Method for producing dental polymerizable composition or dental polymerizable composition intermediate

Abstract

The present invention provides a method for producing a dental polymerizable composition or a dental polymerizable composition intermediate. The purpose of the present invention is to provide a method for producing a dental polymerizable composition (beta) or a dental polymerizable composition intermediate (gamma) having excellent storage stability at a high yield. [Solution] A method for producing a dental polymerizable composition (beta) or a dental polymerizable composition intermediate (gamma) that does not substantially contain a filler, said method using a production machine provided with a container and substantially not provided with a stirring blade, and a method for producing a dental polymerizable composition (beta) or a dental polymerizable composition intermediate (gamma). The manufacturing method comprises the following steps: a step of arranging a composition (alpha) containing (a) a polymerizable monomer and (b) a polymerization inhibitor in a container so that the porosity of the container is 10-90%; and a step for operating the container.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a polymeric composition for dental use or an intermediate of a polymeric composition for dental use. Background Technology

[0002] Traditionally, dental polymeric compositions or intermediates for dental polymeric compositions contain polymeric monomers and polymerization inhibitors, and are manufactured by stirring and mixing these components using a manufacturing machine equipped with stirring blades.

[0003] For example, in Patent Document 1, materials are added to a beaker that is an open container at the top, the stirring tank itself is not working, and the components are mixed by stirring with stirring blades to obtain a dental polymeric composition.

[0004] However, in the manufacturing method described in Patent Document 1, when the stirring blade is removed from the mixture after stirring, there is a problem that the mixture adheres to the stirring blade and the yield becomes relatively poor.

[0005] In addition, Patent Document 2 discloses a method for manufacturing a dental polymeric composition using a self-rotating and revolution-rotating mixer.

[0006] However, Patent Document 2 relates to a manufacturing method that uses a rotating and revolving mixer to uniformly disperse fumed silica, which is an inorganic dispersion, in a dispersion medium containing polymeric monomers and / or organic solvents. It does not disclose any method for manufacturing a dental polymeric composition or a dental polymeric composition intermediate that does not contain fumed silica, and the above-mentioned problem has not been solved.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2012-012314

[0010] Patent Document 2: Japanese Patent Application Publication No. 2014-181183 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] The object of the present invention is to provide a method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) with excellent preservation stability in high yield.

[0013] Solution for solving the problem

[0014] The inventors conducted in-depth research and found that the above-mentioned problems can be solved by a specified method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ).

[0015] (Project 1)

[0016] A method for manufacturing a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ), wherein the method uses a manufacturing machine having a container but substantially lacking stirring blades, the manufacturing method comprising the steps of: disposing a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor in a container such that the container has a porosity of 10 to 90%; and operating the container.

[0017] (Project 2)

[0018] A method for manufacturing a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ), wherein the method uses a manufacturing machine having a container but substantially lacking stirring blades, the manufacturing method comprising the steps of: disposing of a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor in a container such that the container has a porosity of 10 to 90%; heating the container to 30 to 70°C; and operating the container.

[0019] (Project 3)

[0020] The method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) according to Project 1 or 2, wherein the container of the manufacturing machine having a container but not substantially having stirring blades performs one or more operations selected from rotation, hyperbolic motion and vibration.

[0021] (Project 4)

[0022] According to the method for manufacturing the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) described in Project 1 or 2, the container of the manufacturing machine, which has a container but substantially no stirring blades, is subjected to a process selected from 60 minutes. -1 Rotation speed at the following rate, 50 minutes -1 The following speed hyperbolic motion and 400 minutes -1 The operation involves one or more of the following vibration speeds.

[0023] (Project 5)

[0024] A method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) according to any one of items 1 to 4, wherein the porosity of the container is 20 to 80%.

[0025] (Project 6)

[0026] A method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) according to any one of items 1 to 5, wherein the composition (α) contains (c) an organic solvent.

[0027] The effects of the invention

[0028] According to the manufacturing method of the present invention, a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) containing a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor, with excellent storage stability, can be obtained in high yield. Detailed Implementation

[0029] This invention discloses a method for manufacturing a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) that is substantially free of fillers. This method utilizes a manufacturing machine equipped with a container but substantially without stirring blades. The manufacturing method includes the following steps: disposing of a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor in a container, such that the container has a porosity of 10-90%; and operating the container. The manufacturing method of this invention will be described in detail below.

[0030] <Dental polymeric composition (β) or dental polymeric composition intermediate (γ)>

[0031] The dental polymeric composition (β) or dental polymeric composition intermediate (γ) of the present invention is a mixture comprising (a) a polymeric monomer and (b) a polymerization inhibitor, and substantially free of fillers. Furthermore, the dental polymeric composition (β) or dental polymeric composition intermediate (γ) of the present invention preferably has a viscosity of 5000 mPa·s or less at 25°C. Dental polymeric compositions (β) with viscosity exceeding 5000 mPa·s have poor dischargeability from storage containers due to their high viscosity, and dental polymeric composition intermediates (γ) with viscosity exceeding 5000 mPa·s are difficult to process in subsequent manufacturing processes and are therefore impractical.

[0032] The viscosity determination method for dental polymeric compositions (β) or dental polymeric composition intermediates (γ) can be used without any restrictions, as long as it is a general analytical method. For example, B-type viscometers, E-type viscometers, and dynamic viscoelasticity measuring devices can be used.

