Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present disclosure relates to dental material compositions, dental materials and antibacterial compositions.
• Patent Document 1 discloses an antibacterial dental polymer containing a (meth)acrylic acid ester compound (A) having a 10-undecenoxy group and an ethoxy group and a polymerization initiator (D) represented by a specific structural formula. A sexual composition is described.
• Patent Document 1 JP-A-2004-189661
• the antibacterial properties of the dental material composition are considered to be the antibacterial properties of the dental material composition before curing and the antibacterial properties of the cured product obtained by curing the dental material composition. be done. From the viewpoint of suppressing plaque formation when using a dental material, the antibacterial properties of the cured product obtained by curing the dental material composition are considered to be particularly important. Regarding this point, the antibacterial dental polymerizable composition of Patent Document 1 has room for improvement in terms of the antibacterial properties of the cured product obtained by curing the composition.
• the problem to be solved by one embodiment of the present disclosure is to provide a dental material composition from which a cured product having excellent antibacterial properties can be obtained, and a dental material and antibacterial composition containing the cured product.
• Means for solving the above problems include the following aspects.
• the polymerizable compound (A) has a number average molecular weight Mn of 200 or more.
• the polymerizable compound (A) contains a compound represented by the following formula (1).
• R 1 is an organic group having 1 to 24 carbon atoms or a hydroxyl group that does not contain a polymerizable group
• R 2 is a hydrogen atom or a methyl group
• X is a divalent divalent group having 2 to 6 carbon atoms. It is a hydrocarbon group
• n is an integer of 2 or more.
• the one polymerizable group in the polymerizable compound (A) is a (meth)acryloyl group, and further includes a (meth)acrylate compound (B) other than the polymerizable compound (A) ⁇ 1> ⁇
• the dental material composition according to any one of ⁇ 5>.
• ⁇ 7> According to ⁇ 6>, the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is 15% by mass or more relative to the total mass of the dental material composition. dental material composition.
• the content of the polymerizable compound (A) is 1% by mass to 50% by mass with respect to the total content of the polymerizable compound (A) and the (meth)acrylate compound (B).
• a dental material 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.
• ⁇ 12> The dental material composition according to any one of ⁇ 1> to ⁇ 11>, which is used as a bonding material or a composite resin.
• a dental material comprising a cured product of the dental material composition according to any one of ⁇ 1> to ⁇ 12>.
• An antibacterial composition containing a polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups.
• the antibacterial composition according to ⁇ 14> which is used as a coating agent.
• a dental material composition from which a cured product having excellent antibacterial properties can be obtained and a dental material and an antibacterial composition containing the cured product.
• the numerical range indicated using “-” includes the numerical values before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. .
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• “(meth)acryloyl” means acryloyl or methacryloyl
• “(meth)acrylate” means acrylate or methacrylate.
• the amount of the multiple substances present in the composition means total volume.
• the dental material composition of the present disclosure includes a first embodiment and a second embodiment. Each embodiment is described below.
• the dental material composition of the first embodiment contains a polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups.
• a cured product having excellent antibacterial properties can be obtained.
• the reason for this is presumed to be as follows. Two or more oxyalkylene groups in the polymerizable compound (A) have antibacterial activity, and further, one polymerizable group causes the surface of the cured product to have two or more oxyalkylene groups when cured. It is presumed that this is because the existence of
• one embodiment of the dental material composition of the first embodiment can also obtain a cured product with excellent adhesive strength.
• the polymerizable compound (A) contains one polymerizable group and two or more oxyalkylene groups.
• One polymerizable group is not particularly limited.
• a (meth)acryloyl group, a vinyl group, and the like can be mentioned.
• one polymerizable group is preferably a (meth)acryloyl group.
• 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 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms.
• Two or more oxyalkylene groups may or may not be consecutive, but are preferably consecutive.
• the polymerizable compound (A) preferably contains a compound represented by the following formula (1).
• R 1 is an organic group having 1 to 24 carbon atoms or a hydroxyl group that does not contain a polymerizable group
• R2 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 more.
• R 1 in formula (1) is preferably an alkoxy group having 1 to 24 carbon atoms or a hydroxyl group.
• R 1 preferably has 1 to 18 carbon atoms, more preferably 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 a divalent hydrocarbon group having 2 carbon atoms. is more preferable.
• n is preferably an integer of 3 or more.
• the number average molecular weight of the polymerizable compound (A) is preferably 200 or more, more preferably 300 or more, 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.
