JP2017081153A - Material set for stereo molding, manufacturing method of stereo molded article, manufacturing method of dental prosthetic, and manufacturing apparatus for stereo molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material set for stereo molding which enables simple and efficient manufacture of a stereo molded article having a complex three-dimensional shape, and provides high strength immediately after molding.SOLUTION: A material set for stereo molding includes: at least one of organic particles and inorganic particles; a material A for stereo molding that contains a polymerization initiator A; and a polymerizable material B containing a polymerizable compound B. Preferable are: an embodiment where the material A for stereo molding is in a liquid state or a powder state and an embodiment where the organic particles includes at least one selected from polymethyl methacrylate, polycarbonate, polyester, polyamide, and polyether ether ketone.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a three-dimensional modeling material set, a manufacturing method of a three-dimensional modeling object, a manufacturing method of a dental prosthesis, and a manufacturing apparatus of a three-dimensional modeling object.

  Conventionally, dental prostheses (artificial teeth) have been made and used from metal materials such as cobalt chrome alloys, ceramic materials such as zirconia, and organic materials such as hybrid resins combining the ceramic materials and resins. .

  An artificial tooth using a material containing a crosslinking agent, a reaction accelerator and the like in the organic material can be expected to obtain much higher strength than an artificial tooth containing a polymethyl methacrylate single material. High strength can also be expected by using an organic material such as a hybrid resin in which the resin and a filler such as zirconia or glass are combined.

  However, when a resin is used as a main component in an artificial tooth, the resin may be thermally decomposed, so that there is a problem that it cannot be sintered with a normal laser and cannot be layered. In addition, there is a problem that color adjustment is impossible with a laser.

  Then, the manufacturing method of the three-dimensional structure which piles up a powder layer, adding a binder using the inkjet method is proposed (for example, refer patent document 1).

  An object of the present invention is to provide a three-dimensional modeling material set that can easily and efficiently manufacture a three-dimensional model having a complicated three-dimensional shape, and that can obtain high strength immediately after modeling.

  The three-dimensional modeling material set of the present invention as a means for solving the above-described problems is a three-dimensional modeling material A including at least one of organic particles and inorganic particles, and a polymerization initiator A, and a three-dimensional modeling material B. And a modeling material B.

  According to the present invention, it is possible to provide a three-dimensional modeling material set that can easily and efficiently manufacture a three-dimensional object having a complicated three-dimensional shape and obtain high strength immediately after modeling.

FIG. 1 is a schematic diagram illustrating an example of a manufacturing apparatus for a three-dimensional structure according to the present invention. FIG. 2 is a schematic diagram illustrating another example of the manufacturing apparatus for a three-dimensional structure according to the present invention.

(3D modeling material set)
The three-dimensional modeling material set of the present invention (sometimes referred to as a “three-dimensional modeling material set”) includes at least one of organic particles and inorganic particles, and a three-dimensional modeling material A including a polymerization initiator A (“layer modeling material”). A ”) and three-dimensional modeling material B containing polymerizable compound B (sometimes also referred to as“ laminated modeling material B ”), and other materials as necessary. Have.
In the three-dimensional structure material set of the present invention, when the conventional method for producing a three-dimensional structure is used, the binder to be used does not react immediately or does not dissolve, so that the three-dimensional structure is finished after the additive manufacturing is finished. It is based on the knowledge that when a binder (resin) is used, the binder cannot be removed because it does not sinter and remains as an impurity until the end. is there.

<Three-Dimensional Modeling Material A (Layered Modeling Material A)>
The three-dimensional modeling material A (layered modeling material A) includes at least one of organic particles and inorganic particles, and a polymerization initiator A, and further includes other materials as necessary. The three-dimensional modeling material A may be in a liquid state or a powder state, and can be appropriately selected as necessary.
When the three-dimensional modeling material A is in a liquid state, it is preferable to further include a polymerizable compound A.
The “liquid state” means that the state of the material for three-dimensional modeling at 25 ° C. is liquid or fluid, and is a term including, for example, a slurry.

<< Organic particles >>
The material of the organic particles is not particularly limited and may be appropriately selected depending on the purpose. For example, polymethyl methacrylate (hereinafter sometimes referred to as “PMMA”), polycarbonate (hereinafter also referred to as “PC”). A polyamide such as polyamide 12 (hereinafter also referred to as “PA12”), a polyether ether ketone (hereinafter also referred to as “PEEK”). May be included). The weight average molecular weight of each polymer can be handled from high to low as required. These may be used individually by 1 type and may use 2 or more types together. The polyamide 12 is a polyamide obtained by ring-opening polycondensation of lauryl lactam and has 12 carbon atoms.

The weight average molecular weight (Mw) of the organic particles is preferably 100,000 or more and 1,500,000 or less. When the weight average molecular weight is 100,000 or more, the composition in which organic particles swell and become wrinkled can be prevented from becoming too flexible, the shaping can be performed well, and the amount is 1,500,000 or less. The organic particles swell faster and the molding speed can be improved.
The weight average molecular weight can be calculated based on the molecular weight distribution of the isolated organic particles obtained by, for example, gel permeation chromatography (GPC).

The volume average particle diameter (Dv) of the organic particles is preferably less than 1 μm when the three-dimensional modeling material A is in a liquid (dispersion) state. When the volume average particle diameter (Dv) in the liquid state is less than 1 μm, the dispersed organic particles are difficult to settle, and the formed slurry layer can be made uniform. On the other hand, when the three-dimensional modeling material A is in a powder state, it is preferably 1 μm or more and 100 μm or less. When the volume average particle diameter in the powder state is 1 μm or more, the swelling speed can be slowed, and the reaction can be prevented from being completed without the solid modeling material B soaking into the lower layer. Moreover, fluidity | liquidity can be improved irrespective of the kind of organic particle, powder conveyance is favorable, and modeling precision can be improved as it is 100 micrometers or less.
The volume average particle size can be measured according to a known method using a known particle size measuring device such as Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (manufactured by Sysmex Corporation). .

  As content of the said organic particle, when the said three-dimensional modeling material A is a liquid state, 20 mass% or more and 70 mass% or less are preferable with respect to the three-dimensional modeling material A whole quantity, and 30 mass% or more and 50 mass% are preferable. The following is more preferable. On the other hand, when the said three-dimensional modeling material A is a powder state, 80 to 99 mass% is preferable with respect to the three-dimensional modeling material A whole quantity, and 90 to 99 mass% is more preferable.

<< Inorganic particles >>
There is no restriction | limiting in particular as a material of the said inorganic particle, According to the objective, it can select suitably, For example, a zirconia, an alumina, a silica, a silicate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the silicate include lithium disilicate.
When zirconia is used as the inorganic particles, yttria as a sintering aid, alumina as an impurity, or the like may be contained.

  As content of the said zirconia, 90 mass% or more is preferable with respect to the said inorganic particle whole quantity, and 94 mass% or more is more preferable. When the content of the zirconia is 90% by mass or more, the relative amount of impurities decreases, so that the mechanical strength is excellent and discoloration hardly occurs.

  The content of the yttria is preferably 2% by mass to 6% by mass, and more preferably 3% by mass to 5% by mass with respect to the total amount of the inorganic particles. When the yttria content is in the range of 2% by mass or more and 6% by mass or less, the function as a sintering aid is sufficiently exhibited, and cracks are hardly generated during firing.

  The content of alumina as the impurity is preferably 3% by mass or less, and more preferably 1% by mass or less, based on the total amount of the inorganic particles. When the content of the alumina is 3% by mass or less, the function as a sintering aid is good, and the color is hardly affected.

  As the inorganic particles, commercially available products may be used. As the commercially available products, trade names: 3YZ-E (manufactured by Tosoh Corporation) as zirconia, trade names: AHP200 (manufactured by Nippon Light Metal Co., Ltd.) as alumina, silica As trade name: H201 (manufactured by Asahi Glass Co., Ltd.).

  The contents of zirconia, yttria, and alumina in the inorganic particles can be measured, for example, by ICP emission spectroscopy.