[0033] <(a) Polymerizable monomers>

[0034] (a) Any known polymerizable monomer may be used without restriction as long as it has one or more polymerizable groups. The polymerizable monomer is preferably a polymerizable monomer exhibiting free radical polymerization properties. From the viewpoint of ease of free radical polymerization, the polymerizable group is preferably a free radical polymerizable group, more preferably (meth)acryloyl and / or (meth)acrylamide group. It should be noted that in this specification, "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid, "(meth)acryloyl" refers to acryloyl and / or methacryloyl, and "(meth)acrylate" refers to acrylate and / or methacrylate.

[0035] As (a) a polymerizable monomer, examples may be selected from one or more of the following: a polymerizable monomer that does not have an acidic group and a sulfur atom, (a1) a polymerizable monomer that has an acidic group, and (a2) a polymerizable monomer that has a sulfur atom.

[0036] As a polymerizable monomer that does not have an acidic group and a sulfur atom, examples may be selected from one or more of the following: a polymerizable monomer having one free radical polymerizable group, a polymerizable monomer having two free radical polymerizable groups, and a polymerizable monomer having three or more free radical polymerizable groups.

[0037] As a polymerizable monomer having one free radical polymerizable group, examples may be selected from one or more of the following substances: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)propylene Amides, N,N-(dihydroxyethyl)(meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acrylamide.

[0038] As a polymerizable monomer having two free radical polymerizable groups, examples can be selected from one or more of the following substances: 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis( 4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydi(triethoxy)phenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)propane 2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitic ester, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di... (Meth)acrylates, polyethylene glycol di(meth)acrylates, 1,3-butanediol di(meth)acrylates, 1,5-pentanediol di(meth)acrylates, 1,6-hexanediol di(meth)acrylates, 1,10-decanediol di(meth)acrylates, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.Among these, from the viewpoint of improving the mechanical strength of the final composition made from the dental polymeric composition (β) or the dental polymeric composition intermediate (γ), one or more selected from 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane and 1,6-bis(methacryloylethoxycarbonylamino)-2,2,4-trimethylhexane are preferred. Furthermore, from the viewpoint of having the effect of reducing the viscosity of the dental polymeric composition (β) or the dental polymeric composition intermediate (γ), one or more selected from triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate and glycerol di(meth)acrylate are preferred.

[0039] As a polymerizable monomer having three or more free radical polymerizable groups, examples can be selected from one or more of the following substances: trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxyl)propane-1,3-diol]tetramethacrylate, and 1,7-disacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane. Among these, trimethylolpropane tri(meth)acrylate is preferred from the viewpoint of improving the mechanical strength of the final composition manufactured from the dental polymerizable composition (β) or the dental polymerizable composition intermediate (γ).

[0040] In addition to the polymerizable monomers mentioned above, there are no restrictions on using oligomers or prepolymers that have at least one polymerizable group within the molecule. Furthermore, there are no issues with the presence of substituents such as fluorine groups within the same molecule. The polymerizable monomers described above can be used individually or in combination.

[0041] The polymeric monomer (a) of the present invention may include a polymeric monomer (a1) having an acidic group. As the polymeric monomer (a1) having an acidic group, any polymeric monomer having one or more polymeric groups and one or more acidic groups can be used without limitation. Examples of acidic groups include one or more selected from phosphate groups, pyrophosphate groups, thiophosphate groups, phosphonic acid groups, sulfonic acid groups, and carboxylic acid groups. By including a polymeric monomer (a1) having an acidic group, it is possible to impart adhesiveness to tooth enamel and repair devices to the final composition manufactured from the dental polymeric composition (β) or the dental polymeric composition intermediate (γ).

[0042] As a polymerizable monomer having a phosphate group, examples include one or more of the following substances: 2-(meth)acryloyloxyethyl dihydrophosphate, 3-(meth)acryloyloxypropyl dihydrophosphate, 4-(meth)acryloyloxybutyl dihydrophosphate, 5-(meth)acryloyloxypentyl dihydrophosphate, 6-(meth)acryloyloxyhexyl dihydrophosphate, 7-(meth)acryloyloxyheptyl dihydrophosphate, 8-(meth)acryloyloxyoctyl dihydrophosphate, 9-(meth)acryloyloxynonyl dihydrophosphate, 10-(meth)acryloyloxydecyl dihydrophosphate, 11-(meth)acryloyloxyundecyl dihydrophosphate, 12-(meth)acryloyloxydodecyl dihydrophosphate, 16-(meth)acryloyloxyhexadecyl dihydrophosphate, 20-(meth)acryloyloxy Eicosyl dihydrophosphate, 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)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrophosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; their acyl chlorides, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.

[0043] Examples of polymerizable monomers having a pyrophosphate group include one or more of the following substances: bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; their acyl chlorides, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.

[0044] As polymerizable monomers having a thiophosphate group, one or more of the following substances may be selected as examples: 2-(meth)acryloyloxyethyl dihydrothiophosphate, 3-(meth)acryloyloxypropyl dihydrothiophosphate, 4-(meth)acryloyloxybutyl dihydrothiophosphate, 5-(meth)acryloyloxypentyl dihydrothiophosphate, 6-(meth)acryloyloxyhexyl dihydrothiophosphate, 7-(meth)acryloyloxyheptyl dihydrothiophosphate, 8-(meth)acryloyloxyoctyl dihydrothiophosphate, 9-( (Meth)acryloyloxynonyl dihydrothiophosphate, 10-(meth)acryloyloxydecyl dihydrothiophosphate, 11-(meth)acryloyloxyundecyl dihydrothiophosphate, 12-(meth)acryloyloxydodecyl dihydrothiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrothiophosphate, 20-(meth)acryloyloxyeicosyl dihydrothiophosphate; their acyl chlorides, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.

