JP7395830B2 - Medical three-dimensional model, three-dimensional model, and method for producing medical three-dimensional model - Google Patents

Description

The present invention relates to a medical three-dimensional structure , a three-dimensional structure, and a method for producing a medical three-dimensional structure .

In recent years, a method for manufacturing resin molded products has been to selectively polymerize and harden curable resin compositions using active energy rays such as ultraviolet lasers, based on three-dimensional shape data designed using three-dimensional design systems such as three-dimensional CAD. Accordingly, optical stereolithography (stereolithography) is used to create three-dimensional objects. This optical three-dimensional modeling method can handle complex shapes that are difficult to produce by cutting, and because it takes a short manufacturing time and is easy to handle, it can be used to manufacture prototype models of industrial products as well as resin molded products. It is becoming widely used.

A typical example of optical stereolithography is to irradiate a computer-controlled spot-shaped ultraviolet laser from above onto a liquid photocurable resin placed in a container to harden a single layer of a predetermined thickness, and then create a model. An example of this method is to lower the object by one layer, supply a liquid resin onto the layer, cure it with ultraviolet laser light in the same manner as described above, and laminate the layers.By repeating this operation, a three-dimensional object can be obtained. Recently, in addition to the pointillist method using a spot-shaped ultraviolet laser, DMD (digital micromirror device), which uses a light source other than a laser such as an LED and has multiple digital micromirror shutters arranged in a planar manner, has been developed. Through a so-called planar drawing mask, UV light is irradiated from below through a transparent container containing a photocurable resin to harden one layer of a predetermined cross-sectional pattern, and the model is lifted up by one layer. Therefore, the surface exposure method, in which the next layer is irradiated and cured in the same way as described above, and three-dimensional objects are obtained by sequentially laminating layers, is increasing.

The properties required for the photocurable resin used in the optical three-dimensional modeling method include various properties such as low viscosity, the ability to form a smooth liquid surface, and excellent curability. As such photocurable resins, resin compositions mainly containing radically polymerizable compounds are known (see, for example, Patent Documents 1 and 2), but these may cause deformation such as warping during curing. There was a problem. Furthermore, when a medical three-dimensional object is modeled using the resin composition, there are problems such as poor biological safety.

Therefore, there has been a need for a material that can form a cured product with excellent biological safety.

Japanese Patent Application Publication No. 7-228644 Japanese Patent Application Publication No. 2008-189782

The problem to be solved by the present invention is to provide a cured product, a three-dimensional molded product, and a method for producing the cured product that have excellent biological safety.

As a result of intensive studies to solve the above problems, the present inventors have discovered that a cured product, which is a curing reaction product of a curable resin composition, is an extract obtained by extracting the cured product under specific conditions. The inventors have discovered that the above-mentioned problems can be solved by using a cured product characterized in that the amount of potassium manganate reducing substance consumed is 10 ml or less, and the present invention has been completed.

That is, the present invention relates to a cured product which is a curing reaction product of a curable resin composition, and the extract obtained by adding 20 ml of ion-exchanged water to 4 g of the cured product and extracting at 70° C. for 24 hours is obtained by reducing potassium permanganate. The present invention relates to a cured product, a three-dimensional molded product, and a method for producing the cured product, characterized in that the amount of a physical substance is 10 ml or less.

Since the cured product of the present invention has excellent biological safety, it can be used for medical materials, composite resins, bonding materials, resin cement, resin blocks for CAD/CAM, etc. Among these, it can be suitably used for dental hard resin materials such as surgical guides for dental treatment, temporary teeth, bridges, and orthodontic appliances.

The cured product of the present invention is a curing reaction product of a curable resin composition, and the amount of potassium permanganate reducing substance in the extract obtained by adding 20 ml of ion-exchanged water to 4 g of the curing reaction product and extracting at 70°C for 24 hours. is 10 ml or less.

