other than the polymerizable compound (C) in the description of the section <(meth)acrylate compound (B)> in the first embodiment.

[0068] The dental composition of the second embodiment may contain <other components>, a <polymerization initiator>, a <filler>, a <solvent>, and the like. Details of specific examples, preferred specific examples, preferred aspects, etc. of <other components>, <polymerization initiator>, <filler> and <solvent> in the second embodiment are the same as the details of specific examples, preferred specific examples, preferred aspects, etc. described in the sections of <other components>, <polymerization initiator>, <filler> and <solvent> in the first embodiment.

[0069] The polymerizable compound (A) and the polymerizable compound (C) may be commercially available products or may be produced by a known method. For example, the polymerizable compound (A) and the polymerizable compound (C) having a (meth)acryloyl group as a polymerizable group can be produced by reacting an alcohol compound having an oxyalkylene group (including those having an alkoxy group or an alkenyloxy group in addition to an oxyalkylene group) with (meth)acryl chloride in the presence of triethylamine in methylene chloride, removing the methylene chloride, and then purifying the product.

[0070] ≪Applications≫ Details of specific applications, preferred specific applications, etc. of the dental material composition of the second embodiment are similar to details of specific applications, preferred specific applications, etc. of the dental material composition of the first embodiment. When the dental material composition of the second embodiment is used as a bonding material, the preferred contents of water, organic solvent, etc. are the same as the preferred contents of water, organic solvent, etc. when the dental material composition of the first embodiment is used as a bonding material. Details of specific examples of organic solvents in the second embodiment are similar to those of specific examples of organic solvents in the first embodiment. When the dental material composition of the second embodiment is used as a composite resin, the preferred contents of water, organic solvent, etc. are the same as the preferred contents of water, organic solvent, etc. when the dental material composition of the first embodiment is used as a composite resin.

[0071] ≪Cured product≫ The cured product of the present disclosure is a cured product of the dental material composition of the present disclosure. The cured product of the present disclosure has excellent antibacterial properties. Furthermore, one embodiment of the cured product of the present disclosure also has excellent adhesive strength.

[0072] <Dental materials> The dental material of the present disclosure includes a hardened product of the dental material composition of the present disclosure. The dental material composition of the present disclosure is preferably used for producing a dental material by stereolithography.

[0073] ≪Antibacterial composition≫ The dental material composition of the present disclosure can be suitably used as an antibacterial composition. The antibacterial composition of the present disclosure includes the dental material composition of the present disclosure. One embodiment of the antibacterial composition of the present disclosure may include a polymerizable compound (A) that includes one polymerizable group and two or more oxyalkylene groups.

[0074] The antibacterial composition of the present disclosure, when containing the above-mentioned components, can give a cured product with excellent antibacterial properties. The antibacterial composition of the present disclosure can be used for a wide range of antibacterial purposes other than dental material applications. For example, the antibacterial composition of the present disclosure may be used as a paint, a coating agent, or the like.

[0075] In the antibacterial composition of the present disclosure, details such as specific embodiments and preferred embodiments of the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups are the same as the details of specific embodiments and preferred embodiments of the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups described in the section titled “Dental Material Composition”.

[0076] The antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A). It is more preferable that the antibacterial composition of the present disclosure has the one polymerizable group in the polymerizable compound (A) be a (meth)acryloyl group, and further contains a (meth)acrylate compound (B) other than the polymerizable compound (A).

[0077] In the antibacterial composition of the present disclosure, details of the specific embodiment, preferred embodiment, etc. of the (meth)acrylate compound (B) are the same as the details of the specific embodiment, preferred embodiment, etc. of the (meth)acrylate compound (B) described in the section “Dental material composition”.

[0078] From the viewpoint of obtaining a cured product having excellent antibacterial properties, the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is preferably 15 mass% or more, more preferably 20 mass% or more, and even more preferably 25 mass% or more, based on the total mass of the antibacterial composition. The total content of the polymerizable compound (A) and the (meth)acrylate compound (B) may be 99 mass % or less, or 80 mass % or less, based on the total mass of the antibacterial composition.

[0079] The antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A).

[0080] Another embodiment of the antibacterial composition of the present disclosure may contain a polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups.

[0081] In the antibacterial composition of the present disclosure, details such as specific embodiments and preferred embodiments of the polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups are the same as the details of specific embodiments and preferred embodiments of the polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups described in the section titled “Dental Material Composition”.