[0045] Examples of polymerizable monomers having phosphonic acid groups include one or more of the following substances: 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; their acyl chlorides, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.

[0046] As a polymerizable monomer having a sulfonic acid group, examples may be selected from one or more of 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylic acid.

[0047] Examples of polymerizable monomers having a carboxyl group include one or more selected from (meth)acrylic acid compounds having one carboxyl group in the molecule and (meth)acrylic acid compounds having multiple carboxyl groups in the molecule. Examples of (meth)acrylic acid compounds having one carboxyl group in the molecule include one or more selected from the following substances: (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acrylic acid, etc. Acyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate; their acyl halides; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds. As a (meth)acrylic acid compound having multiple carboxyl groups within its molecule, examples can be selected from one or more of the following substances: 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1 ,1-Dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; their anhydrides, acyl halides; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.

[0048] The polymerizable monomer (a) of the present invention may include (a2) a polymerizable monomer having a sulfur atom. The polymerizable monomer having a sulfur atom (a2) can be any known compound without restriction, as long as it is a polymerizable monomer having at least one sulfur atom and one or more polymerizable groups in the molecule. The sulfur atom is contained in a form that does not form an acidic group such as a sulfonyl group within the molecule. The sulfur atom is contained in a form that forms a structure other than an acidic group within the molecule, such as C=S or CSC. It should be noted that the polymerizable monomer having a sulfur atom (a2) preferably does not have an acidic group. Examples of the polymerizable monomer having a sulfur atom (a2) include compounds capable of generating a thiol group through tautomerism, disulfide compounds, and chain or cyclic thioether compounds. Examples of polymerizable monomers having a sulfur atom in (a2) include 10-methacryloyloxydecyl-6,8-dithiooctanoate, 6-methacryloyloxyhexyl-6,8-dithiooctanoate, 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate, and 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole. One type of polymerizable monomer having a sulfur atom in (a2) may be used, or two or more may be used in combination. By including a polymerizable monomer having a sulfur atom in (a2), adhesion to noble metals can be imparted to the final composition made from the dental polymerizable composition (β) or the dental polymerizable composition intermediate (γ).

[0049] <(b) Polymerization inhibitors>

[0050] As the polymerization inhibitor (b) compounded in the dental polymeric composition (β) and the dental polymeric composition intermediate (γ) of this disclosure, known polymerization inhibitors can be used without any limitations. Examples of polymerization inhibitors selected from one or more of butylated hydroxytoluene, hydroquinone, butylated hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butylphenol, and 2,6-di-tert-butyl-4-methylphenol are also available.

[0051] (b) The polymerization inhibitor is preferably blended in a ratio of 5 parts by mass or less relative to 100 parts by mass of the polymeric monomer (a). When the amount of polymerization inhibitor blended in a ratio of 5 parts by mass relative to 100 parts by mass of the polymeric monomer (a), there is a high possibility that the polymerization and curing of the final composition made from the manufactured dental polymeric composition (β) or the dental polymeric composition intermediate (γ) will be hindered.

[0052] <(c) Organic solvents>

[0053] From the viewpoint of improving mixing efficiency, the present invention preferably includes (c) an organic solvent. As the (c) organic solvent, it is generally an organic solvent with a boiling point of 150°C or less at atmospheric pressure, and a solubility in water of 5% by mass or more at 25°C, more preferably 30% by mass or more, and most preferably an organic solvent capable of dissolving in water in any proportion. Preferably, it is a water-soluble volatile organic solvent with a boiling point of 100°C or less at atmospheric pressure. Examples of water-soluble volatile organic solvents with a boiling point of 100°C or less at atmospheric pressure include one or more selected from ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran. Furthermore, the aforementioned water-soluble volatile organic solvent is preferably selected from one or more selected from acetone, ethanol, and isopropanol. The (c) organic solvent can be used alone or in combination of two or more.

[0054] (c) The amount of organic solvent mixed with the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) is preferably selected such that the viscosity of the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) to be manufactured is less than 5000 mPa·s at 25°C.

[0055] <(d) Polymerization initiator>

[0056] The composition (α) of the present invention may be compounded (d) with a polymerization initiator to manufacture a dental polymeric composition (β) or a dental polymeric composition intermediate (γ).

[0057] <(d1) Photopolymerization initiator>

[0058] The polymerization initiators (d) that can be mixed in the composition (α) of the present invention include: (d1) photopolymerization initiators and (d2) chemical polymerization initiators. A photopolymerization initiator is a polymerization initiator capable of initiating polymerization by irradiation with light. Examples of photopolymerization initiators that can be mixed in the composition (α) of the present invention include one or more selected from photosensitizers, photoacid generators, and photopolymerization accelerators. Commonly used and known compounds can be used without any limitations. It should be noted that when mixing the (d1) photopolymerization initiator into the composition (α), it is preferable to perform the operation in a dark room where light in the absorption wavelength region of the (d1) photopolymerization initiator is shielded.

[0059] If a photosensitizer that can be mixed in the composition (α) of the present invention is specifically exemplified, it may be selected from one or more of α-diketones, benzoin alkyl ethers, thioxanones, benzophenones, acylphosphine oxides, and acylgermanium compounds. As an α-diketone, it may be selected from one or more of camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid. As a benzoin alkyl ether, it may be selected from one or more of benzoin, benzoin methyl ether, and benzoin ethyl ether. As a thioxanone, it may be selected from one or more of 2-isopropylthioxanone, 2-methoxythioxanone, 2-hydroxythioxanone, 2,4-diethylthioxanone, and 2,4-diisopropylthioxanone. As a benzophenone, it may be selected from one or more of benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone. Examples of acylphosphine oxides include one or more selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Examples of acylgermanium compounds include one or more selected from bisbenzoyldiethylgermanium and bisbenzoyldimethylgermanium.