Here, the "potassium permanganate reducing substance amount" refers to the difference in potassium permanganate solution consumption between the test liquid and the blank test liquid in the potassium permanganate reducing substance amount test.

The potassium permanganate reducing substance amount test is conducted in accordance with the method shown in JIS K0102 (2013) Factory Effluent Test Method, and specifically, is a test conducted by the following method.

[Potassium permanganate reducing substance amount test]
Six test pieces (4 g) each measuring 20 mm x 15 mm x 2 mm were immersed in 20 ml of distilled water, placed in a constant temperature dryer at 70°C, extracted for 24 hours, then allowed to cool to room temperature, and the extracted liquid was used as the test liquid. use. Separately, 20 ml of distilled water was placed in a constant temperature dryer at 70°C, extracted for 24 hours, and then allowed to cool to room temperature, and used as a blank test liquid. Put 20 ml of each of the test solution and the blank test solution into a stoppered flask, add 20.0 ml of a 0.002 mol/l potassium permanganate aqueous solution and 1.0 ml of a 0.01 mol/l sulfuric acid aqueous solution, and boil for 3 minutes. After cooling, further add 0.1 g of potassium iodide, seal the cap, shake well and leave for 10 minutes, then titrate with 0.01 mol/l sodium thiosulfate aqueous solution (indicator: 5 drops of starch solution). Calculate the difference in potassium permanganate consumption between the test solution and the blank test solution (test solution - blank test solution).

Examples of the curable resin composition include those containing a compound having at least one polymerizable unsaturated bond in one molecule.

Examples of the compound having at least one polymerizable unsaturated bond in one molecule include (meth)acrylate compound (A).

In the present invention, "(meth)acrylate" means acrylate and/or methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and/or methacrylic.

Examples of the (meth)acrylate compound (A) include a (meth)acrylate compound (a1) represented by the following structural formula (1).

［式（１）中、Ｒ^１は、それぞれ独立して水素原子またはメチル基であり、Ｒ^２は、それぞれ独立して水素原子またはメチル基であり、Ｒ^３は、それぞれ独立して水素原子またはメチル基である。Ｘは、－Ｏ－、－ＳＯ_２－、下記構造式（２）で表される構造、または下記構造式（３）で表される構造であり、ｍは、０または１～１０の整数であり、ｎは、０または１～１０の整数であり、ｍ＋ｎは、１～２０の整数である。］

[In formula (1), R ¹ is each independently a hydrogen atom or a methyl group, R ² is each independently a hydrogen atom or a methyl group, and R ³ is each independently a hydrogen atom or a methyl group. It is a methyl group. X is -O-, -SO ₂ -, a structure represented by the following structural formula (2), or a structure represented by the following structural formula (3), and m is 0 or an integer from 1 to 10. , n is 0 or an integer from 1 to 10, and m+n is an integer from 1 to 20. ]

［式（２）中、Ｒ^４、Ｒ^５は、水素原子または炭素原子数１～１０の炭化水素基である。］

[In formula (2), R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ]

The content of the (meth)acrylate compound (a1) in the (meth)acrylate compound (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and 80 to 100% by mass. Particularly preferred is a range of %.

Further, as the (meth)acrylate compound (A), other (meth)acrylate compounds other than the (meth)acrylate compound (a1) can also be used.