[0082] The antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B') other than the polymerizable compound (C). In the antibacterial composition of the present disclosure, details of the specific aspects, preferred aspects, etc. of the (meth)acrylate compound (B') are the same as the details of the specific aspects, preferred aspects, etc. of the (meth)acrylate compound (B') described in the section "Dental Material Composition".

[0083] The preferred range of the total content of the polymerizable compound (C) and the (meth)acrylate compound (B') is the same as the preferred range of the total content of the polymerizable compound (A) and the (meth)acrylate compound (B).

[0084] The antibacterial composition of the present disclosure may contain other components than the above-mentioned components as appropriate depending on the purpose. The components that may be contained in the antibacterial composition of the present disclosure are not particularly limited as long as they are known components. Details of specific aspects, preferred aspects, etc. of the components that may be contained in the antibacterial composition of the present disclosure are the same as the details of specific aspects, preferred aspects, etc. described in the section <Other Components> of <Dental Material Composition>. EXAMPLES

[0085] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.

[0086] The abbreviations for the compounds used in the examples are shown below. PEGMEMA500: Polyethylene glycol methyl ether methacrylate PEGMEMA500 was polyethylene glycol methyl ether methacrylate (catalog number 447943) from Sigma-Aldrich. The structure of PEGMEMA500 is shown below.

[0087] [ka]

[0088] PEGMEMA950: Polyethylene glycol methyl ether methacrylate PEGMEMA950 was polyethylene glycol methyl ether methacrylate (catalog number 447951) from Sigma-Aldrich. The structure of PEGMEMA950 is shown below.

[0089] [ka]

[0090] PEGMEA480: Polyethylene glycol methyl ether acrylate PEGMEA480 was polyethylene glycol methyl ether acrylate (catalog number 454990) from Sigma-Aldrich. The structure of PEGMEA480 is shown below.

[0091] [ka]

[0092] PEGMEMA300: Polyethylene glycol methyl ether methacrylate PEGMEMA300 was polyethylene glycol methyl ether methacrylate (catalog number 447935) from Sigma-Aldrich. The structure of PEGMEMA300 is shown below.

[0093] [ka]

[0094] PEGDEMA: Polyethylene glycol dodecyl ether methacrylate PEGDEMA was synthesized according to the following synthesis example.

[0095] <Synthesis Example> An example of the synthesis of PEGDEMA is given below. 13.74 g of decaethylene glycol monododecyl ether (catalog number P9769) from Sigma-Aldrich was dissolved in 200 mL of methylene chloride in a 500 mL eggplant flask under a nitrogen atmosphere, and 7.6 mL of triethylamine (Sigma-Aldrich, catalog number T0886) was added and stirred on an ice bath. 2.9 mL of methacrylic chloride (Tokyo Chemical Industry Co., Ltd., product code M0556) was added dropwise over 10 minutes, and the mixture was returned to room temperature and stirred for 40 hours. After removing the methylene chloride using a rotary evaporator, water was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated using a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography (solvent was ethyl acetate, followed by ethyl acetate containing 10% methanol) to obtain 10.76 g (yield 71% by mass) of PEGDEMA. The structure of PEGDEMA is shown below.

[0096] [ka]

[0097] PEGMA500: Polyethylene glycol methacrylate PEGMA500 was polyethylene glycol methacrylate (catalog number 409529) from Sigma-Aldrich. The structure of PEGMA500 is shown below.

[0098] [ka]

[0099] ML-4G: ω-undecylenylethylene oxide 4 moles added methacrylate As ML-4G, NK Ester TE-ML4G manufactured by Shin-Nakamura Chemical Co., Ltd. was used. The structure of ML-4G is shown below.

[0100] [ka]

[0101] DMA: Dodecyl methacrylate As the DMA, dodecyl methacrylate (product code M0083) from Tokyo Chemical Industry Co., Ltd. was used. The structure of DMA is shown below.

[0102] [ka]

[0103] UA: 10-undecenyl acrylate The UA used was 10-undecenyl acrylate (catalog number 760447-1G) from Sigma-Aldrich. The structure of a UA is shown below.

[0104] [ka]

[0105] 9G: Nonaethylene glycol dimethacrylate For 9G, polyethylene glycol dimethacrylate (product code P2709) from Tokyo Chemical Industry Co., Ltd. was used. The structure of 9G is shown below.

[0106] [ka]

[0107] 3G: Triethylene glycol dimethacrylate For 3G, NK Ester 3G from Shin-Nakamura Chemical Co., Ltd. was used. The structure of 3G is shown below.

[0108] [ka]

[0109] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate UDMA was used as Sigma-Aldrich diurethane dimethacrylate, isomer mixture (catalog number 436909). The structure of UDMA is shown below.