[0060] As a photoacid-generating agent that can be mixed in the composition (α) of the present invention, examples include one or more selected from triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonate compounds. Among these, from the viewpoint of high polymerizability when used in combination with a sensitizer, one or more selected from triazine compounds and iodonium salt compounds are preferred. Iodonium salt compounds are preferably selected from one or more selected from 4-isopropyl-4'-methyldiphenyliodonium tetra(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium tetra(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and diphenyliodonium-2-carboxylate monohydrate.

[0061] As a photopolymerization accelerator that can be composable in the composition (α) of the present invention, an amine compound can be used. Examples of amine compounds selected from one or more of the following are possible: ethyl p-dimethylaminobenzoate, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and N,N-diisopropylaminoethyl methacrylate.

[0062] <(d2) Chemical polymerization initiators>

[0063] As a polymerization initiator (d) that can be mixed in the composition (α) of the present invention, a chemical polymerization initiator can be exemplified. Chemical polymerization refers to a polymerization method that cures without the need for special equipment such as a light irradiator, and a chemical polymerization initiator is a polymerization initiator capable of initiating chemical polymerization. They can use commonly used and well-known compounds without any restrictions.

[0064] As a specific example of a transition metal compound that can be mixed in the composition (α) of the present invention, a copper (Cu) compound or a vanadium (V) compound may preferably be used. Examples of copper (Cu) compounds selected include cuprous chloride (monovalent), cuprous bromide (monovalent), copper chloride (divalent), copper acetate (divalent), copper gluconate (divalent), copper acetylacetonate (divalent), and copper methacrylate (divalent). Examples of vanadium compounds selected include vanadium acetylacetonate (trivalent), vanadium tetroxide (quadrivalent), vanadium acetylacetonate oxyacetate (quadrivalent), vanadium stearate oxyacetate (quadrivalent), vanadium oxalate oxyacetate (quadrivalent), vanadium sulfate oxyacetate (quadrivalent), bis(1-phenyl-1,3-butanedione) vanadium oxyacetate (quadrivalent), bis(maltol) vanadium oxyacetate (quadrivalent), vanadium pentoxide (pentavalent), and sodium metavanadate (pentavalent).

[0065] Examples of thiourea compounds that can be mixed in the composition (α) of the present invention include one or more selected from dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylidene thiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and dicyclohexylthiourea. Among these, one or more selected from (2-pyridyl)thiourea, N-acetylthiourea, N-benzoylthiourea, and N-benzylthiourea are preferred.

[0066] The organic peroxides that can be mixed in the composition (α) of the present invention may be selected, for example, from one or more of the following: acyl peroxides, peroxide esters, dialkyl peroxides, peroxide ketals, ketone peroxides, peroxide esters, peroxide dicarbonates, and hydroperoxides. Specifically, they may be selected, for example, from one or more of the following: tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyacetate, tert-amyl peroxybenzoate, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0067] Examples of other chemical polymerization initiators include one or more selected from phosphine compounds, sulfinic acid compounds, borate compounds, barbituric acid derivatives, and ascorbic acid compounds. Examples of phosphine compounds include one or more selected from triphenylphosphine and 4-(phenylphosphine)benzoic acid. Examples of sulfinic acid compounds include sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate. Examples of borate compounds include salts of tetraarylborate compounds (selected from sodium, lithium, and potassium salts) and tetrabutylammonium salts. Examples of barbituric acid derivatives include one or more selected from 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and salts (sodium or calcium) of the aforementioned barbituric acid derivatives. As an ascorbic acid compound, examples may be selected from one or more of ascorbic acid, ascorbic acid 6-palmitate, and salt compounds of the aforementioned ascorbic acid compounds.

[0068] <(e) Filler>

[0069] (e) The filler may contribute to improving the mechanical strength of the dental polymeric composition (β) or the dental polymeric composition intermediate (γ), but in a manufacturing machine equipped with a container that substantially lacks stirring blades and whose container operates in a mixer selected from rotation, hyperbolic motion, and vibration, it is difficult to uniformly disperse the (e) filler in the composition (α). Therefore, it is preferable that the (e) filler is substantially not mixed in the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) of the present invention. However, a step of dispersing the (e) filler in the dental polymeric composition intermediate (γ) manufactured in the present invention may be included in subsequent manufacturing processes. As a method for dispersing the (e) filler in the dental polymeric composition intermediate (γ), examples include mixing using a manufacturing machine such as a rotary mixer, a dissolver, or a planetary mixer, and removing air bubbles under reduced pressure as needed. In particular, the dispersion method using a rotary mixer is preferred because it does not have stirring blades, thus enabling the final mixture to be obtained in high yield. In this invention, "substantially free of fillers" means that the composition (α) does not contain filler (e).

[0070] Examples of fillers (e) include (e1) inorganic fillers, (e2) organic fillers, and (e3) organic-inorganic composite fillers.