Examples of the other (meth)acrylate compounds include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, and hexadecyl (meth)acrylate. , octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxy Propyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, benzyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, nonylphenoxyethyl Tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetracyclododecanyl (meth)acrylate , cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, 2-(meth)acryloyloxymethyl-2-methylbicycloheptane adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, ) acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, 2-(meth)acryloyloxymethyl-2-methylbicycloheptane adamantyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 3 -Methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate Acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, polypropylene glycol di(meth)acrylate (meth)acrylate, di(meth)acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, ethylene oxide-modified phosphoric acid (meth)acrylate, ethylene oxide-modified alkylated phosphorus Acid di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyether(meth)acrylate, diethylaminoethyl(meth)acrylate, norbornane dimethanol di(meth)acrylate (meth)acrylate, norbornane dimethanol di(meth)acrylate, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to norbornane dimethanol, tricyclodecane dimethanol di(meth)acrylate, tricyclo Decane diethanol di(meth)acrylate, diol di(meth)acrylate obtained by adding 2 moles of ethylene oxide or propylene oxide to tricyclodecane dimethanol, pentacyclopentadecane dimethanol di(meth)acrylate, pentacyclopentadecane diethanol diethanol (Meth)acrylate, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to pentacyclopentadecane dimethanol, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to pentacyclopentadecane diethanol. Di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl hydroxypivalate glycol di(meth)acrylate, bis(2-acryloyloxyethyl)hydroxyethyl isocyanurate, bis(2-acryloyloxypropyl) Hydroxypropyl isocyanurate, bis(2-acryloyloxybutyl)hydroxybutyl isocyanurate, bis(2-methacryloyloxyethyl)hydroxyethyl isocyanurate, bis(2-methacryloyloxypropyl)hydroxypropyl isocyanurate, bis(2-methacryloyloxy) butyl) hydroxybutyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, tris (2-acryloyloxybutyl) isocyanurate, tris (2-methacryloyloxyethyl) isocyanurate , tris (2-methacryloyloxypropyl) isocyanurate, tris (2-methacryloyloxybutyl) isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, penta Erythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di- or triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane. Examples include tri(meth)acrylate and poly(meth)acrylate of dipentaerythritol. These other (meth)acrylate compounds can be used alone or in combination of two or more.

Further, as the other (meth)acrylate compounds, urethane (meth)acrylate, epoxy (meth)acrylate, etc. can also be used.

The urethane (meth)acrylate generally has a polyurethane chain produced by polycondensation of a polyisocyanate compound and a polyol compound. A (meth)acryloyl group or a (meth)acryloyloxy group may be introduced at both ends of this polyurethane chain.

As the urethane (meth)acrylate, for example, a polyol compound and a polyisocyanate compound are reacted in a ratio in which the isocyanate groups are in excess of the hydroxyl groups to prepare a urethane resin in which the molecular terminal is an isocyanate group, and then Examples include those obtained by a method of reacting radically polymerizable monomers having a hydroxyl group and a (meth)acryloyl group (or (meth)acryloyloxy group).

The reaction between the polyol compound and the polyisocyanate compound is performed when the equivalent ratio [(NCO)/(OH)] between the hydroxyl group (OH) of the polyol compound and the isocyanate group (NCO) of the polyisocyanate compound is 1.5 to 1. A range of 2 is preferred.

Examples of the polyol compounds include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, dipropylene glycol, and triethylene glycol. Propylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neo Pentyl glycol ester, cyclohexane dimethylol, 1,4-cyclohexane diol, ethylene oxide adduct of hydroquinone, propylene oxide adduct of hydroquinone, spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A, and 1,6-hexane diol Polyols such as polycarbonate diols; polyester polyols obtained by condensing the above polyols with α,β-unsaturated polycarboxylic acids, saturated polycarboxylic acids, or their acid anhydrides; and β-propiolactone. Examples include polyester polyols obtained by ring-opening polymerization of lactones such as , β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. These polyol compounds can be used alone or in combination of two or more.

Examples of α,β-unsaturated polycarboxylic acids and their acid anhydrides that can be condensed with the polyols to produce polyester polyols include maleic acid, fumaric acid, itaconic acid, citraconic acid, and chlorinated maleic acid. Various α,β-unsaturated polycarboxylic acids or anhydrides thereof may be mentioned. Examples of saturated polycarboxylic acids and their acid anhydrides that are condensed with the polyols to produce polyester polyols include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, monochlorophthalic acid, dichlorophthalic acid, trichlorophthalic acid, Het acid, chlorendic acid, dimer acid, adipic acid, pimelic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, terephthalic acid, dimethylterephthalic acid, 2-sodium Sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylene dicarboxylic acid, muconic acid, oxalic acid , saturated polycarboxylic acids such as malonic acid, glutaric acid, hexahydrophthalic acid, and tetrabromophthalic acid, or acid anhydrides thereof. These can be used alone or in combination of two or more.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate and other aromatic diisocyanate compounds; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); isocyanurate modified products, biuret modified products thereof, Examples include modified allophanate. Moreover, these polyisocyanate compounds can be used alone or in combination of two or more types.