[0110] [ka]

[0111] Bis-GMA: Bisphenol A glycidyl methacrylate Bis-GMA was bisphenol A glycerolate dimethacrylate (catalog number 494356) from Sigma-Aldrich. The structure of Bis-GMA is shown below.

[0112] [ka]

[0113] PDM: 10-(phosphonooxy)decyl methacrylate The PDM used was 10-(phosphonooxy)decyl methacrylate (product code QH-4069) from Fujifilm Wako Pure Chemical Industries, Ltd. The structure of PDM is shown below.

[0114] [ka]

[0115] HEMA: 2-hydroxyethyl methacrylate HEMA was 2-hydroxyethyl methacrylate from Sigma-Aldrich (catalog number 128635). The structure of HEMA is shown below.

[0116] [ka]

[0117] CQ: (±)-camphorquinone The CQ used was (±)-camphorquinone (product code 032-12871) from Fujifilm Wako Pure Chemical Industries, Ltd.

[0118] BEDB: 2-butoxyethyl 4-(dimethylamino)benzoate BEDB used was 2-butoxyethyl 4-(dimethylamino)benzoate (product code D1848) from Tokyo Chemical Industry Co., Ltd.

[0119] EDB: Ethyl p-dimethylaminobenzoate Ethyl p-dimethylaminobenzoate (product code 050-06002) from Fujifilm Wako Pure Chemical Industries, Ltd. was used as EDB.

[0120] PPGDEA: Polypropylene glycol 12-mol dodecyl ether acrylate PPGDEA was synthesized by Shin-Nakamura Chemical Co., Ltd. The structure of PPGDEA is shown below.

[0121] [ka]

[0122] PPGUEA: ω-undecyenyl propylene oxide 12 mole adduct acrylate PPGUEA was synthesized by Shin-Nakamura Chemical Co., Ltd. The structure of PPGUEA is shown below.

[0123] [ka]

[0124] <Examples 1 to 9 and Comparative Examples 1 to 6> The components were mixed in the mass ratios shown in Table 1 and then stirred at 50° C. until homogenous, to prepare the compositions of Examples 1 to 9 and Comparative Examples 1 to 6.

[0125] <Antibacterial evaluation (plate hardening)> A 25 μm thick PET film was placed on the glass, and a 1 mm thick silicone mold was placed on top of the PET film. The composition prepared by the above method was placed in the mold, and another PET film was placed on the composition, and then the glass was placed on top. The two pieces of glass were then pressed together and irradiated with light for three minutes each on the front and back sides using an Alpha Light V LCR11 (Morita Corporation) to completely harden the glass, yielding a plate-shaped hardened product. The obtained plate-shaped test piece of the cured product (3.5 cm long, 3.5 cm wide, and 1 mm thick) was ultrasonically cleaned in ethanol for 10 minutes, and then the ethanol was replaced with ultrapure water and ultrasonically cleaned again for 10 minutes to remove any remaining polymerizable compound. Next, the above-mentioned plate-shaped cured product was subjected to an antibacterial test against Streptococcus mutans NBRC13955 (distributed by the National Institute of Technology and Evaluation, Biotechnology Center) in accordance with the method described in JIS Z 2801:2012, and the antibacterial activity value was calculated. The antibacterial activity value is an index of antibacterial properties, and is preferably 2.0 or more.

[0126] The antibacterial activity evaluation method is explained below. First, three test pieces were disinfected with a 70% ethanol solution and thoroughly dried. Next, Streptococcus mutans cultured overnight in Brain Heart Infusion Medium (Becton Dickinson Japan, model number 237500) was added to the same medium until the number of bacteria reached 2.5 × 10 5 pieces / mL~10×10 5 The solution was diluted to cells / mL, 225 μL was placed on each test piece, and then a sterilized PET film (3 cm long, 3 cm wide, and 25 μm thick) was placed on top and adhered tightly. The test specimens were cultured for 24 hours at 37°C under microaerobic conditions (i.e., oxygen concentration of 6% by volume) using an anaerobic / microaerobic culture jar system, Anoxomat Mark II (Central Scientific Trading Co., Ltd.). The culture solution was then recovered and diluted using phosphate-buffered saline, and inoculated onto brain heart infusion agar medium, cultured for 48 hours at 37°C under microaerobic conditions, and the viable cell count was measured. The formula for calculating the antibacterial activity value R is as follows: In this test, Comparative Example 5 was used as an unprocessed test piece. The larger the antibacterial activity value R, the higher the antibacterial activity. A value of 2.0 or higher is considered to have antibacterial activity. The results are shown in Table 1.