[0071] As an inorganic filler (e1), examples include one or more selected from silica, silica-based minerals, silica-based ceramics containing metal oxides, and glass. As a silica-based mineral, examples include one or more selected from kaolin, clay, mica, and tungsten. As a metal oxide, examples include one or more selected from Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO2, CaO, and P2O5. As a glass, examples suitable for use in the dental field include one or more selected from lanthanum glass, barium glass, strontium glass, sodium glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass. (e1) Preferred examples of inorganic fillers are selected from one or more of the following: crystalline quartz, hydroxyapatite, alumina, titanium dioxide, yttrium oxide, zirconium oxide, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride.

[0072] As an (e2) organic filler, examples may be selected from one or more of polymethyl methacrylate, polyethyl methacrylate, polymers of polyfunctional methacrylates, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber and styrene-butadiene rubber.

[0073] (e3) Organic-inorganic composite filler is a filler containing inorganic filler and monomer polymer, which is obtained as follows: polymerizable monomers are added to inorganic filler in advance, and after being made into a paste, it is polymerized and crushed to obtain the filler.

[0074] As filler (e), this also includes fillers that have been pre-treated with known surface treatment agents such as silane coupling agents. Examples of surface treatment agents include one or more selected from vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0075] As fillers (e), particulate fillers with a primary particle size of 0.001 to 0.1 μm are also included. Specific examples include "AEROSIL OX50", "AEROSIL 50", "AEROSIL 200", "AEROSIL 380", "AEROSIL R972", "AEROSIL R974", "AEROSIL 130", "AEROSIL RX200" or "AEROSIL R711" (all of which are product names manufactured by Evonik).

[0076] <Other Ingredients>

[0077] As long as it does not impair the effects of the present invention, one or more components selected from water, ultraviolet absorbers, α-alkylstyrene compounds, thiols, chain transfer agents, metal trapping agents, anti-discoloration agents, antibacterial materials, and other conventionally known additives may be added to the composition (α) of the present invention as needed to manufacture a dental polymeric composition (β) or a dental polymeric composition intermediate (γ). Examples of ultraviolet absorbers include one or more selected from benzophenone-based and benzotriazole-based compounds. Examples of thiols include one or more selected from n-butanethiol and n-octylthiol. Examples of chain transfer agents include terpenoid compounds. Examples of terpenoid compounds include one or more selected from limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinene oleene, β-pinene, and α-pinene. Examples of metal trapping materials include one or more selected from aminocarboxylic acid chelating agents and phosphonic acid chelating agents.

[0078] <Container manufacturing machine>

[0079] The container manufacturing machine of the present invention can be used without particular restriction as long as it is a machine that does not substantially have stirring blades, has a container capable of feeding the composition (α), and is capable of mixing the components within the container. Preferably, the container manufacturing machine is (1) a mixer in which the container rotates, (2) a mixer in which the container undergoes hyperbolic motion, or (3) a mixer in which the container vibrates. By using (1) a mixer in which the container rotates, (2) a mixer in which the container undergoes hyperbolic motion, or (3) a mixer in which the container vibrates, it is possible to easily obtain, with high yield, a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ) with excellent storage stability. Rotation refers to the container operating around a point or axis of the container. Hyperbolic motion refers to the container operating in a manner that depicts the shape of a hyperbola. Specifically, it refers to a cyclical motion in which the container moves in one direction, then in the opposite direction, and then again in the original direction. Through hyperbolic motion, the container moves not only horizontally but also sometimes at an angle. Vibration refers to the repetitive back-and-forth motion of a container in the forward-backward, up-down, or left-right directions.

[0080] The mixer that rotates as a container (1) can also be a commercially available mixer. Examples of mixers that rotate as a container (1) include products with names such as "Tabletop Tumbler Labo" (EISHIN Co., Ltd.), "Portable TumblerLabo" (EISHIN Co., Ltd.), "Tumbler Mini" (EISHIN Co., Ltd.), "TumblerMixer" (EISHIN Co., Ltd.), "Drum Mixer" (EISHIN Co., Ltd.), or "SK-1100TVII" (Shashin Chemical Co., Ltd.).

[0081] Regarding the rotation speed (in minutes) of the mixer when using container (1) for rotation. -1 There are no particular limitations on the rotation speed and operating time, as long as the composition (α) is stirred and mixed to produce a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ). However, since there is a possibility of generating heat of mixing and reducing the mutual solubility of raw materials, the rotation speed is preferably 100 minutes. -1 The following is a further preferred option: 60 minutes. -1 the following.

[0082] The mixer that performs hyperbolic motion in container (2) can also be a commercially available mixer. Examples of mixers that perform hyperbolic motion in container (2) include "Turbula Shaker-Mixer T2G" (Shinmaru Enterprises Corporation), "Turbula Shaker-Mixer T2GE" (Shinmaru Enterprises Corporation), "Turbula Shaker-Mixer T2F" (Shinmaru Enterprises Corporation), "Turbula Shaker-Mixer T10B" (Shinmaru Enterprises Corporation), or "Turbula Shaker-Mixer T50A" (Shinmaru Enterprises Corporation).

[0083] Regarding the speed (in minutes) of hyperbolic motion when using a mixer with container (2) for hyperbolic motion. -1There are no particular limitations on the operation time, as long as the composition (α) is stirred and mixed to produce a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ), but since mixing heat may be generated, the hyperbolic speed is preferably 50 minutes. -1 the following.