For the reaction between the polyol compound and the polyisocyanate compound, a urethanization catalyst may be used as necessary, and examples of the urethanization catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine. , triphenylphosphine, phosphines such as triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,1 , 3,3-tetrabutyl-1,3-dodecanoyl distanoxane, etc., organometallic compounds such as zinc octylate, bismuth octylate, inorganic tin compounds such as tin octoate, inorganic metal compounds, etc. It will be done. These urethanization catalysts can be used alone or in combination of two or more.

Examples of the radical polymerizable monomer having a hydroxyl group and a (meth)acryloyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, pentaerythritol triacrylate, and isocyanuric acid. Hydroxyl group-containing (meth)acrylates such as acid ethylene oxide-modified diacrylates, ethylene oxide adducts of the hydroxyl group-containing (meth)acrylates, propylene oxide adducts of the hydroxyl group-containing (meth)acrylates, and tetra of the hydroxyl group-containing (meth)acrylates. Examples include methylene glycol adducts and lactone adducts of the hydroxyl group-containing (meth)acrylates. These radically polymerizable monomers having a hydroxyl group and a (meth)acryloyl group can be used alone or in combination of two or more.

Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy resin with (meth)acrylic acid or its anhydride.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Examples include reactive epoxy resins, biphenylaralkyl epoxy resins, fluorene epoxy resins, xanthene epoxy resins, dihydroxybenzene epoxy resins, trihydroxybenzene epoxy resins, and the like. These epoxy resins can be used alone or in combination of two or more.

The method for producing the curable resin composition is not particularly limited, and any method may be used.

The curable resin composition may optionally contain a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a silicone additive, a fluorine additive, a silane coupling agent, a phosphate ester compound, Various additives such as organic fillers, inorganic fillers, rheology control agents, defoaming agents, and colorants can also be contained.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-1-butanone and the like. Among these, phosphorus has excellent reactivity with (meth)acrylate compounds, contains less unreacted (meth)acrylate compounds in the resulting cured product, and provides a cured product with excellent biological safety. The compounds are preferred, and specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are preferred. Further, these photopolymerization initiators can be used alone or in combination of two or more types.

Examples of commercially available photopolymerization initiators include "Omnirad-1173," "Omnirad-184," "Omnirad-127," "Omnirad-2959," "Omnirad-369," and "Omnirad-379." , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", " "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA" ”, “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Bicure-10”, “Bicure-55” (manufactured by Stouffer Chemical Co., Ltd.), “Trigonal P1” (manufactured by Akzo Corporation), “Sandray 1000” ( Sandoz), ``Deep'' (Upjohn), ``Quantacure-PDO'', ``Quantacure-ITX'', ``Quantacure-EPD'' (Ward Blenkinsop), ``Runtecure-1104'' (Runtec) (manufactured by a company), etc. Among these, " Omnirad-TPO" and "Omnirad-819" are preferred.

The amount of the photopolymerization initiator added is preferably 0.1% by mass or more and 4.5% by mass or less, and 0.5% by mass or more and 3% by mass or less, for example, in the curable resin composition. It is more preferable to use it within a range.

Further, the curable resin composition may further have a photosensitizer added thereto to improve its curability, if necessary.

Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, and s-benzylisothiuronium-p-toluenesulfonate. Examples include compounds.

Examples of the ultraviolet absorber include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, Triazine derivatives such as 3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2 -xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.