The volume average particle diameter (Dv) of the inorganic particles is preferably less than 1 μm when the three-dimensional modeling material A is in a liquid (dispersion) state. When the volume average particle diameter (Dv) in the liquid state is less than 1 μm, the dispersed inorganic particles are difficult to settle, and the formed slurry layer can be made uniform. On the other hand, when the three-dimensional modeling material A is in a powder state, it is preferably 1 μm or more and 100 μm or less. When the volume average particle size in the powder state is 1 μm or more, fluidity can be improved, powder conveyance is improved, and when it is 100 μm or less, modeling accuracy can be improved.
The volume average particle size can be measured according to a known method using a known particle size measuring device such as Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (manufactured by Sysmex Corporation). .

  The method for producing the inorganic particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a thermal decomposition method, a coprecipitation method, a hydrolysis method, a method of synthesizing from an aqueous metal salt solution of zirconia or yttria. Etc. Among these, the method by a thermal decomposition method or a coprecipitation method is preferable.

In the thermal decomposition method, zirconium oxychloride and a yttrium chloride aqueous solution are mixed in a predetermined amount, and sodium chloride (or potassium chloride) is added in an amount of 0.1% by mass to 1% by mass with respect to the total amount of zirconium oxychloride, Mix. This mixture is subjected to instantaneous drying such as spray drying to obtain a dry powder.
The instantaneous drying is a technique that can be dried within 10 seconds, and the drying temperature is preferably performed in heated air of 200 ° C. or higher.
Next, the calcined oxide powder is obtained by thermally decomposing the dry powder in air at a temperature of 800 ° C. or more and 1,200 ° C. or less. The calcined oxide powder is pulverized by a wet pulverization method so that the pulverized diameter is 2 μm or less, and washed with water. There is no restriction | limiting in particular as the method of the said water washing, Although it can select suitably according to the objective, The continuous washing filtration method which uses a membrane filter is preferable.
By the water washing, the water is sufficiently washed so that the sodium (or potassium) concentration in the inorganic particles is in the range of 10 ppm or more and 100 ppm or less as an amount converted to oxide. By drying the slurry after washing with water, inorganic particles (zirconia powder) are obtained.

  In the coprecipitation method, zirconium oxychloride and an yttrium chloride aqueous solution are mixed. Here, in order to form a metal complex so that the pH at which each hydrate from zirconium oxychloride and yttrium chloride precipitates is kept constant, the molar ratio of sodium sulfate (or potassium sulfate) to zirconia is preferably 0. .3 to 0.7 and add at a temperature of 50 ° C. to 100 ° C. for several hours or more. An alkaline aqueous solution such as sodium hydroxide or ammonia is added to this mixed solution with stirring, and the pH of the aqueous solution is adjusted to 8 or more and 10 or less. The obtained coprecipitated hydrate particles are thoroughly washed with water, and it is confirmed that sodium (or potassium) when converted to an oxide is in the range of 10 ppm to 100 ppm. Hydrated fine particles after water washing are dehydrated and dried, and calcined in air at a temperature of 800 ° C. or higher and 1,200 ° C. or lower to obtain a calcined oxide powder. The obtained oxide calcined powder is wet-pulverized to 2 μm or less and dried to obtain inorganic particles (zirconia powder).

  As content of the said inorganic particle, when the said three-dimensional modeling material A is a liquid state, 20 mass% or more and 70 mass% or less are preferable with respect to the said three-dimensional modeling material A whole quantity, 30 to 50 mass% is preferable. % Or less is more preferable. On the other hand, when the said three-dimensional modeling material A is a powder state, 50 mass% or more and 99 mass% or less are preferable with respect to the three-dimensional modeling material A whole quantity, and 80 mass% or more and 95 mass% or less are more preferable.

<< Polymerization initiator A >>
Examples of the polymerization initiator A include peroxides and tertiary amines.
When the three-dimensional modeling material A contains the peroxide, the tertiary amine is preferably contained in the three-dimensional modeling material B. By including the peroxide and the tertiary amine separately in the three-dimensional modeling material A and the three-dimensional modeling material B, the three-dimensional modeling material A and the three-dimensional modeling material B are mixed. In this case, a radical reaction is initiated, and a compound of the polymerized polymerizable compound A and at least one of the organic particles and the inorganic particles is obtained. At this time, external energy such as light and heat is not required, and the compound can be obtained immediately after mixing the three-dimensional modeling material A and the three-dimensional modeling material B. Therefore, a three-dimensional model can be obtained simply and efficiently. It is advantageous in that it can.

  Examples of the peroxide include aromatic diacyl peroxides and peroxyesters such as perbenzoic acid esters. Specifically, benzoyl peroxide (BPO), 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl Examples include -2,5-di (benzoylperoxy) hexane. These may be used individually by 1 type and may use 2 or more types together. Among these, benzoyl peroxide (BPO) is preferable.

There is no restriction | limiting in particular as the addition method of the said peroxide, What is necessary is just to mix uniformly with an organic particle and / or an inorganic particle, or to disperse | distribute in an organic particle and / or an inorganic particle. If the peroxide is solid at room temperature, it may be mixed with organic particles and / or inorganic particles, or dispersed in organic particles and / or inorganic particles, but organic particles and / or inorganic particles When mixed with Henschel, mixing with a Henschel mixer or air blow is preferable. At that time, the material of the apparatus is preferably stainless steel (SUS).
Moreover, when using organic particle | grains, it can synthesize | combine by organic polymerization by emulsion polymerization, and can put it into a masterbatch by putting a suitable quantity of the said peroxide in it. When the peroxide is a liquid at room temperature, it is necessary to make it soak into the organic particles, but by soaking it in an appropriate amount, the deterioration of the fluidity of the powder can be suppressed to prevent the powder from being transported. it can.

  The content of the peroxide is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 1 part by mass or more and 3 parts by mass or less with respect to at least one of 100 parts by mass of the organic particles and inorganic particles. When the content is 1 part by mass or more, the radical reaction is fast, a three-dimensional structure can be obtained at a desired speed, the mechanical strength can be improved, and when the content is 5 parts by mass or less, Residues of lumps can be suppressed, peroxide can be uniformly dispersed in the particles, and generation of plosives and unevenness in strength can be prevented during radical reaction. Moreover, yellowing can be suppressed.

  As content of the said polymerization initiator A, 1 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of said three-dimensional modeling material A, and 1 mass part or more and 3 mass parts or less are more preferable. When the content is 1 part by mass or more, the radical reaction is fast, a three-dimensional structure can be obtained at a desired speed, the mechanical strength can be improved, and when the content is 5 parts by mass or less, Residues of lumps can be suppressed, peroxide can be uniformly dispersed in the particles, and generation of plosives and unevenness in strength can be prevented during radical reaction. Moreover, yellowing can be suppressed.

-Other polymerization initiators-
Examples of other polymerization initiators include room temperature polymerization initiators in combination with the peroxide.
Examples of the room temperature polymerization initiator include pyrimidinetrione derivatives, organometallic compounds, and organic halogen compounds. Among these, when the three-dimensional modeling material A contains a pyrimidinetrione derivative and an organometallic compound, the three-dimensional modeling material B preferably contains an organic halogen compound, and the three-dimensional modeling material A contains an organic halogen compound. When it contains, it is preferable to make the said three-dimensional modeling material B contain a pyrimidinetrione derivative and an organometallic compound.

  Examples of the pyrimidinetrione derivative include 1-cyclohexyl-5-ethylpyrimidinetrione, 1-benzyl-5-phenylpyrimidinetrione, 5-butylpyrimidinetrione, 5-phenylpyrimidinetrione, 1,3-dimethylpyrimidinetrione, 5 -Ethylpyrimidinetrione and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the organometallic compound include copper acetylacetone, copper 4-cyclohexylbutyrate, cupric acetate, copper oleate, manganese acetylacetone, manganese naphthenate, manganese octylate, acetylacetone cobalt, cobalt naphthenate, lithium acetylacetone, and lithium acetate. Zinc acetylacetone, zinc naphthenate, acetylacetone nickel, nickel acetate, acetylacetone aluminum, acetylacetone calcium, acetylacetone chromium, acetylacetone iron, sodium naphthenate, rare earth octoate, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the organic halogen compound include dilauryldimethylammonium chloride, lauryldimethylammonium chloride, tetra-n-butylammonium chloride, trioctylmethylammonium chloride, benzyldimethylcetylammonium chloride, and benzyldimethylstearylammonium chloride. These may be used individually by 1 type and may use 2 or more types together.