[0084] The mixer used to vibrate the container in (3) can also be a commercially available mixer. Examples of mixers used to vibrate the container in (3) include the product name "Vortex3" (IKA Japan Co., Ltd.), the product name "VORTEX Genius 3" (IKA Japan Co., Ltd.), the product name "CPS-20" (Biosan), the product name "Rocking shaker" (Seiwa Giken Co., Ltd.), the product name "Vacuum Degassing Vibrating Mixer VVS-10" (Seiwa Giken Co., Ltd.), or the product name "Vacuum Degassing Vibrating Mixer VS-15" (Seiwa Giken Co., Ltd.).

[0085] Regarding the vibration speed (in minutes) when using a vibrating mixer with container (3) -1 There are no particular limitations on the vibration speed and operating time, as long as the composition (α) is stirred and mixed to produce a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ). However, since there is a possibility of generating heat during mixing, a vibration speed of 400 minutes is preferred. -1 the following.

[0086] The container of the manufacturing machine in this invention is made of a material that does not react with the components constituting the composition (α), and can be used without particular restriction as long as it is the shape provided by the manufacturing machine. Considering mixing efficiency, it is preferable to add the composition (α) with a container porosity of 10-90%, and more preferably with a container porosity of 20-80%. When the container porosity is less than 10% or more than 90%, the mixing efficiency of the composition (α) decreases, making it difficult to obtain a uniform composition (α).

[0087] An example of the manufacturing method disclosed in this invention is the following manufacturing method, which includes the following steps:

[0088] 1-1. A process of placing a composition (α) comprising (a) a polymerizable monomer and (b) a polymerization inhibitor into a container of a manufacturing machine having a container but substantially lacking stirring blades, such that the porosity of the container is 10-90%; and,

[0089] 1-2. The process of making the container work.

[0090] An example of the manufacturing method disclosed in this invention is the following manufacturing method, which includes the following steps:

[0091] 2-1. A process of placing a composition (α) comprising (a) a polymerizable monomer and (b) a polymerization inhibitor into a container of a manufacturing machine having a container but not substantially having stirring blades, such that the porosity of the container is 10 to 90%.

[0092] 2-2. The process of heating the container to 30~70℃; and,

[0093] 2-3. Procedures for making the container work.

[0094] In this invention, "substantially lacking stirring blades" means that the manufacturing machine does not have a stirring part for stirring, i.e., blades or blades mounted on the rotating shaft of the device. In this invention, "porosity" means ([space where various substances (flowable polymerizable monomers and / or organic solvents and / or water, etc.) do not enter] / [the overall space of the container]) × 100. Steps 1-1 and 2-1 are preferably performed at room temperature (approximately 10~30°C). In this invention, "making the container work" means that the container performs one or more actions selected from rotation, hyperbolic motion, and vibration. When performing the step of "heating the container to 30~70°C", (a) the viscosity of the polymerizable monomer decreases and the mixing efficiency of the composition (α) increases, so this step is preferred.

[0095] Consider including the following step (L) before steps 1-1 and 2-1. After step (L), a uniform (a) polymerizable monomer can be obtained. By performing step (L) before steps 1-1 and 2-1, the time required to uniformly mix the raw materials through the mixing steps 1-2 and 2-3 to obtain a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) can be shortened.

[0096] (L) The process of mixing multiple (a) polymerizable monomers.

[0097] Consider the following steps (M) to (O) in addition to steps 1-1 to 1-2 and 2-1 to 2-3. These steps can be performed either before or after steps 1-1 to 1-2 and 2-1 to 2-3. When steps (M) to (O) are performed after the "step of operating the container" in the manufacturing method of the present invention, it is considered that stirring is performed using a manufacturing machine that has a container but does not substantially have stirring blades, or a manufacturing machine that has both stirring blades and a container, so that the obtained substance is homogeneous. Steps (M) to (O) are preferably performed after steps 1-1 to 1-2 and 2-1 to 2-3.

[0098] (M) The process of preparing (c) organic solvent in the container of a manufacturing machine that has a container but does not actually have stirring blades.

[0099] (N) The process of preparing (d) polymerization initiator in the container of a manufacturing machine that has a container but does not actually have stirring blades.

[0100] (O) The process of preparing other ingredients in the container of a manufacturing machine that has a container but does not actually have stirring blades.

[0101] The process of (P) can be continued after the manufacturing method disclosed in this invention. Alternatively, the process of (P) can also be carried out by slowly dispersing the filler (e) by repeatedly preparing the filler (e) in a container and stirring it.

[0102] (P) A process of preparing and stirring a dental polymeric composition (β) or a dental polymeric composition intermediate (γ) and (e) a filler in a container of a manufacturing machine equipped with stirring blades and a container.

[0103] Example

[0104] The following shows the materials used in the embodiments and comparative examples, along with their abbreviations. It should be noted that the present invention is not limited to these embodiments.

[0105] <(a) Polymerizable monomers>

[0106] • BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (density: approx. 1.16 g / mL at 25°C)

[0107] UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate (density: approx. 1.11 g / mL at 25°C)

[0108] • TEGDMA: Triethylene glycol dimethacrylate (density: approx. 1.07 g / mL at 25°C)

[0109] • GDMA: Glyceryl dimethacrylate (density: approximately 1.12 g / mL at 25°C)

[0110] HEMA: Hydroxyethyl methacrylate (density: approximately 1.02 g / mL at 25°C)

[0111] • MDP: 10-Methacryloxydecyl dihydrophosphate (density: approx. 1.14 g / mL at 25°C)

[0112] MHPA: 6-Methacryloxyhexylphosphonoacetate (density: approx. 1.20 g / mL at 25°C)

[0113] • META: 4-Methacryloxyethoxycarbonylphthalic anhydride (Density (g / mL at 25°C) is not specified as it is a powder).