Examples of the polymerization inhibitor include hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylated hydroxytoluene, and nitrosamine salts.

Examples of the silicone additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified copolymer. Dimethylpolysiloxane copolymers, polyorganosiloxanes with alkyl groups or phenyl groups such as amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes with polyether-modified acrylic groups, polydimethylsiloxanes with polyester-modified acrylic groups, etc. Can be mentioned. These silicon-based additives can be used alone or in combination of two or more.

Examples of the fluorine-based additive include the "Megaface" series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, - Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1 , 3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3- ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, allyltri Vinyl silane coupling agents such as chlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane;

Diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Epoxy-based silane coupling agents such as ethoxysilane;

Styrenic silane coupling agents such as p-styryltrimethoxysilane;

(Meta) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Acryloxy-based silane coupling agent;

N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Amino-based silane coupling such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. agent;

A ureido-based silane coupling agent such as 3-ureidopropyltriethoxysilane;

Chloropropyl-based silane coupling agent such as 3-chloropropyltrimethoxysilane;

Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;

Sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide;

Examples include isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

Examples of the phosphoric acid ester compounds include those having a (meth)acryloyl group in the molecular structure, and commercially available products include, for example, "Kayamar PM-2" and "Kayamar PM-2" manufactured by Nippon Kayaku Co., Ltd. 21", "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A (N)", manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", manufactured by SOLVAY, " SIPOMER PAM 300'', ``SIPOMER PAM 4000'', Osaka Organic Chemical Industry Co., Ltd. ``Viscoat #3PA'', ``Viscoat #3PMA'', Daiichi Kogyo Seiyaku Co., Ltd. ``New Frontier S-23A''; allyl ether group in the molecular structure. Examples include "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphoric acid ester compound having the following.

Examples of the organic filler include plant-derived solvent-insoluble substances such as cellulose, lignin, and cellulose nanofibers, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, Examples include organic beads such as acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluoroethylene resin beads, and polyethylene resin beads. These organic fillers can be used alone or in combination of two or more.

Examples of the inorganic filler include inorganic fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These inorganic fillers can be used alone or in combination of two or more. Further, the average particle size of the inorganic fine particles is preferably in the range of 95 to 250 nm, particularly preferably in the range of 100 to 180 nm.

When containing the above-mentioned inorganic fine particles, a dispersion aid can be used. Examples of the dispersion aid include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These dispersion aids can be used alone or in combination of two or more. In addition, commercially available products of the dispersion aid include, for example, "Kayamar PM-21" and "Kayamar PM-2" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd. .

Examples of the rheology control agent include amide waxes such as "Disparon 6900" manufactured by Kusumoto Kasei Co., Ltd.; urea-based rheology control agents such as "BYK410" manufactured by Big Chemie; and "Disparon 4200" manufactured by Kusumoto Kasei Co., Ltd. and cellulose acetate butyrate such as "CAB-381-2" and "CAB 32101" manufactured by Eastman Chemical Products.

Examples of the defoaming agent include oligomers containing fluorine or silicon atoms, or oligomers such as higher fatty acids and acrylic polymers.

Examples of the coloring agent include pigments and dyes.

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

Examples of the inorganic pigment include titanium oxide, antimony red, red red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine blue, carbon black, and graphite.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, Examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These pigments can be used alone or in combination of two or more.

Examples of the dye include azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, and naphthoquinone. Examples include dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, and triallylmethane dyes. These dyes can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Further, when ultraviolet rays are used as the active energy rays, in order to efficiently perform the curing reaction by ultraviolet rays, the irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere.

As a source of ultraviolet light, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. can be mentioned. Among these, it is preferable to use an LED as the light source because stable illuminance can be obtained over a long period of time.

The wavelength of the active energy ray is preferably in the range of 350 to 410 nm since stable illuminance can be obtained.