<< Polymerizable Compound A >>
The polymerizable compound A is preferably contained in the three-dimensional modeling material A when the three-dimensional modeling material A is in a liquid state.
The polymerizable compound A is not particularly limited as long as it has a certain degree of viscosity, and can be appropriately selected according to the purpose. Examples thereof include a polymerizable compound having a vinyl group.
Examples of the polymerizable compound having a vinyl group include monofunctional polymerizable compounds and polyfunctional polymerizable compounds. These may be used individually by 1 type and may use 2 or more types together. Among these, in order to impart a thickening effect, it is preferable to use a monofunctional polymerizable compound and a polyfunctional polymerizable compound in combination. The monofunctional polymerizable compound and the polyfunctional polymerizable compound may be in a mixed state or in an oligomer state chemically bonded to each other.

-Monofunctional polymerizable compound-
Examples of the monofunctional polymerizable compound include monofunctional acrylic compounds and monofunctional methacrylic compounds. These may be used individually by 1 type and may use 2 or more types together. Among these, monofunctional methacrylic compounds are preferable, and monofunctional methacrylic compounds having a methyl methacrylate skeleton are more preferable.

  Examples of the monofunctional methacrylic compound having a methyl methacrylate skeleton include methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butoxyethyl methacrylate, and 2-ethylhexyl methacrylate. Alkyl methacrylate; Hydroxyalkyl methacrylate (HAMA) such as 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, hydroxypropyl methacrylate; Tetrahydrofurfuryl methacrylate, glycidyl methacrylate , Ethylene glycol methacrylate, 2-methoxyethyl methacrylate Rate include benzyl methacrylate. These may be used individually by 1 type and may use 2 or more types together. Among these, the combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable from the viewpoint of balance of fracture toughness of the prosthesis, and methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) are preferable. Is more preferable.

  The number of carbon atoms in the alkyl chain of the hydroxyalkyl methacrylate (HAMA) is preferably 2 or more and 4 or less. When the carbon number is 2 or more and 4 or less, the mechanical strength can be improved.

  The content of the hydroxyalkyl methacrylate is preferably 10 parts by mass or more and 30 parts by mass or less, and more preferably 15 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the three-dimensional modeling material A. When the content is 10 parts by mass or more, the fracture toughness is high and can be prevented from being broken in the oral cavity. When the content is 30 parts by mass or less, the bending strength can be improved and the oral cavity can be prevented from being broken. it can.

  The content of the monofunctional polymerizable compound is preferably 30 parts by mass or more and 80 parts by mass or less, and more preferably 40 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the three-dimensional modeling material A. When the content is 30 parts by mass or more, the viscosity of the liquid decreases and it becomes easy to spread a liquid layer with a doctor blade or the like, and when it is 80 parts by mass or less, the bending strength can be improved and the oral cavity is damaged. Can be prevented.

-Polyfunctional polymerizable compound-
Examples of the polyfunctional polymerizable compound include polyfunctional acrylic compounds and polyfunctional methacrylic compounds. Among these, a polyfunctional methacrylic compound is preferable, and a polyfunctional methacrylic compound having a methyl methacrylate skeleton is more preferable.

  Examples of the polyfunctional methacrylic compound having a methyl methacrylate skeleton include diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, tetraethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate ( UDMA), bisphenol A diglycidyl methacrylate (Bis-GMA), and the like. These may be used alone or in combination of two or more. Among these, urethane dimethacrylate (UDMA) and bisphenol A diglycidyl methacrylate (Bis-GMA) having high viscosity are preferable, and bisphenol A diglycidyl methacrylate (Bis-GMA) is more preferable.

  The content of at least one of the polyfunctional acrylic compound and the polyfunctional methacrylic compound is preferably 30 parts by mass or more and 80 parts by mass or less, and 40 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the three-dimensional modeling material A. Part or less is more preferable. When the content is 30 parts by mass or more, adjustment with a desired viscosity is possible, and the liquid layer laid by the doctor blade can hardly flow and can stably remain at a desired position. If it exists, the increase in an unreacted component can be suppressed and the damage in the oral cavity by the deterioration of mechanical strength can be prevented.

<< Other ingredients >>
There is no restriction | limiting in particular as said other component, Although it can select suitably according to the objective, For example, a fluidizing agent, a filler, etc. are mentioned. When the three-dimensional modeling material A is in a powder state, it is preferable that the fluidizing agent is included in that the layer or the like by the three-dimensional modeling material A can be easily and efficiently formed, and a cured product obtained when the filler is included. It is preferable in that voids are less likely to be generated.

-Physical properties of 3D modeling material A-
As a viscosity in case the said three-dimensional modeling material A is a liquid state, 50 mPa * s or more and 200 mPa * s or less are preferable in 25 degreeC. When the viscosity is 50 mPa · s or more and 200 mPa · s or less, stable discharge of the three-dimensional modeling material A becomes good, and the dimensional accuracy and mechanical strength of the model can be improved. In addition, the said viscosity can be measured based on JIS-K7117, for example, and it is 25 degreeC using B type rotational viscometer (device name: TVB-10M, Toki Sangyo Co., Ltd. make). Can be measured.

<Three-Dimensional Modeling Material B (Layered Modeling Material B)>
The three-dimensional modeling material B (layered modeling material B) includes a polymerizable compound B, and further includes a polymerization initiator B and other materials as necessary.
The three-dimensional modeling material B is preferably in a liquid state.

<< Polymerizable Compound B >>
There is no restriction | limiting in particular as said polymeric compound B, According to the objective, it can select suitably, For example, the polymeric compound etc. which have a vinyl group are mentioned.
Examples of the polymerizable compound having a vinyl group include a monofunctional polymerizable compound and a polyfunctional polymerizable compound. Among these, it is preferable to use a monofunctional polymerizable compound and a polyfunctional polymerizable compound in combination. The monofunctional polymerizable compound and the polyfunctional polymerizable compound may be in a mixed state or in an oligomer state chemically bonded to each other.

-Monofunctional polymerizable compound-
Examples of the monofunctional polymerizable compound include monofunctional acrylic compounds and monofunctional methacrylic compounds. Among these, monofunctional methacrylic compounds are preferable, and monofunctional methacrylic compounds having a methyl methacrylate skeleton are more preferable.

  Examples of the monofunctional polymerizable compound include alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butoxyethyl methacrylate, and 2-ethylhexyl methacrylate; 2 -Hydroxyalkyl methacrylate (HAMA) such as hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, hydroxypropyl methacrylate; tetrahydrofurfuryl methacrylate, glycidyl methacrylate, ethylene glycol methacrylate, 2-methoxyethyl methacrylate, benzyl methacrylate, etc. . These may be used individually by 1 type and may use 2 or more types together. Among these, the combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable from the viewpoint of balance of fracture toughness of the prosthesis, and methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) are preferable. Is more preferable.

  The number of carbon atoms in the alkyl chain of the hydroxyalkyl methacrylate (HAMA) is preferably 2 or more and 4 or less. When the carbon number is 2 or more and 4 or less, the mechanical strength can be improved.

  The content of the monofunctional polymerizable compound is preferably 10 parts by mass to 30 parts by mass, and more preferably 15 parts by mass to 25 parts by mass with respect to 100 parts by mass of the three-dimensional modeling material B. When the content is 10 parts by mass or more, the fracture toughness is high and can be prevented from being broken in the oral cavity. When the content is 30 parts by mass or less, the bending strength can be improved and the oral cavity can be prevented from being broken. it can.

  The content of the hydroxyalkyl methacrylate is preferably 10 parts by mass or more and 30 parts by mass or less, and more preferably 15 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the three-dimensional modeling material B. When the content is 10 parts by mass or more, the fracture toughness is high and can be prevented from being broken in the oral cavity. When the content is 30 parts by mass or less, the bending strength can be improved and the oral cavity can be prevented from being broken. it can.

-Polyfunctional polymerizable compound-
Examples of the polyfunctional polymerizable compound include polyfunctional acrylic compounds and polyfunctional methacrylic compounds. Among these, a polyfunctional methacrylic compound is preferable, and a polyfunctional methacrylic compound having a methyl methacrylate skeleton is more preferable.

  Examples of the polyfunctional polymerizable compound include diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, tetraethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), and bisphenol. A diglycidyl methacrylate (Bis-GMA), 2-hydroxy-1,3-dimethacryloxypropane, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, tetraethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), and bisphenol A diglycidyl methacrylate (Bis-GMA) are preferable, and bisphenol A diglycidyl methacrylate (Bis-GMA) is more preferable.