[0114] <(b) Polymerization inhibitors>

[0115] MEHQ: Hydroquinone monomethyl ether

[0116] BHT: Butylated hydroxytoluene

[0117] <(c) Organic solvents>

[0118] • Acetone (density: approximately 0.78 g / mL at 25°C)

[0119] • Ethanol (density: approximately 0.78 g / mL at 25°C)

[0120] <(d) Polymerization initiator>

[0121] •CQ: Camphorquinone

[0122] ·BAPO: Phenylenol bis(2,4,6-trimethylbenzoyl)phosphine oxide

[0123] DMBE: Ethyl 4-N,N-dimethylaminobenzoate

[0124] • IPIFP: 4-Isopropylphenyl(p-Tolyl)iodonium tri(pentafluoroethyl)trifluorophosphate

[0125] DEPT: N,N-Di(2-hydroxyethyl)-p-toluidine

[0126] •BPO: Benzoyl peroxide

[0127] • CHP: Cucurbitene hydroperoxide (density: approx. 1.02 g / mL at 25°C)

[0128] •TMBH: 1,1,3,3-Tetramethylbutyl hydroperoxide (density: approx. 0.89 g / mL at 25°C)

[0129] •VOA: Vanadyl acetylacetonate

[0130] •COA: Copper Acetylacetone

[0131] PTU: N-pyridylthiourea

[0132] <(e) Filler>

[0133] • R-974: Aerosil R-974 (manufactured by Evonik, 12nm primary particle size, hydrophobic silica surface-treated with dimethyldichlorosilane)

[0134] <Container manufacturing machine>

[0135] Manufacturing Machine 1: Desktop Tumbler Labo (EISHIN Co.,Ltd.)

[0136] Manufacturing Machine 2: Turbula Shaker-Mixer T2G (Shinmaru Enterprises Corporation)

[0137] Manufacturing Machine 3: Rocking Shaker (Seiwa Giken Co., Ltd.)

[0138] <Manufacturing machines other than those equipped with container manufacturing machines>

[0139] Manufacturing Machine 4: MAZELA ZZ-1200 (Tokyo Rikka Equipment Co., Ltd.) Agitator Blades: T-1A type (Tokyo Rikka Equipment Co., Ltd.)

[0140] (Example 1)

[0141] Add 138g BisGMA, 92g GDMA, 0.23g BHT, 2.3g CQ, and 2.3g DMBE to a 2L transparent polyethylene container. Close the container lid and heat it in a thermostat at 50°C for 1 hour. Then, place the container in manufacturing machine 2 and heat for 50 minutes. -1 Mix at a certain speed to prepare a mixture.

[0142] (Example 2)

[0143] Add 1212g BisGMA, 808g GDMA, 2.02g MEHQ, 20.2g CQ, 20.2g DMBE, and 20.2g DEPT to a 2L transparent polyethylene container. Close the container lid and heat it in a thermostat at 50°C for 1 hour. Then, place the container in manufacturing machine 1 and heat for 60 minutes. -1 Mix at a certain speed to prepare a mixture.

[0144] (Example 3)

[0145] Add 132g of UDMA, 88g of TEGDMA, and 2.2g of BHT to a 2L transparent polyethylene container. Close the container lid and place it in manufacturing machine 3 for 400 minutes. -1 Mix at a certain speed to prepare a mixture.

[0146] (Examples 4-27, Comparative Examples 1-13)

[0147] Prepare a mixture by changing the components and mixing amounts without changing the mixing conditions described in any of Examples 1-3 (using the same apparatus and the same speed). It should be noted that when the composition contains BisGMA but not an organic solvent, after adding all components to the container, heat it in a thermostat at 50°C for 1 hour before performing the mixing process.

[0148] (Example 28)

[0149] Add 138g BisGMA, 92g GDMA, 0.23g BHT, and 2.3g CQ to a 2L transparent polyethylene container. Close the container lid and heat in a thermostat at 50°C for 1 hour. Then, place the container in manufacturing machine 2 and heat for 50 minutes. -1 Mix at a set speed. After 5 hours of mixing, temporarily remove the container from the manufacturing machine and add 2.3g of CHP to it. Then, place the container back into manufacturing machine 2 and mix for 50 minutes. -1 Mix at a certain speed to prepare a mixture.

[0150] (Example 29)

[0151] Add 1212g BisGMA, 808g GDMA, 2.02g MEHQ, 20.2g CQ, and 20.2g DMBE to a 2L transparent polyethylene container. Close the container lid and heat it in a thermostat at 50°C for 1 hour. Then, place the container in manufacturing machine 1 and heat for 60 minutes. -1 Mix at a set speed. After 5 hours of mixing, temporarily remove the container from the manufacturing machine and add 20.2g of TMBH to the container. Then, set the container back into manufacturing machine 1 and mix for 60 minutes. -1 Mix at a certain speed to prepare a mixture.

[0152] (Example 30)

[0153] Add 132g of UDMA, 88g of TEGDMA, 0.22g of BHT, and 2.2g of CQ to a 2L transparent polyethylene container. Close the container lid and place it in manufacturing machine 3 for 400 minutes. -1 Mix at a set speed. Five hours after mixing begins, temporarily remove the container from the manufacturing machine and add 2.2g of BPO into it. Then, place the container back into manufacturing machine 3 and mix for 400 minutes. -1 Mix at a certain speed to prepare a mixture.