The cumulative amount of active energy rays is not particularly limited, but is preferably 50 to 50,000 mJ/cm ² , more preferably 300 to 50,000 mJ/cm ² . It is preferable that the cumulative light amount is within the above range because it is possible to prevent or suppress the occurrence of uncured portions.

Note that the irradiation with the active energy rays may be performed in one step, or may be performed in two or more steps.

The three-dimensional object of the present invention can be produced by a known optical three-dimensional modeling method.

Examples of the optical stereolithography method include a stereolithography (SLA) method, a digital light processing (DLP) method, and an inkjet method.

The stereolithography (SLA) method is a method in which a tank of liquid curable resin composition is irradiated with active energy rays such as laser beams at points, and is cured layer by layer while moving the modeling stage to create three-dimensional modeling. .

The digital light processing (DLP) method is a method in which a bath of a liquid curable resin composition is irradiated with active energy rays from an LED or the like on a surface, and the material is cured layer by layer while moving the modeling stage to create three-dimensional modeling. be.

The inkjet stereolithography method is a method in which micro droplets of a curable resin composition for stereolithography are ejected from a nozzle so as to draw a predetermined shape pattern, and then irradiated with ultraviolet rays to form a cured thin film. .

Among these optical three-dimensional modeling methods, the DLP method is preferred because it enables high-speed modeling using surfaces.

The DLP stereolithography method is not particularly limited as long as it uses a DLP stereolithography system, but the modeling conditions are as follows: The lamination pitch is in the range of 0.01 to 0.2 mm, the irradiation wavelength is in the range of 350 to 410 nm, the light intensity is in the range of 0.5 to 50 mW/cm ² , and the cumulative light amount per layer is 1 -100 mJ/cm ² , and in particular, the stacking pitch of stereolithography should be in the range of 0.02 to 0.1 mm because it improves the precision of three-dimensionally modeled objects. It is preferable that the irradiation wavelength is in the range of 380 to 410 nm, the light intensity is in the range of 5 to 15 mW/cm ² , and the cumulative amount of light per layer is in the range of 5 to 15 mJ/cm ² .

The three-dimensional structure of the present invention can be used for, for example, automobile parts, aerospace-related parts, electrical and electronic parts, building materials, interiors, jewelry, medical materials, etc., and because it has excellent biological safety, it can be used as a medical material. It can be suitably used in the following applications.

Examples of the medical materials include hard resin materials for dental treatments such as surgical guides, temporary teeth, bridges, and orthodontic appliances.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

In the present invention, the amount of potassium permanganate reducing substance is calculated by the following method.

[Amount of potassium permanganate reducing substance]
The cured products of 20 mm x 15 mm x 2 mm obtained in the following Examples and Comparative Examples were used as test pieces, and the 6 test pieces (4 g) were immersed in 20 ml of distilled water and placed in a constant temperature dryer at 70 ° C. After extraction for 24 hours, the mixture was allowed to cool to room temperature, and this extract was used as a test solution. Separately, 20 ml of distilled water was placed in a constant temperature dryer at 70° C., extracted for 24 hours, and then allowed to cool to room temperature, which was used as a blank test solution. Put 20 ml of each of the test liquid and the blank test liquid into a stoppered flask, add 20.0 ml of a 0.002 mol/l potassium permanganate aqueous solution and 1.0 ml of a 0.01 mol/l sulfuric acid aqueous solution, boil for 3 minutes, and cool. After that, 0.1 g of potassium iodide was added, the container was sealed tightly, the mixture was shaken well and left for 10 minutes, followed by titration with a 0.01 mol/l aqueous sodium thiosulfate solution (indicator: 5 drops of starch solution). The difference in consumption of potassium permanganate between the test solution and the blank test solution (test solution - blank test solution) was defined as the amount of potassium permanganate reducing substance.