  As content of the said polyfunctional polymerizable compound, 10 mass parts or more and 30 mass parts or less are preferable with respect to 100 mass parts of said three-dimensional modeling material B, and 15 mass parts or more and 25 mass parts or less are more preferable. When the content is 10 parts by mass or more, the mechanical strength can be improved, and damage to the oral cavity can be prevented. When the content is 30 parts by mass or less, an increase in unreacted components can be suppressed, and the mechanical strength is increased. It is possible to prevent breakage in the oral cavity due to the deterioration of.

  The content of at least one of the polyfunctional acrylic compound and the polyfunctional methacrylic compound is preferably 10 parts by mass or more and 30 parts by mass or less, and 15 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of the three-dimensional modeling material B. Part or less is more preferable. When the content is 10 parts by mass or more, the mechanical strength can be improved, and damage to the oral cavity can be prevented. When the content is 30 parts by mass or less, an increase in unreacted components can be suppressed, and the mechanical strength is increased. It is possible to prevent breakage in the oral cavity due to the deterioration of.

<Polymerization initiator B>
As said polymerization initiator B, the thing similar to the said three-dimensional modeling material A can be used.
When the three-dimensional modeling material A contains a peroxide as the polymerization initiator A, the three-dimensional modeling material B preferably contains a tertiary amine.

The tertiary amine preferably has a structure in which an aromatic group is directly substituted with a nitrogen atom, and more preferably has a toluidine skeleton.
Examples of the tertiary amine having a toluidine skeleton include N, N-dimethyl-p-toluidine (DMPT), N, N-diethyl-p-toluidine (DEPT), and N, N-di (β-hydroxyethyl). ) -P-toluidine, N, N-di (β-hydroxypropyl) -p-toluidine and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, N, N-dimethyl-p-toluidine (DMPT) and N, N-diethyl-p-toluidine (DEPT) are preferable, and N, N-dimethyl-p-toluidine (DMPT) is more preferable.

  As content of the said tertiary amine, 1 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of said three-dimensional modeling material B, and 1.5 mass parts or more and 3 mass parts or less are more preferable. When the content is 1 part by mass or more, the radical reaction is fast, and a three-dimensional model can be obtained at a desired rate. When the content is 5 parts by mass or less, yellowing of the three-dimensional model can be suppressed.

  As content of the said polymerization initiator B, 1 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of said three-dimensional modeling material B, and 1.5 mass parts or more and 3 mass parts or less are more preferable. When the content is 1 part by mass or more, the radical reaction is fast, and a three-dimensional model can be obtained at a desired rate. When the content is 5 parts by mass or less, yellowing of the three-dimensional model can be suppressed.

-Other polymerization initiators-
As another polymerization initiator, the same thing as the other polymerization initiator used with the said three-dimensional modeling material A can be used.

<< Other ingredients >>
The other components can be appropriately selected in consideration of various conditions such as the type of means for discharging the three-dimensional modeling material B, the usage frequency, and the content thereof. For example, to a liquid discharge head in an inkjet printer or the like The organic solvent, the viscosity modifier, the pigment, the stabilizer and the like can be mentioned.
Examples of the organic solvent include alcohols such as ethanol, ethers, and ketones. Among these, ethanol is preferable.

-Physical properties of 3D modeling material B-
The viscosity of the three-dimensional modeling material B is preferably 4 mPa · s or more and 20 mPa · s or less, and more preferably 5 mPa · s or more and 8 mPa · s or less at 25 ° C. When the viscosity is 4 mPa · s or more and 20 mPa · s or less, the three-dimensional modeling material B can be stably discharged, and the dimensional accuracy and mechanical strength of the model can be improved. In addition, the said viscosity can be measured based on JIS-K7117, for example, and it is 25 degreeC using B type rotational viscometer (device name: TVB-10M, Toki Sangyo Co., Ltd. make). Can be measured.

  The surface tension of the three-dimensional modeling material B is preferably 50 mN / m or less, and more preferably 30 mN / m or less. When the surface tension is 50 mN / m or less, the three-dimensional modeling material B can be stably discharged, the dimensional accuracy of the modeled article is good, and the mechanical strength is also improved.

(Manufacturing method of three-dimensional structure (layered object), manufacturing apparatus of three-dimensional object (layered object), manufacturing method of dental prosthesis, and manufacturing apparatus of dental prosthesis)
The manufacturing method of the three-dimensional molded item (laminated molded item) of the present invention includes a layer forming step and a material B applying step, and further includes other steps as necessary.
The manufacturing apparatus of the three-dimensional molded item (laminated molded item) used by this invention has a layer formation means and the material B provision means, and also has another means as needed.
The method for producing a dental prosthesis according to the present invention includes a layer formation step and a material B application step, and further includes other steps as necessary.
The apparatus for manufacturing a dental prosthesis includes a layer forming unit and a material B applying unit, and further includes other units as necessary.
The manufacturing method of the three-dimensional modeled object (layered modeled object) of the present invention can be suitably implemented using the manufacturing apparatus for the three-dimensional modeled object (layered modeled object) used in the present invention. The material B applying step can be preferably performed by the material B applying unit, and the other step can be preferably performed by the other unit. it can.
The method for manufacturing a dental prosthesis according to the present invention can be preferably carried out by using the dental prosthesis manufacturing apparatus used in the present invention, and the layer forming step is preferably carried out by the layer forming means. The material B application step can be preferably performed by the material B application unit, and the other steps can be performed preferably by the other unit.

<Layer forming step and layer forming means>
The layer forming step is a step of forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set of the present invention.
The layer forming means is means for forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set of the present invention.

-Formation of 3D modeling material A layer-
There is no restriction | limiting in particular as a method of arrange | positioning the said three-dimensional modeling material A on a support body, Although it can select suitably according to the objective, For example, as a method of arrange | positioning in a thin layer, patent 3607300 gazette A method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in 1), or a method of spreading the three-dimensional modeling material A into a thin layer using a member such as a brush, roller or blade A method of pressing the surface of the three-dimensional modeling material A layer with a pressing member to expand it into a thin layer, a method of using a known material additive manufacturing apparatus, and the like are preferable.

-Support-
The support is not particularly limited as long as the three-dimensional modeling material A can be placed thereon, can be appropriately selected depending on the purpose, and has a table having a placement surface for the three-dimensional modeling material A, Examples thereof include a base plate in the apparatus shown in FIG. 1 of Japanese Utility Model Publication No. 2000-328106. The surface of the support, that is, the mounting surface on which the three-dimensional modeling material A is mounted may be, for example, a smooth surface, a rough surface, or a flat surface. It may be a curved surface.

  In order to place the three-dimensional modeling material A in a thin layer on the support using the counter rotating mechanism (counter roller), the brush or blade, the pressing member, etc., for example, as follows: It can be carried out. That is, for example, it is disposed in an outer frame (sometimes referred to as “mold”, “hollow cylinder”, “tubular structure”, etc.) so as to be movable up and down while sliding on the inner wall of the outer frame. The three-dimensional modeling material A is placed on the support using the counter rotation mechanism (counter roller), the brush, a roller or a blade, the pressing member, and the like. At this time, when using the support that can move up and down in the outer frame, the support is arranged at a position slightly lower than the upper end opening of the outer frame, that is, the three-dimensional modeling The three-dimensional modeling material A is placed on the support body by being positioned below the thickness of the material A layer. As described above, the three-dimensional modeling material A can be placed in a thin layer on the support.

  In addition, when the said three-dimensional modeling material B is made to act with respect to the said three-dimensional modeling material A mounted in the thin layer in this way, hardening will arise. On the thin layer cured product obtained here, in the same manner as described above, the three-dimensional modeling material A is placed on a thin layer, and the three-dimensional modeling material A (layer) placed on the thin layer is placed. On the other hand, when the three-dimensional modeling material B is allowed to act, curing occurs. Curing at this time is not only in the three-dimensional modeling material A (layer) placed on the thin layer, but also with the cured product of the thin layer obtained by curing first, which exists under the material. It also occurs between. As a result, a cured product (three-dimensional model, layered model) having a thickness of about two layers of the three-dimensional material A (layer) placed on the thin layer is obtained.