• polyethylene glycol methyl ether (meth)acrylate polyethylene glycol dodecyl ether (meth)acrylate, and polyethylene glycol (meth)acrylate are preferable.
• the dental material composition of the first embodiment preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A). Further, in the dental material composition of the first embodiment, one polymerizable group in the polymerizable compound (A) is a (meth)acryloyl group, and a (meth)acrylate compound (B) other than the polymerizable compound (A) ) is further included.
• the (meth)acrylate compound (B) can be used without particular limitation as long as it is a (meth)acrylate compound other than the polymerizable compound (A).
• the (meth)acrylate compound (B) is a (meth)acrylate compound containing two or more polymerizable groups, a (meth)acrylate compound containing no oxyalkylene group or containing only one oxyalkylene group. etc. Specific examples of the (meth)acrylate compound (B) are described below.
• ((Meth)acrylate compound containing two or more (meth)acryloyloxy groups) (Meth)acrylate compound (B) may include a (meth)acrylate compound containing two or more (meth)acryloyloxy groups.
• (Meth)acrylate compounds containing two or more (meth)acryloyloxy groups include bifunctional (meth)acrylate compounds and trifunctional or higher (meth)acrylate compounds.
• bifunctional (meth)acrylate compounds include aromatic compound-based bifunctional (meth)acrylate compounds, aliphatic compound-based bifunctional (meth)acrylate compounds, (meth)acrylate compounds containing two or more urethane bonds, Examples thereof include (meth)acrylate compounds containing two or more thiourethane bonds.
• 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, 2,2-bis (4-(meth)acryloyloxypolypropoxyphenyl)propane and the like.
• 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl)propane also referred to as Bis-GMA
• 2,2-bis(4-methacryloyloxypolyethoxyphenyl) at least one selected from the group consisting of propane.
• aliphatic compound-based bifunctional (meth) acrylate compounds include aliphatic compound-based bifunctional (meth) acrylates that do not contain urethane bonds and thiourethane bonds, and two or more urethane bonds (meth) Examples include acrylate compounds and (meth)acrylate compounds containing two or more thiourethane bonds.
• Examples of aliphatic compound-based bifunctional (meth)acrylates that do not contain urethane bonds and thiourethane bonds 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 ) acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1, 5-pent
• glycerol dimethacrylate triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate (also called HexDMA), neopentyl glycol dimethacrylate (also called NPG), and 1,2-bis(3 -methacryloyloxy-2-hydroxypropyloxy)ethane is preferred.
• the (meth)acrylate compound containing two or more urethane bonds is, for example, an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups and a (meth)acrylate compound containing a hydroxy group described later. It can be produced as a reaction product.
• the number of urethane bonds is preferably two.
• the (meth)acrylate compound containing two or more urethane bonds is not particularly limited. Examples include 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (also referred to as UDMA).
• a (meth)acrylate compound containing two or more thiourethane bonds is, for example, a thiol compound containing two or more thiol groups (pentaerythritol tetrakis (3-mercaptopropionate), etc.) and an iso(thio)cyanate group. It can be produced as a reaction product of an iso(thio)cyanate compound containing two or more and a (meth)acrylate compound containing a hydroxy group.
• 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.
• trifunctional or higher (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, penta Erythritol 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.
• iso(thio)cyanate compound examples of iso(thio)cyanate compounds containing two or more iso(thio)cyanate groups that can be used as raw materials for (meth)acrylate compounds containing two or more urethane bonds or thiourethane bonds include the following isocyanate compounds and Examples include isothiocyanate compounds.
• isocyanate compounds include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.
• isophorone diisocyanate bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl) bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate and the like.
• the isocyanate compound one kind may be used, or two or more kinds may be combined.
• isothiocyanate compounds include alicyclic polyisothiocyanate compounds such as hexamethylene diisothiocyanate; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate; sulfur-containing heterocycles such as 2,5-diisothiocyanatothiophene. polyisothiocyanate compounds; and the like.
• isothiocyanate compound one kind may be used, or two or more kinds may be used in combination.
• iso(thio)cyanate compounds 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(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2, It preferably contains at least one selected from the group consisting of 6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate.
• ((Meth)acrylate compound containing a hydroxy group) As a (meth)acrylate compound 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, 2-hydroxyethyl (meth)acrylate (also referred to as HEMA), 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like.
• the (meth)acrylate compound containing a hydroxy group preferably contains at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
• the (meth)acrylate compound containing no oxyalkylene group or containing only one oxyalkylene group in the (meth)acrylate compound (B) of the first embodiment includes, for example, one polymerizable group and oxy Examples include (meth)acrylate compounds having one or less alkylene groups.