(Example 1: Preparation of cured product (1))
In a container equipped with a stirrer, 100 parts by mass of bisphenol A ethylene oxide modified (4 mole addition) dimethacrylate (hereinafter abbreviated as "(meth)acrylate compound (C)") and 2,4,6-trimethylbenzoyl. 2 parts by mass of diphenylphosphine oxide ("Omnirad TPO" manufactured by IGM, hereinafter abbreviated as "photopolymerization initiator (A)") was blended, and stirred and mixed for 1 hour while controlling the liquid temperature to 60°C until uniform. A curable resin composition (1) was obtained by dissolving the resin composition. Next, a cured product (1') was created from the obtained curable resin composition (1) using a digital light processing (DLP) stereolithography system ("DLP Printer VITTRO" manufactured by 3 Delight). At this time, the lamination pitch for stereolithography was 0.05 to 0.1 mm, the irradiation wavelength was 380 to 390 nm, and the light irradiation time was 2 to 6 seconds per layer. After the cured product (1') is ultrasonically cleaned in ethanol, it is post-cured by irradiating light for 10 minutes each from the front and back surfaces of the three-dimensional structure using a post-curing device equipped with an LED light source. The desired cured product (1) was obtained.

(Examples 2 to 8: Production of cured products (2) to (8))
Cured products (2) to (8) were prepared in the same manner as in Example 1, except that the (meth)acrylate compound and photopolymerization initiator used in Example 1 were changed to the composition and blending amount shown in Table 1. Obtained.

(Comparative Examples 1 to 4: Production of cured products (C1) to (C4))
Cured products (C1) to (C4) were prepared in the same manner as in Example 1, except that the (meth)acrylate compound and photopolymerization initiator used in Example 1 were changed to the composition and blending amount shown in Table 1. Obtained.

The following evaluations were performed using the cured products obtained in Examples 1 to 8 and Comparative Examples 1 to 4 above.

[Biological safety evaluation method]
Biological safety was evaluated based on the amount of potassium permanganate reducing substance according to the following criteria.
○: The amount of potassium permanganate reducing substance is 10 ml or less ×: The amount of potassium permanganate reducing substance exceeds 10 ml

Table 1 shows the compositions and evaluation results of the cured products (1) to (8) produced in Examples 1 to 8 and the cured products (C1) to (C4) produced in Comparative Examples 1 to 4.

In Table 1, "(meth)acrylate compound (A)" indicates bisphenol A epoxy dimethacrylate ("Miramer PE250" manufactured by Miwon Specialty Chemical).

In Table 1, "(meth)acrylate compound (B)" indicates bisphenol A ethylene oxide modified (10 mole addition) dimethacrylate ("Miramer M2101" manufactured by Miwon Specialty Chemical).

In Table 1, "(meth)acrylate compound (C)" indicates bisphenol A ethylene oxide modified (4 mole addition) dimethacrylate ("Miramer M241" manufactured by Miwon Specialty Chemical).

In Table 1, "(meth)acrylate compound ( E )" indicates tricyclodecane dimethanol diacrylate ("Miramer M262" manufactured by Miwon Specialty Chemical).

In Table 1, "(meth)acrylate compound ( F )" indicates neopentyl glycol dimethacrylate ("Miramer M213" manufactured by Miwon Specialty Chemical).

In Table 1, "(meth)acrylate compound ( G )" indicates phenoxyethyl methacrylate ("Miramer M141" manufactured by Miwon Specialty Chemical).

In Table 1, "photopolymerization initiator (A)" indicates 2,4,6-trimethylbenzoylphosphine oxide ("Omnirad TPO-H" manufactured by IGM Resins).

In Table 1, "photopolymerization initiator (B)" indicates bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide ("Omnirad 819" manufactured by IGM Resins).

In Table 1, "photopolymerization initiator (C)" indicates 2,2-dimethoxy-2-phenylacetophenone ("Omnirad 651" manufactured by IGM Resins).