[0154] (Examples 31-33, Comparative Examples 14 and 15)

[0155] The mixture was prepared by changing the components and mixing amounts without changing the mixing conditions described in any of Examples 28-30 (the same speed was used if the same apparatus was used). It should be noted that when the composition includes BisGMA, after adding components other than the organic peroxide to the container, the mixture was heated in a thermostat at 50°C for 1 hour and mixed for 5 hours. Then, the container was temporarily removed from the manufacturing machine, the organic peroxide was added to the container, and mixing was performed again to prepare the mixture.

[0156] (Comparative Example 16)

[0157] Add 672g BisGMA, 448g TEGDMA, 1.12g MEHQ, 11.2g CQ, 11.2g DMBE, and 11.2g DEPT to a 2L transparent polyethylene container. Add the stirring blades installed in manufacturing machine 4 to the container and incubate for 600 minutes. -1 Mix at a certain speed to obtain a mixture.

[0158] (Comparative Examples 17-21)

[0159] A mixture was prepared by changing only the components to be mixed without changing the stirring conditions described in Comparative Example 16 (setting the same speed when using the same apparatus).

[0160] [Mixing time required to achieve homogenization]

[0161] The time required from the start of the mixing process until the components are uniformly dissolved is evaluated as the "mixing time required to achieve homogenization". Whether the components are uniformly dissolved is determined by visual inspection. It should be noted that if the mixing process is divided into multiple stages, the total time required for each mixing stage is used as the "mixing time required to achieve homogenization".

[0162] [Return rate]

[0163] Measure the weight of the container immediately after adding raw materials (denoted as weight m1). Measure the weight of the container after removing it from the mixer following the mixing process (denoted as weight m2). Record the case where the weight m2 divided by the weight m1 is less than 99.9% as "poor" and the result is greater than 99.9% as "good".

[0164] [Viscosity Measurement Methods]

[0165] The resulting mixture was placed in a 50 mL glass bottle and allowed to stand for one day at a constant temperature of 25°C. After standing for one day, the viscosity (mPa·s) was measured at 25°C using a Type B viscometer (BMII type viscometer, manufactured by Toki Sangyo Co., Ltd.). It should be noted that the viscosity is taken from 3 minutes after the start of the measurement.

[0166] [Maintaining stability]

[0167] The resulting mixture was placed into 50 mL glass bottles and stored in a thermostat set at 50°C for 10 weeks. The appearance and viscosity of the mixture before and after storage at 50°C were evaluated for any changes; observed changes were marked with "×", and no observed changes were marked with "〇". It should be noted that the appearance evaluation of the mixture was performed visually. Furthermore, the viscosity was evaluated using the method described above.

[0168] [Table 1]

[0169]

[0170] [Table 2]

[0171]

[0172] [Table 3]

[0173]

[0174] [Table 4]

[0175]

[0176] [Table 5]

[0177]

[0178] The mixtures obtained in Examples 1-33 showed excellent yields and excellent storage stability. It should be noted that, compared to cases where the container porosity was 10-90%, the mixing time required to achieve homogenization of the mixture was shorter when the container porosity was 20-80%. On the other hand, in Comparative Examples 1-10 and Comparative Examples 14 and 15, the mixing time required to achieve homogenization was difficult to extend or homogenize, resulting in poor storage stability of the obtained mixtures. It is believed that when the porosity is less than 10% or greater than 90%, the mixing efficiency decreases, making it difficult to obtain a homogeneous mixture, which adversely affects storage stability.

[0179] In Comparative Examples 11-13, the compounding components contained filler (e), which was difficult to disperse uniformly in the mixture, resulting in poor storage stability of the mixture. It is believed that in order to uniformly disperse filler (e) in the dental composition, it is best to use a manufacturing machine equipped with stirring blades and a container.

[0180] Although Comparative Examples 16-21 yielded homogeneous mixtures in the same manner as the Examples, the yield of the mixtures was poor because the manufacturing machine used stirring blades.

[0181] Industrial availability

[0182] This invention can be industrially utilized in the dental field as a method for manufacturing dental polymeric compositions such as dental dentin bonding materials.

Claims

1. A method for manufacturing a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ), wherein the method uses a manufacturing machine having a container but substantially lacking stirring blades, the manufacturing method comprising the steps of: disposing of a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor in a container, such that the container has a porosity of 10 to 90%; and operating the container.

2. A method for manufacturing a substantially filler-free dental polymeric composition (β) or a dental polymeric composition intermediate (γ), wherein the method uses a manufacturing machine having a container but substantially lacking stirring blades, the manufacturing method comprising the steps of: disposing of a composition (α) comprising (a) a polymeric monomer and (b) a polymerization inhibitor in a container such that the container has a porosity of 10 to 90%; heating the container to 30 to 70°C; and operating the container.

3. The method for manufacturing the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) according to claim 1 or 2, wherein, The container of a manufacturing machine that has a container but does not actually have stirring blades performs one or more operations selected from rotation, hyperbolic motion and vibration.

4. The method for manufacturing the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) according to claim 1 or 2, wherein, The container of the manufacturing machine, which has a container but does not actually have stirring blades, is selected for 60 minutes. -1 Rotation speed at the following rate, 50 minutes -1 The following speed hyperbolic motion and 400 minutes -1 The operation involves one or more of the following vibration speeds.

5. The method for manufacturing the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) according to claim 1 or 2, wherein, The porosity of the container is made to be 20-80%.

6. The method for manufacturing the dental polymeric composition (β) or the dental polymeric composition intermediate (γ) according to claim 1 or 2, wherein, The composition (α) contains (c) an organic solvent.

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