• the (meth)acrylate compound containing one polymerizable group and having one or less oxyalkylene groups includes, for example, a (meth)acrylate compound containing a hydroxy group and a (meth)acrylate containing no hydroxy group. compound.
• (Meth)acrylate compounds containing a hydroxy group include 2-hydroxyethyl (meth)acrylate (also referred to as HEMA), 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( meth)acrylate and the like.
• the (meth)acrylate compound containing a hydroxy group preferably contains at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
• (Meth)acrylate compounds that do not contain a hydroxy group include alkyl (meth)acrylates such as dodecyl (meth)acrylate (DMA).
• the (meth)acrylate compound (B) preferably contains a (meth)acrylate compound containing an acidic group.
• a (meth)acrylate compound containing an acidic group has an affinity for adherends and a demineralizing effect on tooth substance.
• acidic groups examples include phosphoric acid groups, pyrophosphoric acid groups, thiophosphoric acid groups, phosphonic acid groups, sulfonic acid groups, and carboxylic acid groups.
• the acidic group is preferably at least one selected from the group consisting of a phosphoric acid group and a carboxylic acid group, and more preferably a phosphoric acid group.
• Examples of (meth)acrylate compounds containing a phosphoric acid group include (meth)acryloyloxyalkyldihydrogen phosphates such as 10-(phosphonooxy)decyl-(meth)acrylate (also referred to as PDM), bis[2-(meth) acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate gen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2 -(meth)acryloyloxyethylphen
• the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is 15% by mass or more with respect to the total mass of the dental material composition, from the viewpoint of obtaining a cured product having excellent antibacterial properties. It is preferably at least 20% by mass, more preferably at least 25% by mass.
• the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) may be 99% by mass or less, or 80% by mass or less, relative to the total mass of the dental material composition.
• the content of the polymerizable compound (A) is from 1% by mass to the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) from the viewpoint of obtaining a cured product having excellent antibacterial properties. It is preferably 50% by mass, more preferably 10% to 45% by mass, even more preferably 20% to 45% by mass.
• the dental material composition of the first embodiment may appropriately contain components other than the components described above, depending on the purpose.
• Components that may be included in the dental material composition of the first embodiment are not particularly limited as long as they are known components.
• the dental material composition of the first embodiment may contain a polymerization initiator, a filler, a solvent, and the like.
• the dental material composition of the first embodiment may further contain a polymerization initiator.
• a polymerization initiator By containing a polymerization initiator, the dental material composition of the first embodiment has chemical polymerizability, thermal polymerizability, or photopolymerizability, and a cured product can be obtained more satisfactorily.
• the polymerization initiator general polymerization initiators used in the dental field can be used.
• the polymerization initiator is preferably, for example, a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined.
• a redox polymerization initiator When a redox polymerization initiator is used, the oxidizing agent and the reducing agent may be packaged separately and mixed together immediately before use.
• the polymerization initiator for example, any commonly used known polymerization initiator can be used without particular limitation, and is usually selected in consideration of the polymerizability of the polymerizable compound and the polymerization conditions.
• polymerization initiators examples include organic peroxides such as diacyl peroxide such as benzoyl peroxide and decanoyl peroxide/aromatic amine, cumene hydroperoxide/thiourea, ascorbic acid/copper salt, organic A redox polymerization initiator such as a peroxide/amine compound/sulfinic acid (or a salt thereof) system can be used.
• organic peroxides such as diacyl peroxide such as benzoyl peroxide and decanoyl peroxide/aromatic amine, cumene hydroperoxide/thiourea, ascorbic acid/copper salt
• organic A redox polymerization initiator such as a peroxide/amine compound/sulfinic acid (or a salt thereof) system can be used.
• trialkylborane such as tributylborane and its partial oxide, and its partial oxide, 5-butylbarbituric acid, 5-butyl-2-thiobarbit
• polymerization initiators such as peroxides and azo compounds are preferred.
• the peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like.
• the azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile.
• ⁇ -diketones such as camphorquinone (also referred to as CQ) and acetylbenzoyl; benzoyl alkyl ethers such as benzoylethyl ether; thioxanthone derivatives such as 2-chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone and p,p'-methoxybenzophenone; photopolymerization catalysts such as acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide; be done.