Claims (10)

A medical three-dimensional structure that is a curing reaction product of a curable resin composition containing a photopolymerization initiator,
The curable resin composition contains one or more compounds having at least one polymerizable unsaturated bond in one molecule,
Potassium permanganate when titrating with 0.019 mol/l potassium permanganate solution using the extract obtained by adding 20 ml of ion-exchanged water to 4 g of the medical three-dimensional structure and extracting at 70°C for 24 hours. The amount of reducing substance is 10 ml or less,
At least one of the one or more types of compounds having at least one polymerizable unsaturated bond in one molecule is a (meth)acrylate compound (a1) represented by the following structural formula (1),
The content of the (meth)acrylate compound (a1) is 60 to 100% by mass when the total mass of one or more compounds having at least one polymerizable unsaturated bond in one molecule is 100% by mass. A three-dimensional medical object characterized by :

[In formula (1), R ¹ is each independently a hydrogen atom or a methyl group, R ² is each independently a hydrogen atom or a methyl group, and R ³ is each independently a hydrogen atom or a methyl group. It is a methyl group. X is -O-, -SO ₂ -, a structure represented by the following structural formula (2), or a structure represented by the following structural formula (3), and m is 0 or an integer from 1 to 4 . , n is 0 or an integer from 1 to 4 , and m+n is 4 . ]

[In formula (2), R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ]

The medical three-dimensional structure according to claim 1, wherein the (meth)acrylate compound (a1) is bisphenol A ethylene oxide-modified dimethacrylate. The medical three-dimensional structure according to claim 1, wherein the photopolymerization initiator is a phosphorus compound. The medical three-dimensional structure according to claim 3 , wherein the photopolymerization initiator is 2,4,6-trimethylbenzoylphosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. The medical three-dimensional structure according to claim 1, wherein the content of the photopolymerization initiator is 4.5% by mass or less in the curable resin composition. The medical three-dimensional structure according to any one of claims 1 to 5 , wherein the curing condition is irradiation with active energy rays from an LED light source. The medical three-dimensional structure according to claim 6 , wherein the wavelength of the active energy ray is in the range of 350 to 410 nm. A three-dimensional medical object comprising the medical three-dimensional object according to any one of claims 1 to 7 . 9. The method for producing a three-dimensional object according to claim 8 , wherein the three-dimensional object is formed by a digital light processing method (DLP method). A method for manufacturing a medical three-dimensional object obtained using a digital light processing method (DLP method) stereolithography system, comprising:
The medical three-dimensional structure is obtained by subjecting a curable resin composition containing a photopolymerization initiator to a curing reaction,
The curable resin composition contains one or more compounds having at least one polymerizable unsaturated bond in one molecule,
Potassium permanganate when titrating with 0.019 mol/l potassium permanganate solution using the extract obtained by adding 20 ml of ion-exchanged water to 4 g of the medical three-dimensional structure and extracting at 70°C for 24 hours. The amount of reducing substance is 10 ml or less,
At least one of the one or more types of compounds having at least one polymerizable unsaturated bond in one molecule is a (meth)acrylate compound (a1) represented by the following structural formula (1),

[In formula (1), R ¹ is each independently a hydrogen atom or a methyl group, R ² is each independently a hydrogen atom or a methyl group, and R ³ is each independently a hydrogen atom or a methyl group. It is a methyl group. X is -O-, -SO ₂ -, a structure represented by the following structural formula (2), or a structure represented by the following structural formula (3), and m is 0 or an integer from 1 to 4 . , n is 0 or an integer from 1 to 4 , and m+n is 4 . ]

[In formula (2), R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ]

The content of the (meth)acrylate compound (a1) is 60 to 100% by mass when the total mass of one or more compounds having at least one polymerizable unsaturated bond in one molecule is 100% by mass. and
The modeling conditions of the stereolithography system are that the stacking pitch for stereolithography is in the range of 0.01 to 0.2 mm, the irradiation wavelength is in the range of 350 to 410 nm, and the light intensity is 0.5 to 50 mW/ ^cm2 . A method for producing a three-dimensional medical object, characterized in that the integrated light amount per layer is in the range of 1 to 100 mJ/cm ² .