  Moreover, in order to mount the said three-dimensional modeling material A on a thin layer on the said support body, it can also carry out automatically and simply using the said well-known material lamination modeling apparatus. The material additive manufacturing apparatus generally includes a recoater for stacking the three-dimensional object material A, a movable supply tank for supplying the three-dimensional object material A onto the support, and the three-dimensional object material. A is mounted on a thin layer, and a movable molding tank for laminating is provided. In the material additive manufacturing apparatus, the surface of the supply tank can always be slightly raised from the surface of the molding tank by raising the supply tank, lowering the molding tank, or both. The three-dimensional modeling material A can be arranged in a thin layer from the supply tank side using the recoater, and the three-dimensional modeling material A in a thin layer can be laminated by repeatedly moving the recoater. it can.

  There is no restriction | limiting in particular as thickness of the said three-dimensional model | molding material A layer, Although it can select suitably according to the objective, If the said three-dimensional model | molding material A is a liquid state, for example, it is an average thickness per layer. It is preferably 10 μm or more and 70 μm or less, and more preferably 20 μm or more and 50 μm or less. If the average thickness is 10 μm or more, it does not take an enormous amount of time until a shaped product is obtained, and if it is 70 μm or less, the dimensional system of the shaped product can be improved. On the other hand, if the three-dimensional modeling material A is in a powder state, for example, the average thickness per layer is preferably 10 μm to 200 μm, and more preferably 50 μm to 150 μm. If the average thickness is 10 μm or more, enormous time is not required until a shaped product is obtained, and if it is 200 μm or less, the dimensional accuracy of the shaped product can be improved. The average thickness can be measured according to a known method.

<Material B application step and material B application means>
The material B applying step is a step of applying the three-dimensional modeling material B in the three-dimensional modeling material set of the present invention to the three-dimensional modeling material A layer.
The material B applying means is means for applying the three-dimensional modeling material B in the three-dimensional modeling material set of the present invention to the three-dimensional modeling material A layer.

  The method for applying the three-dimensional modeling material B to the three-dimensional modeling material A layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a dispenser method, a spray method, an inkjet method, or the like. Examples of the liquid ejecting means used are listed below. In the present invention, liquid discharge means used in the ink jet method (which discharges droplets from a plurality of nozzles using a vibration element such as a piezoelectric actuator) can form a complicated three-dimensional shape accurately and efficiently. It is preferable that

<Other processes and other means>
As said other process, a surface protection process, a coating process, etc. are mentioned, for example.
Examples of the other means include surface protection means and painting means.

-Surface protection process and surface protection means-
The said surface protection process is a process of forming a protective layer in the molded article formed in the said B addition process with a liquid. By performing the surface protection step, the surface of the three-dimensional object can be provided with durability or the like that allows the three-dimensional object to be used as it is, for example. Specific examples of the protective layer include a water resistant layer, a weather resistant layer, a light resistant layer, a heat insulating layer, and a glossy layer. Examples of the surface protection means include known surface protection devices such as spray devices and coating devices.

-Painting process and painting means-
The painting step is a step of painting the three-dimensional structure. By performing this coating process, the shaped article can be colored in a desired color.
Examples of the coating means include known coating apparatuses, such as a coating apparatus using a spray, a roller, a brush, and the like.

Here, an example of the manufacturing apparatus of the three-dimensional molded item of this invention is shown in FIG. 1 has a modeling-side material storage tank 1 and a supply-side material storage tank 2, and each of these material storage tanks stores the three-dimensional modeling material A and moves up and down. A possible stage 3 is provided, and a layer made of the three-dimensional modeling material A is formed on the stage.
On the modeling side material storage tank 1, it has the inkjet head 5 which discharges the three-dimensional modeling material B4 toward the three-dimensional modeling material A in the said material storage tank, and also modeling from the supply side material storage tank 2 While supplying the three-dimensional modeling material A to the side material storage tank 1, it also has a leveling mechanism 6 (hereinafter also referred to as a recoater) that levels the surface of the three-dimensional modeling material A layer of the modeling side material storage tank 1.

The three-dimensional material B4 is dropped from the inkjet head 5 onto the three-dimensional material A in the modeling material storage tank 1. At this time, the position where the three-dimensional modeling material B4 is dropped is determined by two-dimensional image data (slice data) obtained by slicing a three-dimensional shape to be finally modeled into a plurality of plane layers.
After the drawing for one layer is completed, the stage 3 of the supply-side material storage tank 2 is raised, and the stage 3 of the modeling-side material storage tank 1 is lowered. The difference 3D modeling material A is moved to the modeling-side material storage tank 1 by the leveling mechanism 6.

Thus, a new three-dimensional material A layer is formed on the surface of the three-dimensional material A layer previously drawn. At this time, the average thickness per layer of the material A layer is about several tens μm to 100 μm.
Drawing based on the slice data of the second layer is further performed on the newly formed three-dimensional material A layer, and this series of processes is repeated to obtain a three-dimensional structure.

In FIG. 2, another example of the manufacturing apparatus of the three-dimensional molded item of this invention is shown. The manufacturing apparatus of the three-dimensional structure in FIG. 2 is the same as that in FIG. 1 in principle, but the supply mechanism of the three-dimensional structure material A is different. That is, the supply-side material storage tank 2 is disposed above the modeling-side material storage tank 1. When the drawing of the first layer is completed, the stage 3 of the modeling-side material storage tank 1 is lowered by a predetermined amount, and the supply-side material storage tank 2 is moved while a predetermined amount of the three-dimensional modeling material A is transferred to the modeling-side material storage tank 1. It is dropped and a new three-dimensional modeling material A layer is formed. Thereafter, the leveling mechanism 6 compresses the three-dimensional modeling material A layer to increase the bulk density and uniformly level the height of the three-dimensional modeling material A layer.
According to the material additive manufacturing apparatus having the configuration shown in FIG. 2, the apparatus can be made compact compared to the configuration of FIG. 1 in which two material storage tanks are arranged in a plane.

(3D objects (layered objects) and dental prostheses)
The said three-dimensional molded item (laminated molded item) is manufactured by the manufacturing method of the said three-dimensional molded item of this invention.
The dental prosthesis is manufactured by the method for manufacturing a dental prosthesis of the present invention.
The three-dimensional structure of the present invention can be suitably used as a dental prosthesis.
Examples of the use of the dental prosthesis include artificial teeth, partial dentures, complete dentures, implants, and construction dentures.

-Bending strength of 3D objects-
The bending strength of the three-dimensional structure is preferably 50 MPa or more, and more preferably 80 MPa or more. When the bending strength is 50 MPa or more, sufficient strength can be obtained in the three-dimensional structure. The bending strength can be measured by a three-point bending strength test based on JIS-T-6501 using a desktop precision universal testing machine (device name: AUTOGRAPH-AGS-J, manufactured by Shimadzu Corporation).

-Flexural modulus of 3D objects-
As a bending elastic modulus of the said three-dimensional molded item, 1.5 GPa or more is preferable and 2.0 GPa or more is more preferable. When the bending elastic modulus is 1.5 GPa or more, sufficient strength can be obtained in the three-dimensional structure. The bending strength can be measured by a three-point bending strength test based on JIS-T-6501 using a desktop precision universal testing machine (device name: AUTOGRAPH-AGS-J, manufactured by Shimadzu Corporation).

-Vickers hardness of 3D objects-
The Vickers hardness of the three-dimensional model is preferably 10HV0.2 or more, and more preferably 18HV0.2. When the Vickers hardness is 10HV0.2 or more, sufficient hardness can be obtained in the three-dimensional structure. The Vickers hardness can be measured in accordance with JIS-T-6501 using a Vickers hardness meter (device name: FV-800, manufactured by Futuretec Co., Ltd.). The Vickers hardness is a value when measured with a test force of 0.2 kg.

-Content of residual monomer in three-dimensional model-
The content of the residual monomer in the three-dimensional structure is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less with respect to the total amount of the three-dimensional model. When the content is 10% by mass or less, impurities contained in the three-dimensional structure can be reduced, and the strength and dimensional accuracy of the three-dimensional structure can be improved. The content of the residual monomer in the three-dimensional structure can be measured according to JIS-T6501 using HPLC (device name: LC2010, manufactured by Shimadzu Corporation).
In the present invention, compared with the layered object obtained by the conventional additive manufacturing method, the residual monomer in the obtained three-dimensional object cannot be reduced to zero because it is cured for each layer. it can.