[0127] R = (Ut-U0) - (At-U0) = Ut-At R: Antibacterial activity value U0: The average logarithmic value of the number of viable bacteria immediately after inoculation of the untreated test piece Ut: The average logarithm of the number of viable bacteria on the untreated test piece after 24 hours At: The average logarithmic value of the number of viable bacteria on the antibacterial treated test piece after 24 hours

[0128] [Table 1]

[0129] As shown in Table 1, in the examples using the dental material composition containing the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups, the antibacterial activity value R of the obtained cured product was high, and a cured product with excellent antibacterial properties was obtained. On the other hand, in Comparative Examples 1 to 6 which did not contain the polymerizable compound (A) of the present disclosure, the antibacterial activity value R of the obtained cured product was low, and it was not possible to obtain a cured product with excellent antibacterial properties.

[0130] <Example 10, Example 11, Comparative Example 7, and Comparative Example 8> The components were mixed in the mass ratios shown in Table 2 and then stirred at 50° C. until homogenous, to prepare the compositions of Examples 10 to 11 and Comparative Example 8.

[0131] <Antibacterial evaluation (cured product coated on acrylic plate)> 400 μL of the composition obtained by the above-mentioned method was placed on an acrylic plate (length 3.5 cm, width 3.5 cm, thickness 2 mm), and then the surface was blown with air to spread it over the entire surface. After removing excess composition, the composition was dried until it had lost its fluidity. A 25 μm thick PET film was placed on top of it, and the applied surface was irradiated with light for 3 minutes using an Alphalight V LCR11 to completely cure the coating, yielding a coated cured product. Next, the cured product was subjected to an antibacterial test against Streptococcus mutans NBRC13955 (distributed by the National Institute of Technology and Evaluation, Biotechnology Center) in accordance with the method described in JIS Z 2801:2012 in the same manner as described above, and the antibacterial activity value R was calculated by the method described above. In this test, Comparative Example 7 was treated as an unprocessed test piece. The results are shown in Table 2 below.

[0132] [Table 2]

[0133] As shown in Table 2, in the examples using the antibacterial composition containing the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups, the antibacterial activity value R of the obtained cured product was high, and a cured product with excellent antibacterial properties was obtained. On the other hand, in Comparative Example 7, which is an untreated test piece, and Comparative Example 8, which does not contain the polymerizable compound (A) of the present disclosure, the antibacterial activity value R of the obtained cured product was low, and a cured product with excellent antibacterial properties could not be obtained.

[0134] <Experimental Example 101, and Comparative Experimental Examples 101 to 103> (Antibacterial evaluation (polymerizable compound)) The following polymerizable compounds were subjected to an antibacterial evaluation. PEGDEMA (Example 101) ML-4G: (Comparative Experiment Example 101) DMA (Comparative Experiment Example 102) UA (Comparative Experiment Example 103)

[0135] Measurement of the MIC (minimum inhibitory concentration) value, which is an evaluation of the antibacterial activity of the polymerizable compound, was carried out by the broth microdilution method according to the following procedure. First, the polymerizable compound was diluted with ethanol to 50% by volume and sterilized by filtration using a 0.22 μm sterilizing filter (Merck, Mylex-GP SLGP033RS). Two series of measurements were performed for each sample, and the concentration of the polymerizable compound was diluted two-fold from 5.0% by volume to 0.0024% by volume.

[0136] Specifically, 96 wells of brain heart infusion medium were prepared. 180 μL of the medium was dispensed into the first well of a flat-bottom microplate to which an ethanol solution of the polymerizable compound was to be added, and 100 μL of the medium was dispensed into the other wells. Next, 20 μL of the polymerizable compound diluted with ethanol (50% by volume) was added to the first well to make a concentration of 5.0% by volume (total of 200 μL). Next, 100 μL of the 200 μL contained in the first well was added to the adjacent well (as described above, the well to which 100 μL of the medium had already been dispensed) to perform a two-fold serial dilution. Further, 100 μL of the 200 μL of this 2-fold serial dilution was added to the adjacent well to perform 2-fold serial dilution. Serial two-fold dilutions into adjacent wells as above were performed until the concentration of polymerizable compound was 0.0024% by volume. S. mutans was cultured overnight in Brain Heart Infusion Medium (Becton Dickinson Japan, model no. 237500) and the final inoculum concentration was 5 × 10 5 cfu / mL (5 × 10 4 As controls, wells containing only the brain heart infusion medium and the bacterial solution, and wells containing only the same medium were prepared. After the microplate was incubated at 37°C for 24 hours under microaerobic conditions, the percentage by volume at which growth was completely inhibited by visual observation was taken as the MIC value (volume %), and was converted to the MIC value (mg / mL) based on the specific gravity of the polymerizable compound. The results are shown in Table 3 below. The MIC value (mg / mL) indicates the average of the duplicated MIC values ​​(mg / mL) for each sample. The smaller the MIC value (mg / mL), the higher the antibacterial activity. A MIC value of 1 mg / mL or less indicates good antibacterial activity.