• camphorquinone also referred to as CQ
• benzoyl alkyl ethers such as benzoylethyl ether
• thioxanthone derivatives such as 2-chlorothioxanthone and methylthiox
• co-catalyst components such as amine compounds such as ethyl (also referred to as BEDB), aldehyde compounds such as citronellal and dimethylaminobenzaldehyde, and compounds having a thiol group such as 2-mercaptobenzoxazole and decanethiol.
• the above polymerization initiators may be used singly or in combination of two or more.
• the content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 5% by mass, based on 100% by mass of the dental material composition.
• the dental material composition of the first embodiment may contain a filler.
• the filler is not particularly limited as long as it is a general filler used in the dental field. Fillers are generally divided into organic fillers and inorganic fillers. Examples of organic fillers include fine powders of polymethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.
• inorganic fillers include various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, and clay minerals (montmorillonite, etc.). , activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide and hydroxyapatite.
• inorganic fillers include barium borosilicate glass (Shot 8235, Shot GM27884, Shot G018-053, etc.), strontium boroaluminosilicate glass (Shot G018-163, etc.), lanthanum glass (Shot GM31684, etc.). ), fluoroaluminosilicate glass (Schott G018-117, etc.), boroaluminosilicate glass containing zirconium, cesium, etc. (Schott G018-307, etc.).
• Fillers in the present disclosure are preferably fillers other than pigments.
• fillers other than pigments include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, boroaluminosilicate glass, silica, zirconia, and composites thereof (for example, composite oxidation of silica and zirconia). things), etc.
• fillers may be used individually by 1 type, or 2 or more types may be used.
• the filler content may be appropriately determined in consideration of the operability (viscosity) of the dental material composition (e.g., composite resin composition), bending strength of the cured product, etc. 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 with respect to 100 parts by mass of all components other than the filler contained in the.
• the filler in the present disclosure is a filler other than pigment
• the content of filler other than pigment is preferably within the above range.
• 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.
• 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.
• composites of fillers other than pigments and titania include composite oxides such as silica-titania and silica-titania-zirconia.
• the content of the composite of filler other than pigment and titania is preferably within the above 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 with respect to 100 parts by mass of all components other than the filler contained in the dental material composition, and 50 parts by mass. Parts to 1000 parts by mass is more preferable, and 100 to 600 parts by mass is even more preferable.
• the content of titania in the composite of filler other than pigment and titania is preferably, for example, 5 mol % to 30 mol %.
• the dental material composition of the first embodiment preferably contains a solvent.
• solvents include organic solvents and water.
• the dental material composition of the first embodiment preferably contains an organic solvent and water.
• Ethanol, isopropyl alcohol, acetone, etc. can be used as the organic solvent.
• examples of water include distilled water and ultrapure water.
• the total content of pigments and dyes is preferably 10% by mass or less, more preferably 5.0% by mass or less, and 1.0% by mass or less. More preferably, it is free of pigments and dyes.
• Pigments include fillers that are not fillers (barium borosilicate glass, etc.) other than the pigments described above. Examples of pigments include titanium dioxide, iron oxide, and carbon black.
• the dental material composition of the first embodiment when titania is used as a composite with a filler other than the pigment, the dental material composition of the first embodiment has a total content of the pigment other than titania and the dye of 10 mass % or less, more preferably 5.0 mass % or less, even more preferably 1.0 mass % or less, and more preferably free of pigments and dyes.
• the total content of pigments and dyes may be 0% by mass or more, or 0.01% by mass or more.
• the dental material composition of the first embodiment may contain a polymerization inhibitor, for example, to improve storage stability.
• a polymerization inhibitor for example, to improve storage stability.
• it may contain known pigments, dyes, and other dyes.
• a known reinforcing material such as fiber may be included.
• the dental material composition of the first embodiment may optionally contain additives such as bactericides, disinfectants, stabilizers, and preservatives as long as the effects of the present disclosure are achieved.
• the dental material composition of the first embodiment is suitably used for applications relating to dental materials.
• the dental material composition of the first embodiment is used as a bonding material or a composite resin.
• the dental material composition contains 10 parts by mass to 250 parts by mass of water and 10 parts by mass of an organic solvent with respect to 100 parts by mass of the polymerizable compound. parts to 250 parts by mass.
• the dental material composition of the first embodiment is used as a bonding material
• the total content of water and organic solvent in the dental material composition is 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound.
• the organic solvent is not particularly limited, ethanol, acetone and isopropyl alcohol are preferred, and ethanol is more preferred.
• the total content of water and organic solvent in the dental material composition is 1% by mass or less with respect to the total mass of the dental material composition. or free of water and organic solvents.
• the dental material 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. .
• a cured product having excellent antibacterial properties can be obtained. The reason for this is presumed to be as follows. Since the polymerizable compound (C) contains an oxypropylene structure, steric hindrance is more likely to occur than with an oxyethylene structure. It is presumed that this makes it difficult for the polymerizable compound (C) to be incorporated into the inside of the cured product, making it easier for the oxypropylene structure having antibacterial activity to exist on the surface.
• one embodiment of the dental material composition of the second embodiment can also obtain a cured product with excellent adhesive strength.
• 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, preferably 8-16.
• One (meth)acryloyl group is preferably one acryloyl group from the viewpoint of antibacterial activity.
• the polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups contains one (meth)acryloyl group and 8 to 20 carbon atoms. and a polymerizable compound (C) containing an alkenyloxy group and two or more oxypropylene groups. That is, except that the polymerizable compound (A) is changed to the polymerizable compound (C), specific examples, preferred specific examples, content, etc. of each component described in the section of the first embodiment are , can also be applied to the dental material composition of the second embodiment.
• the dental material composition of the second embodiment preferably further contains a (meth)acrylate compound (B') other than the polymerizable compound (C).
• a (meth)acrylate compound (B′) other than the polymerizable compound (C)
• Specific examples of the (meth)acrylate compound (B′), preferred specific examples, details of preferred aspects including the content, etc. are described in the section ⁇ (meth)acrylate compound (B)> in the first embodiment, The details of the specific examples, preferred specific examples, and preferred aspects including the content of the (meth)acrylate compound other than the polymerizable compound (C) are the same as those described above.
• the dental material composition of the second embodiment may contain ⁇ other components>, ⁇ polymerization initiator>, ⁇ filler>, ⁇ solvent>, and the like. Details such as specific examples, preferred specific examples, and preferred aspects of ⁇ other components>, ⁇ polymerization initiator>, ⁇ filler> and ⁇ solvent> in the second embodiment are described in ⁇ other components>, ⁇ other components>, Details such as specific examples, preferred specific examples, and preferred embodiments described in the sections ⁇ Polymerization initiator>, ⁇ Filler> and ⁇ Solvent> are the same.
• the polymerizable compound (A) and the polymerizable compound (C) may be commercially available products or may be produced by known methods.
• the polymerizable compound (A) having a (meth)acryloyl group as a polymerizable group and the polymerizable compound (C) are alcohol compounds having an oxyalkylene group (an oxyalkylene group, an alkoxy group or an alkenyloxy group). ) and (meth)acryl chloride in the presence of triethylamine in methylene chloride to remove the methylene chloride and then purify.
• the cured product of the present disclosure is the cured product of the dental material composition of the present disclosure.
• the cured product of the present disclosure has excellent antibacterial properties.
• one embodiment of the cured product of the present disclosure is also excellent in adhesive strength.
• the dental material of the present disclosure includes a cured product of the dental material composition of the present disclosure.
• the composition for dental materials of the present disclosure is preferably used for manufacturing dental materials by stereolithography.
• the dental material composition of the present disclosure can be suitably used as an antibacterial composition.
• Antimicrobial compositions of the present disclosure include compositions for dental materials of the present disclosure.
• One embodiment of the antimicrobial composition of the present disclosure may comprise a polymerizable compound (A) comprising one polymerizable group and two or more oxyalkylene groups.
• the antibacterial composition of the present disclosure can obtain a cured product having excellent antibacterial properties by including the above configuration.
• the antibacterial composition of the present disclosure can be used in a wide range of antibacterial applications other than dental material applications.
• the antimicrobial compositions of the present disclosure may be used as paints, coating agents, and the like.
• the antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A).
• the one polymerizable group in the polymerizable compound (A) is a (meth)acryloyl group, and a (meth)acrylate compound (B) other than the polymerizable compound (A) is It is more preferable to further include.
• the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) is 15% by mass or more with respect to the total mass of the antibacterial composition from the viewpoint of obtaining a cured product having excellent antibacterial properties. , more preferably 20% by mass or more, and even more preferably 25% by mass or more.
• the total content of the polymerizable compound (A) and the (meth)acrylate compound (B) may be 99% by mass or less, or 80% by mass or less, relative to the total mass of the antibacterial composition. good too.
• the antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B) other than the polymerizable compound (A).
• Another embodiment of the antimicrobial composition of the present disclosure is a polymerizable compound (C ) may be included.
• a specific embodiment 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 For details such as preferred embodiments, polymerization containing one (meth)acryloyl group, an alkenyloxy group having 8 to 20 carbon atoms, and two or more oxypropylene groups described in the section «Dental material composition» The details of specific embodiments, preferred embodiments, etc. of the compound (C) are the same as those described above.
• the antibacterial composition of the present disclosure preferably further contains a (meth)acrylate compound (B') other than the polymerizable compound (C).
• a (meth)acrylate compound (B') other than the polymerizable compound (C).
• the preferred range of the total content of the polymerizable compound (C) and the (meth)acrylate compound (B′) is the preferred range of the total content of the polymerizable compound (A) and the (meth)acrylate compound (B). It is the same.
• the antibacterial composition of the present disclosure may contain ingredients other than those mentioned above, depending on the purpose.
• Components that may be included in the antibacterial composition of the present disclosure are not particularly limited as long as they are known components. Details such as specific aspects and preferred aspects of the components that may be contained in the antibacterial composition of the present disclosure are described in the specific aspects and preferred aspects, etc., in the ⁇ Other components> section of ⁇ Dental material composition>. Same as details.
• PEGMEMA 500 Polyethylene Glycol Methyl Ether Methacrylate
• Sigma-Aldrich catalog number 447943
• the structure of PEGMEMA500 is shown below.
• PEGMEMA 950 Polyethylene Glycol Methyl Ether Methacrylate PEGMEMA 950 used polyethylene glycol methyl ether methacrylate from Sigma-Aldrich (catalog number 447951). The structure of PEGMEMA950 is shown below.
• PEGMEA 480 Polyethylene Glycol Methyl Ether Acrylate PEGMEA 480 was polyethylene glycol methyl ether acrylate from Sigma-Aldrich (catalog number 454990). The structure of PEGMEA480 is shown below.
• PEGMEMA 300 Polyethylene Glycol Methyl Ether Methacrylate PEGMEMA 300 was polyethylene glycol methyl ether methacrylate from Sigma-Aldrich (catalog number 447935). The structure of PEGMEMA300 is shown below.
• PEGDEMA Polyethylene glycol dodecyl ether methacrylate PEGDEMA was synthesized in the following synthesis example.
• PEGMA500 Polyethylene Glycol Methacrylate PEGMA500 was polyethylene glycol methacrylate from Sigma-Aldrich (Catalog No. 409529). The structure of PEGMA500 is shown below.
• ML-4G ⁇ -undecienyl ethylene oxide 4 mol addition methacrylate ML-4G used Shin-Nakamura Chemical Co., Ltd. NK Ester TE-ML4G. The structure of ML-4G is shown below.
• DMA Dodecyl methacrylate Dodecyl methacrylate (product code M0083) from Tokyo Chemical Industry Co., Ltd. was used as DMA. The structure of DMA is shown below.
• UA 10-Undecenyl Acrylate
• Sigma-Aldrich catalog number 760447-1G
• the structure of UA is shown below.
• 9G Nonaethylene glycol dimethacrylate
• polyethylene glycol dimethacrylate product code P2709 from Tokyo Chemical Industry Co., Ltd. was used. The structure of 9G is shown below.
• 3G Triethylene glycol dimethacrylate NK Ester 3G from Shin-Nakamura Chemical Co., Ltd. was used as 3G. The structure of 3G is shown below.
• UDMA 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate
• UDMA was diurethane dimethacrylate, isomer mixture from Sigma-Aldrich (Catalog No. 436909). The structure of UDMA is shown below.
• Bis-GMA Bisphenol A glycidyl methacrylate
• Bis-GMA was bisphenol A glycerolate dimethacrylate from Sigma-Aldrich (catalog number 494356). The structure of Bis-GMA is shown below.
• PDM 10-(Phosphonooxy)decyl-methacrylate
• PDM 10-(phosphonooxy)decyl-methacrylate (product code QH-4069) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used. The structure of PDM is shown below.
• HEMA 2-hydroxyethyl methacrylate
• HEMA was 2-hydroxyethyl methacrylate from Sigma-Aldrich (catalog number 128635). The structure of HEMA is shown below.
• CQ ( ⁇ )-Camphorquinone As CQ, ( ⁇ )-Camphorquinone (product code 032-12871) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used.
• BEDB 2-butoxyethyl 4-(dimethylamino)benzoate 2-butoxyethyl 4-(dimethylamino)benzoate (product code D1848) available from Tokyo Chemical Industry Co., Ltd. was used as BEDB.
• EDB Ethyl p-dimethylaminobenzoate
• EDB used was ethyl p-dimethylaminobenzoate (product code 050-06002) available from Fujifilm Wako Pure Chemical Industries, Ltd.
• PPGDEA Polypropylene glycol 12 mol added dodecyl ether acrylate PPGDEA was synthesized under contract to Shin-Nakamura Chemical Co., Ltd. The structure of PPGDEA is shown below.
• PPGUEA ⁇ -undecienyl propylene oxide 12 mol added acrylate PPGUEA was synthesized by Shin-Nakamura Chemical Co., Ltd. under consignment. The structure of PPGUEA is shown below.
• Examples 1 to 9, and Comparative Examples 1 to 6 After mixing each component in the mass ratio shown in Table 1, the mixture was stirred at 50° C. until uniform, and compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were prepared.
• a PET film having a thickness of 25 ⁇ m was laid on the glass, and a silicone mold having a thickness of 1 mm was placed thereon.
• the composition prepared by the method described above was placed in a mold, another PET film was placed on the composition, and the mold was covered with glass from above. After that, two sheets of glass were pressed together, and the front and back sides were irradiated with light for 3 minutes each using Alphalite VLCR11 (manufactured by Morita Co., Ltd.), and completely cured to obtain a plate-like cured product.
• a test piece of the obtained plate-shaped cured product (3.5 cm long, 3.5 cm wide and 1 mm thick) was ultrasonically cleaned in ethanol for 10 minutes, and then ethanol was changed to ultrapure water for more than 10 minutes. Sonic cleaning was performed to remove residual polymerizable compounds. Subsequently, the plate-shaped cured product was subjected to an antibacterial test against Streptococcus mutans NBRC13955 (distributed from the National Institute of Technology and Evaluation Biotechnology Center) in accordance with the method described in JIS Z 2801: 2012. It was carried out and the antibacterial activity value was calculated.
• the antibacterial activity value is an antibacterial index, and is preferably 2.0 or more.
• the antibacterial evaluation method is described below. First, three test pieces were disinfected with a 70% by mass ethanol aqueous solution and dried sufficiently. Next, Streptococcus mutans cultured overnight in brain heart infusion medium (Nippon Becton Dickinson Model No. 237500) was added to the same medium so that the number of bacteria was 2.5 ⁇ 10 5 cells / mL to 10 ⁇ 10 5 cells / mL. After diluting and placing 225 ⁇ L per test piece, a sterilized PET film (3 cm long, 3 cm wide and 25 ⁇ m thick) was put on and brought into close contact. This test piece was cultured at 37° C.
• the formula for calculating the antibacterial activity value R is as follows. In this test, Comparative Example 5 was treated as an unprocessed test piece. The larger the antibacterial activity value R, the higher the antibacterial activity. Table 1 shows the results.
• the antibacterial activity of the resulting cured product was A cured product having a high value R and excellent antibacterial properties could be obtained.
• Comparative Examples 1 to 6 which do not contain the polymerizable compound (A) in the present disclosure, the antibacterial activity value R of the obtained cured product is low, and a cured product having excellent antibacterial properties could not be obtained.
• Example 10 Example 11, Comparative Example 7, and Comparative Example 8> After mixing each component in the mass ratio shown in Table 2, the mixture was stirred at 50° C. until uniform, and compositions of Examples 10 to 11 and Comparative Example 8 were prepared.
• ⁇ Antibacterial evaluation (coated cured product on acrylic plate)> After placing 400 ⁇ L of the composition obtained by the above method on an acrylic plate (3.5 cm long, 3.5 cm wide and 2 mm thick), the surface is air blown to spread it over the entire surface. After dropping off, the composition was dried until it no longer flowed. A PET film having a thickness of 25 ⁇ m was placed thereon, and the coated surface was irradiated with light for 3 minutes using Alphalite VLCR11, and completely cured to obtain a coated cured product.
• the cured product is subjected to antibacterial treatment against Streptococcus mutans NBRC13955 (distributed from the National Institute of Technology and Evaluation Biotechnology Center) in the same manner as described above in accordance with the method described in JIS Z 2801: 2012.
• a sex test was performed, and the antibacterial activity value R was calculated by the method described above.
• Comparative Example 7 was treated as an unprocessed test piece. The results are shown in Table 2 below.
• the MIC (Minimum Inhibitory Concentration) value which is an evaluation of the antibacterial properties of the polymerizable compound, was measured by the liquid trace dilution method according to the following procedure.
• the polymerizable compound was diluted with ethanol to 50% by volume, and sterilized by filtration with a 0.22 ⁇ m sterilizing filter (Merck Co., Milexu GP SLGP033RS). The measurement was carried out in two series per sample, and the concentration of the polymerizable compound was adjusted from 5.0% by volume to 0.0024% by volume by two-fold serial dilution.
• 96 wells of brain heart infusion medium were prepared.
• 180 ⁇ L of the same medium was dispensed to the first well to which the ethanol solution of the polymerizable compound was added, and 100 ⁇ L of the same medium was dispensed to each of the other wells.
• 20 ⁇ L of a polymerizable compound (50% by volume) diluted with ethanol was added to the first well to make 5.0% by volume (200 ⁇ L in total).
• 2-fold serial dilutions were performed by adding 100 ⁇ L of the 200 ⁇ L contained in the first well to adjacent wells (wells to which 100 ⁇ L of medium had already been dispensed, as described above).
• the volume % at which the growth is completely inhibited by visual observation is defined as the MIC value (volume %), and the specific gravity of the polymerizable compound is used to obtain the MIC value (mg / mL).
• the results are shown in Table 3 below.
• the MIC value (mg/mL) indicates the average value of two series of MIC values (mg/mL) for each sample. The smaller the MIC value (mg/mL), the higher the antibacterial activity, and 1 mg/mL or less indicates good antibacterial activity.
• Experimental Example 101 using the polymerizable compound (A) in the present disclosure had a small MIC value and excellent antibacterial properties.
• Comparative Experimental Examples 101 to 103 using compounds that do not correspond to the polymerizable compound (A) in the present disclosure had large MIC values and were inferior in antibacterial properties.
• Example 201 Comparative Example 201> After mixing each component in the mass ratio shown in Table 4, the mixture was stirred at 50° C. until uniform, and compositions of Example 201 and Comparative Example 201 were prepared.
• the evaluation method of adhesive strength is as follows. After removal of the bovine tooth adherend, the refrigerated bovine mandibular anterior tooth was thawed by pouring water, followed by cutting the root and extracting the pulp. This was placed in a plastic cylindrical container with a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. The bovine tooth adherend was polished with water-resistant emery paper (P400) immediately before use, and the smooth surface of the enamel and dentin was scraped out before use.
• P400 water-resistant emery paper
• Example 201 or Comparative Example 201 After drying by blowing compressed air on the adherend surface for about 1 second, the composition of Example 201 or Comparative Example 201 was applied to the flat surface of enamel or dentin, and after 20 seconds, the volatile was dried with a dental air syringe. After that, each composition was irradiated with light for 10 seconds using an LED visible light irradiator (Translux 2 Wave) to cure the composition, and then a plastic mold with a diameter of 2.38 mm (manufactured by Ultradent Japan Co., Ltd.
• LED visible light irradiator Translux 2 Wave
• Adhesion strength was measured by applying a shear load at a crosshead speed of 1.0 mm / min parallel to the dentin surface of the bovine tooth and forming a columnar photopolymerizable material on the surface of the bovine tooth (CLEARFIL APEX , manufactured by Kuraray Noritake Dental Co., Ltd.) was obtained from the shear load when the cured product was separated from the surface.
• Example 201 using a composition comprising a polymerizable compound (A) containing one polymerizable group and two or more oxyalkylene groups was used to improve penetration of the adhesive monomer.
• the adhesive strength of the obtained cured product was equivalent. That is, Example 201 was confirmed to function as an adhesive monomer. From this, it can be said that the present polymerizable compound (A) may be used as an alternative to HEMA, which is used as an adhesive monomer and whose GHS classification is Category 2 for skin corrosion/irritation.
• Example 301 Comparative Example 301> After mixing each component in the mass ratio shown in Table 5, the mixture was stirred at 50° C. until uniform to prepare compositions of Example 301 and Comparative Example 301.
• Antibacterial properties were evaluated for each example and comparative example.
• the evaluation method was the same as the method described in the above section ⁇ Antibacterial property evaluation (platy hardening)>.
• a dental material composition containing 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 antibacterial activity value R of the obtained cured product was high, and it was possible to obtain a cured product excellent in antibacterial properties.
• Comparative Example 301 which does not contain the polymerizable compound (C) in the present disclosure, the obtained cured product had a low antibacterial activity value R, and a cured product having excellent antibacterial properties could not be obtained.

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