  By the manufacturing method and the manufacturing apparatus of the above three-dimensional modeled object, a three-dimensional modeled object having a complicated three-dimensional shape mainly composed of resin can be modeled simply and efficiently, and a modeled object that can express high strength immediately after modeling. Can be obtained. The three-dimensional model obtained in this way has sufficient strength, excellent dimensional accuracy, and can reproduce fine irregularities, curved surfaces, etc., so it has excellent aesthetic appearance, high quality, and is suitable for various uses. be able to.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  Moreover, the volume average particle diameter (Dv) of the organic particles and the inorganic particles in the three-dimensional modeling material A, the viscosity of the three-dimensional modeling material A and the three-dimensional modeling material B, and the content of the residual monomer of the three-dimensional modeling object are as follows. I asked for it.

-Volume average particle diameter (Dv) of organic particles and inorganic particles in three-dimensional modeling material A-
Using Coulter Multisizer III (manufactured by Coulter Counter) as a measuring device, an interface for outputting the number distribution and volume distribution (manufactured by Nikkaki Co., Ltd.) and a personal computer are connected. 1 mass% NaCl aqueous solution was prepared using it. As a measuring method, a surfactant (alkylbenzene sulfonate) is added in an amount of 0.1 mL to 5 mL as a dispersing agent in a 1% by mass NaCl aqueous solution of 100 mL to 150 mL as the electrolytic solution, and 2 mg or more of the solid modeling material A is added. 20 mg or less was added, and dispersion treatment was performed for 1 minute or more and 3 minutes or less with an ultrasonic disperser. Further, 100 mL or more and 200 mL or less of the electrolytic aqueous solution was put into another beaker, and the sample dispersion was added to a predetermined concentration therein, and 50,000 pieces were used with the Coulter Multisizer III as a 100 μm aperture. The average value of the particles was measured. The measurement was performed by dropping the dispersion liquid of the material for three-dimensional modeling A so that the concentration indicated by the apparatus was 8% by mass ± 2% by mass.

-Viscosity of 3D modeling material A and 3D modeling material B-
The viscosities of the three-dimensional modeling material A and the three-dimensional modeling material B were measured at 25 ° C. using a B-type rotational viscometer (device name: TVB-10M, manufactured by Toki Sangyo Co., Ltd.).

-Content of residual monomer in three-dimensional model-
Content of the residual monomer in the said three-dimensional molded item was measured using HPLC (Apparatus name: LC2010, Shimadzu Corporation make).

(Preparation example 1 of material A for three-dimensional modeling)
<Preparation of three-dimensional modeling material A1>
100 parts by mass of polymethyl methacrylate (PMMA, manufactured by Kuraray Co., Ltd.) and 1 part by mass of benzoyl peroxide (BPO, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed by air blow to prepare a three-dimensional modeling material A1 in a powder state.

(Preparation example 2 of material A for three-dimensional modeling)
<Preparation of three-dimensional modeling material A2>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to polycarbonate (PC, manufactured by Mitsubishi Engineering Plastics), the three-dimensional modeling in the powder state Material A2 was prepared.

(Preparation example 3 of material A for three-dimensional modeling)
<Preparation of three-dimensional modeling material A3>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to polyamide 12 (PA12, manufactured by Toray Industries, Inc.), the powdered three-dimensional modeling is used. Material A3 was prepared.

(Preparation example 4 of material A for three-dimensional modeling)
<Preparation of three-dimensional modeling material A4>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to polyester (PES, manufactured by Toray Industries, Inc.), the three-dimensional modeling material in a powder state A4 was prepared.

(Preparation example 5 of material A for three-dimensional modeling)
<Preparation of three-dimensional modeling material A5>
The three-dimensional modeling material A1 is prepared in the same manner as the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to polyether ether ketone (PEEK, manufactured by Victrex). Material A5 was prepared.

(Preparation Example 6 of Three-dimensional Modeling Material A)
<Preparation of three-dimensional modeling material A6>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to zirconia (trade name: 3YZ-E, manufactured by Tosoh Corporation), the powder state 3D modeling material A6 was prepared.

(Preparation example 7 of material for three-dimensional modeling A)
<Preparation of three-dimensional modeling material A7>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to alumina (trade name: AHP200, manufactured by Nippon Light Metal Co., Ltd.), A three-dimensional modeling material A7 was prepared.

(Preparation Example 8 of Three-dimensional Modeling Material A)
<Preparation of three-dimensional modeling material A8>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to silica (trade name: H201, manufactured by Asahi Glass Co., Ltd.) A modeling material A8 was prepared.

(Preparation Example 9 for Three-Dimensional Modeling Material A)
<Preparation of three-dimensional modeling material A9>
In the preparation of the three-dimensional modeling material A1, the powdered three-dimensional modeling material A9 is the same as the preparation of the three-dimensional modeling material A1, except that polymethyl methacrylate (PMMA) is changed to lithium disilicate (prototype). Was prepared.

(Preparation example 10 of three-dimensional modeling material A)
<Preparation of three-dimensional modeling material A10>
In the preparation of the three-dimensional modeling material A1, in the same manner as the preparation of the three-dimensional modeling material A1, except that 1 part by mass of the benzoyl peroxide (BPO) is changed to 5 parts by mass of the benzoyl peroxide (BPO), the solid in the powder state A modeling material A10 was prepared.

(Preparation example 11 of three-dimensional modeling material A)
<Preparation of three-dimensional modeling material A11>
In the preparation of the three-dimensional modeling material A1, a powder three-dimensional modeling material A11 was prepared in the same manner as the preparation of the three-dimensional modeling material A1, except that benzoyl peroxide (BPO) was not included.

(Preparation example 12 of three-dimensional modeling material A)
<Preparation of three-dimensional modeling material A12>
40 parts by mass of polymethyl methacrylate (PMMA, manufactured by Kuraray Co., Ltd.), 5 parts by mass of benzoyl peroxide (BPO, manufactured by Tokyo Chemical Industry Co., Ltd.), and 25 parts by mass of methyl methacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 30 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA, Sigma-Aldrich) was mixed to prepare a three-dimensional modeling material A12 in a liquid state. The viscosity was 113 mPa · s.

(Preparation Example 13 for Three-dimensional Modeling Material A)
<Preparation of three-dimensional modeling material A13>
In the preparation of the three-dimensional modeling material A12, in the same manner as the preparation of the three-dimensional modeling material A12, except that the polymethyl methacrylate is changed to polycarbonate (PC, manufactured by Mitsubishi Engineering Plastics), the three-dimensional modeling material A13 in the liquid state Was prepared. The viscosity was 109 mPa · s.

(Preparation Example 14 for Three-Dimensional Modeling Material A)
<Preparation of three-dimensional modeling material A14>
In the preparation of the three-dimensional modeling material A12, in the same manner as the preparation of the three-dimensional modeling material A12, except that the polymethyl methacrylate was changed to zirconia (trade name: 3YZ-E, manufactured by Tosoh Corporation), the three-dimensional modeling in the liquid state Material A14 was prepared. The viscosity was 112 mPa · s.

  The compositions and contents of the prepared three-dimensional modeling materials A1 to A14 are shown in Table 1 below.

(Preparation example 1 of material for three-dimensional modeling B)
<Preparation of three-dimensional modeling material B1>
As a monofunctional polymerizable compound, 60 parts by mass of methyl methacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.), 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and a polyfunctional polymerizable compound, 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA, manufactured by Sigma Aldrich) and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Chemical Industry Co., Ltd.) as a tertiary amine Were mixed to prepare a three-dimensional modeling material B1.

(Preparation example 2 of the three-dimensional modeling material B)
<Preparation of three-dimensional modeling material B2>
Three-dimensional modeling material B1 was prepared in the same manner as the preparation of three-dimensional modeling material B1, except that 2-hydroxyethyl methacrylate (HEMA) was changed to hydroxypropyl methacrylate (HPMA, manufactured by Tokyo Chemical Industry Co., Ltd.). A modeling material B2 was prepared.

(Preparation Example 3 of Material for Solid Modeling B)
<Preparation of three-dimensional modeling material B3>
Three-dimensional modeling is performed in the same manner as the three-dimensional modeling material B1 except that 2-hydroxyethyl methacrylate (HEMA) is changed to hydroxybutyl methacrylate (HBMA, manufactured by Kyoeisha Chemical Co., Ltd.) in the preparation of the three-dimensional modeling material B1. Material B3 was prepared.