[0137] [Table 3]

[0138] As shown in Table 3, Experimental Example 101 using the polymerizable compound (A) of the present disclosure had a small MIC value and excellent antibacterial properties. On the other hand, Comparative Experimental Examples 101 to 103, which used compounds that do not fall under the polymerizable compound (A) of the present disclosure, had large MIC values ​​and poor antibacterial properties.

[0139] <Example 201, Comparative Example 201> The components were mixed in the mass ratios shown in Table 4, and then stirred at 50° C. until homogenous, to prepare compositions of Example 201 and Comparative Example 201.

[0140] <Adhesive strength> The adhesive strength was evaluated as follows. The bovine tooth specimens were made by extracting and then thawing refrigerated mandibular anterior teeth under water, cutting the roots, and removing the pulp. They were placed in a plastic cylindrical container with a diameter of 25 mm and a depth of 25 mm, and embedded in acrylic resin. The bovine tooth specimens were polished with waterproof emery paper (P400) immediately before use, and the smooth surfaces of the enamel and dentin were scraped off. After drying the surface to be adhered by blowing compressed air onto it for approximately 1 second, the composition of Example 201 or Comparative Example 201 was applied to the flat surface of the enamel or dentin, and after 20 seconds, the volatile solvent contained in each composition was dried using a dental air syringe. Each composition was then irradiated with light for 10 seconds using an LED visible light irradiator (Translux 2 Wave) to harden the composition, after which a plastic mold with a diameter of 2.38 mm (Ultradent Japan Co., Ltd.) was placed in it, and a photopolymerizable material (Clearfil APX, Kuraray Noritake Dental Co., Ltd.) was filled in and irradiated with light for 20 seconds using the same LED visible light irradiator to harden the composition. Thereafter, the specimen was immersed in water and stored in a thermostatic chamber at 37° C. for 18 hours, after which the adhesive strength was measured. The adhesive strength was determined by applying a shear load parallel to and in contact with the dentin surface of the bovine teeth at a crosshead speed of 1.0 mm / min, and measuring the shear load at which the cured product of a photopolymerizable material (Clearfil APX, Kuraray Noritake Dental Co., Ltd.) formed in the shape of a pillar on the surface of the bovine teeth separated from the surface.

[0141] [Table 4]

[0142] As shown in Table 4, Example 201, which used a composition containing a polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups, had a similar adhesive strength to Comparative Example 201, which used HEMA, which can be used to improve the penetration of the adhesive monomer. That is, it was confirmed that Example 201 functions as an adhesive monomer. From this, it can be said that this polymerizable compound (A) may be used as an alternative to HEMA, which is used as an adhesive monomer and is classified as Category 2 in the GHS for skin corrosion / irritation.

[0143] <Example 301, Comparative Example 301> The components were mixed in the mass ratios shown in Table 5 and then stirred at 50° C. until homogenous, to prepare compositions of Example 301 and Comparative Example 301.

[0144] <Antibacterial evaluation> The antibacterial properties were evaluated for each of the Examples and Comparative Examples. The evaluation was performed in the same manner as described above in the section <Evaluation of antibacterial properties (plate hardening)>.

[0145] [Table 5]

[0146] As shown in Table 5, in the examples using the dental material composition containing the polymerizable compound (C) containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups, the antibacterial activity value R of the obtained cured product was high, and a cured product with excellent antibacterial properties was obtained. On the other hand, in Comparative Example 301 which did not contain the polymerizable compound (C) of the present disclosure, the antibacterial activity value R of the obtained cured product was low, and a cured product with excellent antibacterial properties could not be obtained.

[0147] The disclosure of Japanese Patent Application No. 2021-060514, filed on March 31, 2021, is incorporated by reference in its entirety into this specification. All publications, patent applications, and standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A dental composition comprising a polymerizable compound (C) consisting of one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and an oxypropylene group having 2 to 35 carbon atoms.

2. A polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups, The dental composition, wherein the polymerizable compound (A) contains a compound represented by the following formula (2): 【Chemistry 1】

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