(Preparation example 4 of three-dimensional modeling material B)
<Preparation of three-dimensional modeling material B4>
In the preparation of the three-dimensional modeling material B1, except that 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) was changed to 10 parts by mass of 2-hydroxyethyl methacrylate (HEMA), the same as the preparation of the three-dimensional modeling material B1, A three-dimensional modeling material B4 was prepared.

(Preparation Example 5 of the material for three-dimensional modeling B)
<Preparation of three-dimensional modeling material B5>
In the preparation of the three-dimensional modeling material B1, except that 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) was changed to 30 parts by mass of 2-hydroxyethyl methacrylate (HEMA), the same as the preparation of the three-dimensional modeling material B1, A three-dimensional material B5 was prepared.

(Preparation example 6 of three-dimensional modeling material B)
<Preparation of three-dimensional modeling material B6>
The preparation of the three-dimensional modeling material B1 is the same as the preparation of the three-dimensional modeling material B1, except that bisphenol A diglycidyl methacrylate (Bis-GMA) is changed to tetraethylene glycol dimethacrylate (TEGDMA, manufactured by Kyoeisha Chemical Co., Ltd.). Thus, a three-dimensional modeling material B6 was prepared.

(Preparation example 7 of material for three-dimensional modeling B)
<Preparation of three-dimensional modeling material B7>
Three-dimensional modeling material B1 was prepared in the same manner as the preparation of three-dimensional modeling material B1, except that bisphenol A diglycidyl methacrylate (Bis-GMA) was changed to urethane dimethacrylate (UDMA, manufactured by Sigma-Aldrich). A modeling material B7 was prepared.

(Preparation example 8 of material for three-dimensional modeling B)
<Preparation of three-dimensional modeling material B8>
In preparation of the three-dimensional modeling material B1, except that 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA) was changed to 10 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA), Similarly, the three-dimensional modeling material B8 was prepared.

(Preparation Example 9 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B9>
In preparation of the three-dimensional modeling material B1, except that 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA) was changed to 30 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA), Similarly, the three-dimensional modeling material B9 was prepared.

(Preparation Example 10 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B10>
In preparation of the three-dimensional modeling material B1, N, N-dimethyl-p-toluidine (DMPT) was changed to N.N. Three-dimensional modeling material B10 was prepared in the same manner as the preparation of the three-dimensional modeling material B1, except that it was changed to N-diethyl-p-toluidine (DEPT, manufactured by Tokyo Chemical Industry Co., Ltd.).

(Preparation Example 11 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B11>
3D modeling except that in the preparation of 3D modeling material B1, 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT) was changed to 1 part by mass of N, N-dimethyl-p-toluidine (DMPT). A three-dimensional modeling material B11 was prepared in the same manner as the preparation of the material B1.

(Preparation example 12 of three-dimensional modeling material B)
<Preparation of three-dimensional modeling material B12>
3D modeling except that in the preparation of 3D modeling material B1, 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT) was changed to 5 parts by mass of N, N-dimethyl-p-toluidine (DMPT). A three-dimensional modeling material B12 was prepared in the same manner as the preparation of the material B1.

(Preparation Example 13 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B13>
In the preparation of the three-dimensional modeling material B1, 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) and 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA) and a viscosity of 10 mPa · s were reduced to 2-hydroxyethyl methacrylate (HEMA). ) 3D modeling material B13 was prepared in the same manner as the preparation of the 3D modeling material B1 except that the viscosity was changed to 4 mPa · s at 10 parts by mass and 10 parts by mass of tetraethylene glycol dimethacrylate (TEGDMA). .

(Preparation example 14 of three-dimensional modeling material B)
<Preparation of three-dimensional modeling material B14>
In preparation of the three-dimensional modeling material B1, 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) and 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA), and a viscosity of 10 mPa · s of hydroxybutyl methacrylate (HBMA) 30 Three-dimensional modeling material B14 was prepared in the same manner as the preparation of three-dimensional modeling material B1, except that the viscosity was changed to 20 mPa · s with 30 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA). .

(Preparation Example 15 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B15>
Three-dimensional modeling is performed in the same manner as the three-dimensional modeling material B14 except that N, N-dimethyl-p-toluidine (DMPT) is changed to N-methylethanamine (MEA) in the preparation of the three-dimensional modeling material B14. Material B15 was prepared.

(Preparation Example 16 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B16>
In the preparation of the three-dimensional modeling material B14, a three-dimensional modeling material B16 was prepared in the same manner as the preparation of the three-dimensional modeling material B14, except that hydroxybutyl methacrylate (HBMA) was not included.

(Preparation Example 17 for Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B17>
A three-dimensional material B17 was prepared in the same manner as the three-dimensional material B16 except that bisphenol A diglycidyl methacrylate (Bis-GMA) was not included in the preparation of the three-dimensional material B16.

(Preparation Example 18 of Three-dimensional Modeling Material B)
<Preparation of three-dimensional modeling material B18>
In preparation of three-dimensional modeling material B1, except that 60 parts by mass of methyl methacrylate (MMA), 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 20 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA) were not included. Prepared the three-dimensional modeling material B18 in the same manner as the preparation of the three-dimensional modeling material B1.

  The compositions and contents of the prepared three-dimensional modeling materials B1 to 18 are shown in Table 2 below.

In Table 2, “HAMA” is hydroxyalkyl methacrylate, and the carbon number of the alkyl chain of HAMA means the carbon number of the alkyl chain of “HEMA”, “HPMA”, or “HBMA”.

Example 1
The obtained three-dimensional modeling material A1 and the three-dimensional modeling material B1 were combined to obtain a three-dimensional modeling material set (layered modeling material set) of Example 1. Using the three-dimensional modeling material set, a three-dimensional model 1 was manufactured as follows using a shape printing pattern of size (length 70 mm × width 12 mm).

  (1) First, the three-dimensional object material A1 is transferred from the supply-side material storage tank to the modeling-side material storage tank using the three-dimensional object manufacturing apparatus (Niigata Co., Ltd., powder jig) shown in FIG. Then, a thin layer made of the three-dimensional material A1 having an average thickness of 100 μm was formed on the support.

  (2) Next, on the surface of the thin layer made of the formed three-dimensional material A1, the three-dimensional material B1 is applied (discharged) from a nozzle using an inkjet printer (manufactured by Ricoh Co., Ltd., SG7100). The three-dimensional modeling material A1 was cured.

  (3) Next, the operations of (1) and (2) are repeated until a total average thickness of 3 mm is reached, and the cured thin layer made of the three-dimensional modeling material A1 is sequentially laminated, A model 1 was manufactured. When the excess three-dimensional modeling material A was removed by air blowing from the obtained three-dimensional model 1, there was no loss of shape. The three-dimensional structure 1 was excellent in strength and dimensional accuracy.

  Next, about the obtained three-dimensional molded item 1, bending strength, a bending elastic modulus, Vickers hardness, a cure rate, and dimensional accuracy were evaluated on the following references | standards. The results are shown in Table 3 below.

<Bending strength and flexural modulus>
About the obtained three-dimensional molded object 1, it measured by the three-point bending strength test based on JIS-T-6501 using the desk-top-type precision universal testing machine (device name: AUTOGRAPH-AGS-J, Shimadzu Corporation make). Based on the following evaluation criteria, bending strength and bending elastic modulus were evaluated.
-Bending strength evaluation criteria-
○: Bending strength is 80 MPa or more. Δ: Bending strength is 50 MPa or more and less than 80 MPa. X: Bending strength is less than 50 MPa.
○: Flexural modulus is 2.0 GPa or more Δ: Flexural modulus is 1.5 GPa or more and less than 2.0 GPa ×: Flexural modulus is less than 1.5 GPa

<Vickers hardness>
About the obtained three-dimensional molded item 1, it measured according to JIS-T-6501 with a test force of 0.2 kg using a Vickers hardness meter (apparatus name: FV-800, manufactured by Futuretec Co., Ltd.). Based on the evaluation criteria, Vickers hardness was evaluated.
-Evaluation criteria-
◯: Vickers hardness is 18HV0.2 or more Δ: Vickers hardness is 10HV0.2 or more and less than 18HV0.2 ×: Vickers hardness is less than 10HV0.2

<Curing speed>
The curing rate of the three-dimensional structure 1 was evaluated according to the following criteria.
-Evaluation criteria-
○: The model can be removed by hand even if only 10 seconds have passed since the three-dimensional modeling. Δ: The model can be finally removed by hand after 10 minutes after the three-dimensional modeling. A state where the object is fragile and cannot be removed

<Dimensional accuracy>
The dimensional accuracy of the three-dimensional structure 1 was evaluated according to the following criteria.
-Evaluation criteria-
○: The surface of the obtained three-dimensional structure is smooth and beautiful, and there is no warping. Δ: The surface of the three-dimensional structure obtained is slightly distorted and slightly warped. The surface of the 3D object is distorted and warped severely

(Examples 2-26 and Comparative Examples 1-2)
<Production of 3D modeling material set>
In Example 1, except that it changed into the combination of the three-dimensional modeling material A and the three-dimensional modeling material B as shown in Table 3 below, in the same manner as in Example 1, each three-dimensional modeled product (laminated modeled product) was used. Prepared and evaluated. The results are shown in Table 3 below. In addition, Comparative Examples 1-2 could not be modeled.

(Example 27)
The obtained three-dimensional modeling material A12 and the three-dimensional modeling material B1 were combined to obtain a three-dimensional modeling material set (layered modeling material set) of Example 27.
In Example 1, except that the modeling process (1) was changed to the following (1 ′), each three-dimensional modeled object (laminated modeled object) was produced and evaluated in the same manner as Example 1. The results are shown in Table 3 below.

  (1 ') First, using the manufacturing apparatus of the three-dimensional structure shown in FIG. 2, the three-dimensional material A12 is dropped from the supply-side material storage tank to the modeling-side material storage tank, and the average thickness is formed on the support. Formed a thin layer made of a three-dimensional modeling material A1 having a thickness of 100 μm.

(Examples 28 to 29)
In Example 27, except that it changed into the combination of the three-dimensional modeling material A and the three-dimensional modeling material B as shown in Table 3 below, in the same manner as in Example 27, each three-dimensional modeled object (laminated modeled object) was changed. Prepared and evaluated. The results are shown in Table 3 below.

In Table 3, the values in parentheses beside the evaluation are values of bending strength, bending elastic modulus, and Vickers hardness, respectively.

As an aspect of this invention, it is as follows, for example.
<1> Solid modeling material A containing at least one of organic particles and inorganic particles, and a polymerization initiator A;
It is a three-dimensional modeling material set characterized by having a three-dimensional modeling material B containing a polymerizable compound B.
<2> The three-dimensional modeling material set according to <1>, wherein the organic particles are at least one selected from polymethyl methacrylate, polycarbonate, polyester, polyamide, and polyether ether ketone.
<3> The three-dimensional modeling material set according to any one of <1> to <2>, wherein the inorganic particles are at least one selected from zirconia, alumina, and silicate.
<4> The three-dimensional modeling material set according to any one of <1> to <3>, wherein the polymerization initiator A is a peroxide.
<5> When the three-dimensional modeling material A is in a liquid state, the volume average particle size of at least one of the organic particles and the inorganic particles is less than 1 μm,
When the three-dimensional modeling material A is in a powder state, the three-dimensional modeling material according to any one of <1> to <4>, wherein the volume average particle diameter of at least one of the organic particles and the inorganic particles is 1 μm or more. Is a set.
<6> The three-dimensional modeling material set according to any one of <1> to <5>, wherein the three-dimensional modeling material A further includes a polymerizable compound A.
<7> The three-dimensional modeling material set according to any one of <1> to <6>, wherein the three-dimensional modeling material A and the three-dimensional modeling material B are both in a liquid state.
<8> The three-dimensional modeling material set according to any one of <1> to <6>, wherein the three-dimensional modeling material A is in a powder state and the three-dimensional modeling material B is in a liquid state.
<9> The three-dimensional modeling material set according to any one of <1> to <8>, wherein the three-dimensional modeling material B further includes a tertiary amine as the polymerization initiator B.
<10> The three-dimensional modeling material set according to any one of <6> to <9>, including a monofunctional polymerizable compound and a polyfunctional polymerizable compound as the polymerizable compound A or the polymerizable compound B.
<11> The three-dimensional modeling material set according to <10>, wherein the monofunctional polymerizable compound or the polyfunctional polymerizable compound is at least one of an acrylic compound and a methacrylic compound.
<12> The three-dimensional modeling material set according to any one of <9> to <11>, wherein the tertiary amine has a toluidine skeleton.
<13> A layer forming step of forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set according to any one of <1> to <12>,
An applying step of applying the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of <1> to <12> to a predetermined region of the three-dimensional modeling material A layer;
Is a method for producing a three-dimensional modeled object characterized by repeating a plurality of times.
<14> A layer forming step of forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set according to any one of <1> to <12>,
An applying step of applying the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of <1> to <12> to a predetermined region of the three-dimensional modeling material A layer;
Is a method for producing a dental prosthesis, characterized in that it is repeated a plurality of times.
<15> Layer forming means for forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set according to any one of <1> to <12>,
An applying unit that applies the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of <1> to <12> to a predetermined region of the three-dimensional modeling material A layer;
It is the manufacturing apparatus of the three-dimensional molded item characterized by having.

  The three-dimensional structure material set according to any one of <1> to <12>, the method for producing a three-dimensional structure according to <13>, the method for producing a dental prosthesis according to <14>, and The manufacturing apparatus of the three-dimensional molded item as described in <15> can solve the said various problems in the past, and can achieve the objective of the said this invention.

JP 2004-330743 A

      4 3D modeling material B

Claims (15)

Three-dimensional modeling material A containing at least one of organic particles and inorganic particles, and a polymerization initiator A;
A three-dimensional modeling material set comprising a three-dimensional modeling material B including a polymerizable compound B.   The three-dimensional modeling material set according to claim 1, wherein the organic particles are at least one selected from polymethyl methacrylate, polycarbonate, polyester, polyamide, and polyetheretherketone.   The three-dimensional modeling material set according to claim 1, wherein the inorganic particles are at least one selected from zirconia, alumina, and silicate.   The three-dimensional modeling material set according to any one of claims 1 to 3, wherein the polymerization initiator A is a peroxide. When the three-dimensional modeling material A is in a liquid state, the volume average particle size of at least one of the organic particles and the inorganic particles is less than 1 μm,
The three-dimensional modeling material set according to any one of claims 1 to 4, wherein when the three-dimensional modeling material A is in a powder state, a volume average particle size of at least one of the organic particles and the inorganic particles is 1 µm or more.   The three-dimensional modeling material set according to any one of claims 1 to 5, wherein the three-dimensional modeling material A further includes a polymerizable compound A.   The three-dimensional modeling material set according to any one of claims 1 to 6, wherein both the three-dimensional modeling material A and the three-dimensional modeling material B are in a liquid state.   The three-dimensional modeling material set according to any one of claims 1 to 6, wherein the three-dimensional modeling material A is in a powder state, and the three-dimensional modeling material B is in a liquid state.   The three-dimensional modeling material set according to any one of claims 1 to 8, wherein the three-dimensional modeling material B further includes a tertiary amine as the polymerization initiator B.   The three-dimensional modeling material set according to any one of claims 6 to 9, comprising a monofunctional polymerizable compound and a polyfunctional polymerizable compound as the polymerizable compound A or the polymerizable compound B.   The three-dimensional modeling material set according to claim 10, wherein the monofunctional polymerizable compound or the polyfunctional polymerizable compound is at least one of an acrylic compound and a methacrylic compound.   The three-dimensional modeling material set according to claim 9, wherein the tertiary amine has a toluidine skeleton. A layer forming step of forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set according to any one of claims 1 to 12,
The provision process of providing the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 12, to a predetermined region of the three-dimensional modeling material A layer,
A method for producing a three-dimensional modeled object characterized by repeating a plurality of times. A layer forming step of forming a three-dimensional material A layer using the three-dimensional material A in the three-dimensional material set according to any one of claims 1 to 12,
The provision process of providing the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 12, to a predetermined region of the three-dimensional modeling material A layer,
A process for producing a dental prosthesis, characterized in that the above is repeated a plurality of times. Layer forming means for forming a three-dimensional modeling material A layer using the three-dimensional modeling material A in the three-dimensional modeling material set according to any one of claims 1 to 12,
Applying means for applying the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 12 to a predetermined region of the three-dimensional modeling material A layer;
An apparatus for producing a three-dimensional structure, characterized by comprising: