JP6825282B2 - Three-dimensional modeling material set, manufacturing method of three-dimensional modeling, manufacturing method of dental prosthesis, manufacturing equipment of three-dimensional modeling - Google Patents

Description

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

Conventionally, tooth prostheses (artificial teeth) have been made and used from metal materials such as cobalt-chromium alloys, ceramic materials such as zirconia, and organic materials such as hybrid resins in which the ceramic materials and resins are combined. ..

An artificial tooth using a material containing a cross-linking agent, a reaction accelerator, or the like in the organic material can be expected to obtain much higher strength than an artificial tooth containing a single polymethylmethacrylate material. Further, high strength can 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 or the like and cannot be laminated. In addition, there is a problem that it is impossible to adjust the color with a laser.

Therefore, a method for producing a three-dimensional model in which powder layers are stacked while adding a binder by using an inkjet method has been proposed (see, for example, Patent Document 1).

An object of the present invention is to provide a three-dimensional modeling material set capable of easily and efficiently producing a three-dimensional model having a complicated three-dimensional shape and obtaining high strength immediately after modeling.

The three-dimensional modeling material set of the present invention as a means for solving the above-mentioned problems includes at least one of organic particles and inorganic particles, a three-dimensional modeling material A containing a polymerization initiator A, and a three-dimensional modeling compound B. It has a molding material B and.

According to the present invention, it is possible to provide a three-dimensional modeling material set capable of easily and efficiently producing a three-dimensional model having a complicated three-dimensional shape and obtaining high strength immediately after modeling.

FIG. 1 is a schematic view showing an example of a three-dimensional model manufacturing apparatus of the present invention. FIG. 2 is a schematic view showing another example of the three-dimensional model manufacturing apparatus of the present invention.

(3D modeling material set)
The three-dimensional modeling material set of the present invention (sometimes also referred to as “laminated modeling material set”) is a three-dimensional modeling material A (“laminated modeling material”) containing at least one of organic particles and inorganic particles, and a polymerization initiator A. A ”) and a three-dimensional modeling material B containing a polymerizable compound B (sometimes referred to as“ laminated modeling material B ”), and other materials as needed. Have.
In the three-dimensional modeling material set of the present invention, when the conventional method for producing a three-dimensional model is used, the binder used does not immediately react or dissolve, so that the three-dimensional model is formed after the laminated modeling is completed. It is based on the knowledge that it is necessary to wait for a long time until it is taken out from the device, and when a binder (resin) is used, the binder cannot be removed because it is not sintered, and it remains as an impurity until the end. is there.

<Material A for 3D modeling (Material A for laminated modeling)>
The three-dimensional modeling material A (laminated modeling material A) contains at least one of organic particles and inorganic particles, and a polymerization initiator A, and further contains other materials if necessary. The three-dimensional modeling material A may be in a liquid state or a powder state, and may be appropriately selected as needed.
When the three-dimensional modeling material A is in a liquid state, it is preferable that the polymerizable compound A is further contained.
The "liquid state" means that the state of the three-dimensional modeling material at 25 ° C. is liquid or fluid, and is a term including, for example, a slurry state.

<< Organic particles >>
The material of the organic particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polymethylmethacrylate (hereinafter, also referred to as “PMMA”) and polycarbonate (hereinafter, “PC”) may be used. Polyamides such as polyester (hereinafter, also referred to as "PES"), polyamide 12 (hereinafter, also referred to as "PA12"), and polyetheretherketone (hereinafter, also referred to as "PEEK"). There are times) and so on. The weight average molecular weight of each polymer can be handled from high to low as required. These may be used alone or in combination of two or more. The polyamide 12 is a ring-opening polycondensation polyamide 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, it is possible to prevent the organic particles from swelling and the rice cake-like composition from becoming too flexible, and the molding can be performed well, and the weight average molecular weight is 1,500,000 or less. , The swelling of organic particles becomes faster, and the modeling speed can be improved.
For the weight average molecular weight, for example, the molecular weight distribution of the isolated organic particles can be obtained by a gel permeation chromatography (GPC) method, and the weight average molecular weight can be calculated based on this.

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 less likely 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 rate can be slowed down, and the reaction can be prevented from ending without the three-dimensional modeling material B permeating to the lower layer. Further, the fluidity can be improved regardless of the type of organic particles, the powder transfer is good, and the molding accuracy can be improved when the size is 100 μm or less.
The volume average particle diameter can be measured according to a known method using a known particle size measuring device, for example, Multisizer III (manufactured by Coulter Counter) or FPIA-3000 (manufactured by Sysmex Corporation). ..

When the three-dimensional modeling material A is in a liquid state, the content of the organic particles is preferably 20% by mass or more and 70% by mass or less, preferably 30% by mass or more and 50% by mass, based on the total amount of the three-dimensional modeling material A. The following is more preferable. On the other hand, when the three-dimensional modeling material A is in a powder state, 80% by mass or more and 99% by mass or less is preferable, and 90% by mass or more and 99% by mass or less is more preferable with respect to the total amount of the three-dimensional modeling material A.

<< Inorganic particles >>
The material of the inorganic particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include zirconia, alumina, silica and silicate. These may be used alone or in combination of two or more.
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.

The content of the zirconia is preferably 90% by mass or more, more preferably 94% by mass or more, based on the total amount of the inorganic particles. 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 is unlikely to occur.

The content of yttria is preferably 2% by mass or more and 6% by mass or less, and more preferably 3% by mass or more and 5% by mass or less, based on 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 less likely to occur during firing.

The content of alumina as the impurity is preferably 3% by mass or less, 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 less affected.

As the inorganic particles, a commercially available product may be used. As the commercially available product, zirconia has a trade name of 3YZ-E (manufactured by Tosoh Corporation), alumina has a trade name of AHP200 (manufactured by Nippon Light Metal Co., Ltd.), and silica. Examples of the product name: H201 (manufactured by Asahi Glass Co., Ltd.) and the like.

The contents of zirconia, yttria, and alumina in the inorganic particles can be measured by, for example, 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 less likely 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 fluidity can be improved, the powder transport becomes good, and when it is 100 μm or less, the molding accuracy can be improved.
The volume average particle diameter can be measured according to a known method using a known particle size measuring device, for example, 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, or a method for synthesizing from an aqueous metal salt solution of zirconia or yttria. And so on. Among these, the method by the thermal decomposition method or the coprecipitation method is preferable.

In the thermal decomposition method, zirconium oxychloride and an aqueous yttrium chloride solution are mixed in a predetermined amount, and sodium chloride (or potassium chloride) is added in an amount of 0.1% by mass or more and 1% by mass or less based on the total amount of zirconium oxychloride. Mix. This mixed solution is instantly dried by a spray drying method or the like to obtain a dry powder.
The instant drying is a method that can be dried within 10 seconds, and the drying temperature is preferably performed in heated air of 200 ° C. or higher.
Next, the dry powder is thermally decomposed in air at a temperature of 800 ° C. or higher and 1,200 ° C. or lower to obtain an oxide calcined powder. The oxide calcined powder is pulverized by a wet pulverization method so that the pulverization diameter is 2 μm or less, and washed with water. The method of washing with water is not particularly limited and may be appropriately selected depending on the intended purpose, but a continuous washing and filtering method using a membrane filter is preferable.
By the water washing, the sodium (or potassium) concentration in the inorganic particles is sufficiently washed with water so that the amount converted into an oxide is in the range of 10 ppm or more and 100 ppm or less. Inorganic particles (zirconia powder) can be obtained by drying the slurry after washing with water.

In the coprecipitation method, zirconium oxychloride and an aqueous solution of yttrium chloride 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 constant, the molar ratio of sodium sulfate (or potassium sulfate) to zirconia is preferably 0. Add so that it is 3 or more and 0.7 or less, and react at a temperature of 50 ° C or more and 100 ° C or less for several hours or more. An alkaline aqueous solution such as sodium hydroxide or ammonia is added to this mixture with stirring to adjust the pH of the aqueous solution to 8 or more and 10 or less. The obtained co-precipitated hydrate particles are thoroughly washed with water, and it is confirmed that the sodium (or potassium) in terms of oxide is in the range of 10 ppm or more and 100 ppm or less. The hydrate fine particles after washing with water are dehydrated and dried, and calcined in air at a temperature of 800 ° C. or higher and 1,200 ° C. or lower to obtain an oxide calcined powder. Inorganic particles (zirconia powder) can be obtained by wet pulverizing the obtained oxide calcined powder to 2 μm or less and drying it.

When the three-dimensional modeling material A is in a liquid state, the content of the inorganic particles is preferably 20% by mass or more and 70% by mass or less, preferably 30% by mass or more and 50% by mass, based on the total amount of the three-dimensional modeling material A. % Or less is more preferable. On the other hand, when the three-dimensional modeling material A is in a powder state, it is preferably 50% by mass or more and 99% by mass or less, more preferably 80% by mass or more and 95% by mass or less, based on the total amount of the three-dimensional modeling material A.

<< Polymerization Initiator A >>
Examples of the polymerization initiator A include peroxides and tertiary amines.
When the peroxide is contained in the three-dimensional modeling material A, it is preferable that the tertiary amine is contained in the three-dimensional modeling material B. By separately containing the peroxide and the tertiary amine 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. At that time, a radical reaction is started, 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, so that a three-dimensional model can be obtained easily and efficiently. It is advantageous in that it can be done.

Examples of the peroxide include aromatic diacyl peroxides and peroxy esters such as perbenzoic acid esters. Specifically, benzoyl peroxide (BPO), 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl. Examples thereof include -2,5-di (benzoyl peroxide) hexane. These may be used alone or in combination of two or more. Among these, benzoyl peroxide (BPO) is preferable.

The method for adding the peroxide is not particularly limited, and may be uniformly mixed with the organic particles and / or the inorganic particles, or dispersed in the organic particles and / or the inorganic particles. As long as the peroxide is a 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 the organic particles and / or inorganic particles may be dispersed. When mixed with, it is preferable to mix with a Henschel mixer or an air blow. At that time, the material of the apparatus is preferably stainless steel (SUS).
When organic particles are used, the organic particles can be synthesized by emulsion polymerization and an appropriate amount of the peroxide can be added therein to form a masterbatch. When the peroxide is a room temperature liquid, it is necessary to impregnate it into the organic particles, but by impregnating it with an appropriate amount, deterioration of the fluidity of the powder is suppressed and the powder cannot be 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 100 parts by mass of any one of the organic particles and the inorganic particles. When the content is 1 part by mass or more, the radical reaction is fast, a three-dimensional model can be obtained at a desired speed, the mechanical strength can be improved, and when it is 5 parts by mass or less, the peroxide It is possible to suppress the residual mass, uniformly disperse the peroxide in the particles, and prevent the occurrence of bursting noise and uneven intensity during the radical reaction. In addition, yellowing can be suppressed.

The content of the polymerization initiator A 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 100 parts by mass of the three-dimensional modeling material A. When the content is 1 part by mass or more, the radical reaction is fast, a three-dimensional model can be obtained at a desired speed, the mechanical strength can be improved, and when it is 5 parts by mass or less, the peroxide It is possible to suppress the residual mass, uniformly disperse the peroxide in the particles, and prevent the occurrence of bursting noise and uneven intensity during the radical reaction. In addition, 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 pyrimidine trione derivatives, organometallic compounds, and organic halogen compounds. Among these, when the three-dimensional modeling material A contains a pyrimidinetrione derivative and an organic metal compound, it is preferable that the three-dimensional modeling material B contains an organic halogen compound, and the three-dimensional modeling material A contains an organic halogen compound. In the case of containing, it is preferable that the three-dimensional modeling material B contains a pyrimidinetrione derivative and an organic metal compound.

Examples of the pyrimidine trione 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 alone or in combination of two or more.

Examples of the organic metal compound include acetylacetone copper, 4-cyclohexylbutyrate copper, cupric acetate, copper oleate, acetylacetone manganese, manganese naphthenate, manganese octylate, cobalt acetylacetone, cobalt naphthenate, lithium acetylacetone, and lithium acetate. , Acetylacetone zinc, 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 alone or in combination of two or more.

Examples of the organic halogen compound include dilauryldimethylammonium chloride, lauryldimethylammonium chloride, tetra-n-butylammonium chloride, trioctylmethylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride and the like. These may be used alone or in combination of two or more.

<< 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 viscosity, and can be appropriately selected depending on the intended purpose. Examples thereof include a polymerizable compound having a vinyl group.
Examples of the polymerizable compound having a vinyl group include a monofunctional polymerizable compound and a polyfunctional polymerizable compound. These may be used alone or in combination of two or more. Among these, it is preferable to use a monofunctional polymerizable compound and a polyfunctional polymerizable compound in combination in order to impart a thickening effect. The monofunctional polymerizable compound and the polyfunctional polymerizable compound may be in a mixed state or in an oligomer state in which they are chemically bonded to each other.

-Monofunctional polymerizable compound-
Examples of the monofunctional polymerizable compound include a monofunctional acrylic compound and a monofunctional methacrylic compound. These may be used alone or in combination of two or more. Among these, a monofunctional methacrylic compound is preferable, and a monofunctional methacrylic compound having a methyl methacrylate skeleton is 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, 2-ethylhexyl methacrylate and the like. 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 , Ethylglycol methacrylate, 2-methoxyethyl methacrylate, benzyl methacrylate and the like. These may be used alone or in combination of two or more. Among these, the combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable from the viewpoint of the fracture toughness of the prosthesis, and methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) are preferable. It is more preferable to use in combination with.

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 number of carbon atoms 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 damage in the oral cavity can be prevented, and when the content is 30 parts by mass or less, the bending strength can be improved and damage in the oral cavity can be prevented. 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 the 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 liquid is damaged in the oral cavity. Can be prevented.

-Polyfunctional polymerizable compound-
Examples of the polyfunctional polymerizable compound include a polyfunctional acrylic compound and a polyfunctional methacrylic compound. 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), and urethane dimethacrylate. UDMA), bisphenol A diglycidyl methacrylate (Bis-GMA), etc. may be mentioned, and 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 viscosities 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. Less than a part is more preferable. When the content is 30 parts by mass or more, the desired viscosity can be adjusted, and the liquid layer laid by the doctor blade does not easily flow and can stably stay at the desired position. At 80 parts by mass or less. If there is, the increase of unreacted components can be suppressed, and damage in the oral cavity due to deterioration of mechanical strength can be prevented.

<< Other ingredients >>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a fluidizing agent and a filler. When the three-dimensional modeling material A is in a powder state, it is preferable to include the fluidizing agent in that a layer or the like formed by the three-dimensional modeling material A can be easily and efficiently formed, and a cured product obtained by containing the filler. It is preferable in that voids and the like are less likely to occur in the surface.

-Physical characteristics of material A for 3D modeling-
When the three-dimensional modeling material A is in a liquid state, the viscosity is preferably 50 mPa · s or more and 200 mPa · s or less at 25 ° C. When the viscosity is 50 mPa · s or more and 200 mPa · s or less, the stable discharge of the three-dimensional modeling material A becomes good, and the dimensional accuracy and mechanical strength of the modeled object can be improved. The viscosity can be measured, for example, in accordance with JIS-K7117, and at 25 ° C. using a B-type rotational viscometer (device name: TVB-10M, manufactured by Toki Sangyo Co., Ltd.). Can be measured.

<Material B for 3D modeling (Material B for laminated modeling)>
The three-dimensional modeling material B (laminated modeling material B) contains a polymerizable compound B, and further contains a polymerization initiator B and other materials, if necessary.
The three-dimensional modeling material B is preferably in a liquid state.

<< Polymerizable Compound B >>
The polymerizable compound B is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polymerizable compound having a vinyl group.
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 in which they are chemically bonded to each other.

-Monofunctional polymerizable compound-
Examples of the monofunctional polymerizable compound include a monofunctional acrylic compound and a monofunctional methacrylic compound. Among these, a monofunctional methacrylic compound is preferable, and a monofunctional methacrylic compound having a methyl methacrylate skeleton is 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; -Hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, hydroxyalkyl methacrylate (HAMA) such as hydroxypropyl methacrylate; tetrahydrofurfuryl methacrylate, glycidyl methacrylate, ethylene glycol methacrylate, 2-methoxyethyl methacrylate, benzyl methacrylate and the like. .. These may be used alone or in combination of two or more. Among these, the combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable from the viewpoint of the fracture toughness of the prosthesis, and methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) are preferable. It is more preferable to use in combination with.

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 number of carbon atoms 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 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 damage in the oral cavity can be prevented, and when the content is 30 parts by mass or less, the bending strength can be improved and damage in the oral cavity can be prevented. 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 damage in the oral cavity can be prevented, and when the content is 30 parts by mass or less, the bending strength can be improved and damage in the oral cavity can be prevented. it can.

-Polyfunctional polymerizable compound-
Examples of the polyfunctional polymerizable compound include a polyfunctional acrylic compound and a polyfunctional methacrylic compound. 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. Examples thereof include A diglycidyl methacrylate (Bis-GMA) and 2-hydroxy-1,3-dimethacryloxypropane. These may be used alone or in combination of two or more. 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.

The content of the polyfunctional polymerizable compound 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 mechanical strength can be improved and damage in the oral cavity can be prevented, and when the content is 30 parts by mass or less, the increase of unreacted components can be suppressed and the mechanical strength can be suppressed. It is possible to prevent damage in the oral cavity due to the deterioration of the above.

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. Less than a part is more preferable. When the content is 10 parts by mass or more, the mechanical strength can be improved and damage in the oral cavity can be prevented, and when the content is 30 parts by mass or less, the increase of unreacted components can be suppressed and the mechanical strength can be suppressed. It is possible to prevent damage in the oral cavity due to the deterioration of the above.

<Polymerization initiator B>
As the polymerization initiator B, the same material as the three-dimensional modeling material A can be used.
When the three-dimensional modeling material A contains a peroxide as the polymerization initiator A, it is preferable that the three-dimensional modeling material B 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 can be mentioned. These may be used alone or in combination of two or more. 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.

The content of the tertiary amine is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 1.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the three-dimensional modeling material B. 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 speed, and when the content is 5 parts by mass or less, yellowing of the three-dimensional model can be suppressed.

The content of the polymerization initiator B is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 1.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the three-dimensional modeling material B. 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 speed, and when the content is 5 parts by mass or less, yellowing of the three-dimensional model can be suppressed.

-Other polymerization initiators-
As the other polymerization initiator, the same other polymerization initiator used in the 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 frequency of use and the content, and for example, to a liquid discharge head in an inkjet printer or the like. It can be selected in consideration of the influence of clogging and the like, and examples thereof include an organic solvent, a viscosity modifier, a pigment, and a stabilizer.
Examples of the organic solvent include alcohols such as ethanol, ethers, ketones and the like. Of these, ethanol is preferable.

-Physical characteristics of material B for 3D modeling-
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 stable discharge of the three-dimensional modeling material B becomes good, and the dimensional accuracy and mechanical strength of the modeled object can be improved. The viscosity can be measured, for example, in accordance with JIS-K7117, and at 25 ° C. using a B-type rotational viscometer (device name: TVB-10M, manufactured by Toki Sangyo Co., Ltd.). Can be measured.

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

(Manufacturing method of three-dimensional model (laminated model) and manufacturing device of three-dimensional model (laminated model), manufacturing method of dental prosthesis and manufacturing device of dental prosthesis)
The method for producing a three-dimensional model (laminated model) of the present invention includes a layer forming step and a material B application step, and further includes other steps as necessary.
The apparatus for producing a three-dimensional model (laminated model) used in the present invention includes a layer forming means and a material B imparting means, and further has other means as needed.
The method for producing a dental prosthesis of the present invention includes a layer forming step and a material B applying step, and further includes other steps if necessary.
The dental prosthesis manufacturing apparatus includes a layer forming means and a material B applying means, and further includes other means as needed.
The method for producing a three-dimensional model (laminated model) of the present invention can be suitably carried out using the three-dimensional model (laminated model) manufacturing apparatus used in the present invention, and the layer forming step is described above. It can be preferably carried out by the layer forming means, the material B applying step can be preferably carried out by the material B applying means, and the other steps can be preferably carried out by the other means. it can.
The method for producing a dental prosthesis of the present invention can be suitably carried out 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 applying step can be suitably carried out by the material B applying means, and the other steps can be preferably carried out by the other means.

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

-Formation of layer A, a material for three-dimensional modeling-
The method of arranging the three-dimensional modeling material A on the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a method of arranging the material A in a thin layer, Japanese Patent No. 3607300 A method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in the above, and a method of spreading the three-dimensional modeling material A into a thin layer using a member such as a brush, a roller, or a 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 laminating modeling apparatus, and the like are preferably mentioned.

-Support-
The support is not particularly limited as long as the three-dimensional modeling material A can be placed on the support, and can be appropriately selected depending on the purpose. A table having a mounting surface for the three-dimensional modeling material A, Examples thereof include a base plate in the apparatus described in FIG. 1 of Japanese Patent Publication No. 2000-328106. The surface of the support, that is, the mounting surface on which the three-dimensional modeling material A is placed 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 on the support in a thin layer by using the counter rotation mechanism (counter roller), the brush or blade, the pressing member, or the like, for example, as follows. It can be carried out. That is, for example, they are arranged in an outer frame (sometimes referred to as a "mold", a "hollow cylinder", a "cylindrical structure", etc.) so as to be able to move 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, the roller or blade, the pressing member, and the like. At this time, when a support that can move up and down in the outer frame is used, 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 material A is positioned below by the thickness of the material A layer, and the three-dimensional modeling material A is placed on the support. As described above, the three-dimensional modeling material A can be placed on the support in a thin layer.

When the three-dimensional modeling material B is allowed to act on the three-dimensional modeling material A placed on the thin layer in this way, curing occurs. On the cured product of the thin layer obtained here, the three-dimensional modeling material A is placed on the thin layer in the same manner as described above, and the three-dimensional modeling material A (layer) placed on the thin layer. On the other hand, when the three-dimensional modeling material B is allowed to act, curing occurs. The 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 previously cured and existing under the material A (layer). It also occurs in between. As a result, a cured product (three-dimensional model, laminated model) having a thickness equivalent to about two layers of the three-dimensional modeling material A (layer) placed on the thin layer can be obtained.

Further, in order to place the three-dimensional modeling material A on the support in a thin layer, it can be automatically and easily performed by using the known material laminating modeling device. The material laminating molding apparatus generally includes a recorder for laminating the three-dimensional modeling material A, a movable supply tank for supplying the three-dimensional modeling material A onto the support, and the three-dimensional modeling material. A is provided with a movable molding tank for placing A on a thin layer and laminating it. In the material laminating molding apparatus, the surface of the supply tank can always be slightly raised above 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 recorder, and the thin layer of the three-dimensional modeling material A can be laminated by repeatedly moving the recorder. it can.

The thickness of the three-dimensional modeling material A layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, if the three-dimensional modeling material A is in a liquid state, for example, the average thickness per layer may be used. It is preferably 10 μm or more and 70 μm or less, and more preferably 20 μm or more and 50 μm or less. When the average thickness is 10 μm or more, it does not take an enormous amount of time to obtain a modeled object, and when it is 70 μm or less, the dimensional system of the modeled object can be improved. On the other hand, when the three-dimensional modeling material A is in a powder state, for example, the average thickness per layer is preferably 10 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. When the average thickness is 10 μm or more, it does not take an enormous amount of time to obtain a modeled object, and when it is 200 μm or less, the dimensional accuracy of the modeled object can be improved. The average thickness can be measured according to a known method.

<Material B applying process and material B applying means>
The material B application 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 a 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 of 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 intended purpose. For example, a dispenser method, a spray method, an inkjet method, or the like can be used. Examples thereof include the liquid discharging means used. In the present invention, a liquid ejection means used in the above-mentioned inkjet method (a device that ejects droplets from a plurality of nozzles using a vibrating element such as a piezoelectric actuator) in that a complicated three-dimensional shape can be formed accurately and efficiently). Is preferable.

<Other processes and other means>
Examples of the other steps include a surface protection step and a painting step.
Examples of the other means include surface protection means, painting means, and the like.

-Surface protection process and surface protection means-
The surface protection step is a step of forming a protective layer on the modeled object formed in the liquid B application step. By performing the surface protection step, the surface of the three-dimensional model can be provided with durability such that the three-dimensional object can 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 a spray device and a coating device.

-Painting process and painting means-
The painting step is a step of painting the three-dimensional model. By performing this painting step, the modeled object can be colored in a desired color.
Examples of the coating means include known coating devices, such as a coating device using a spray, a roller, a brush, or the like.

Here, FIG. 1 shows an example of a three-dimensional model manufacturing apparatus of the present invention. The three-dimensional model manufacturing apparatus of 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. It has a possible stage 3 and forms a layer made of a three-dimensional modeling material A on the stage.
Above the modeling side material storage tank 1, there is an inkjet head 5 that ejects the three-dimensional modeling material B4 toward the three-dimensional modeling material A in the material storage tank, and further, modeling is performed from the supply side material storage tank 2. It has a leveling mechanism 6 (hereinafter, may be referred to as a recorder) that supplies the three-dimensional modeling material A to the side material storage tank 1 and smoothes the surface of the three-dimensional modeling material A layer of the modeling side material storage tank 1.

The three-dimensional modeling material B4 is dropped from the inkjet head 5 onto the three-dimensional modeling material A of the modeling side material storage tank 1. At this time, the position where the three-dimensional modeling material B4 is dropped is determined by the two-dimensional image data (slice data) obtained by slicing the 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 material storage tank 2 on the supply side is raised, and the stage 3 of the material storage tank 1 on the modeling side is lowered. The three-dimensional modeling material A having the difference is moved to the modeling side material storage tank 1 by the leveling mechanism 6.

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

FIG. 2 shows another example of the three-dimensional object manufacturing apparatus of the present invention. The three-dimensional modeling object manufacturing apparatus of FIG. 2 is basically the same as that of FIG. 1, but the supply mechanism of the three-dimensional modeling material A is different. That is, the supply side material storage tank 2 is arranged 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 while the supply side material storage tank 2 is moving, a predetermined amount of the three-dimensional modeling material A is transferred to the modeling side material storage tank 1. It is dropped to form a new three-dimensional modeling material A layer. After that, 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 lamination molding apparatus having the configuration shown in FIG. 2, the apparatus can be made more compact than the configuration of FIG. 1 in which two material storage tanks are arranged in a plane.

(Three-dimensional model (laminated model) and dental prosthesis)
The three-dimensional model (laminated model) is manufactured by the method for manufacturing the three-dimensional model of the present invention.
The dental prosthesis is manufactured by the method for manufacturing the dental prosthesis of the present invention.
The three-dimensional model of the present invention can be suitably used as a dental prosthesis.
Applications of the dental prosthesis include, for example, artificial dentures, removable partial dentures, complete dentures, implants, dentures and the like.

-Bending strength of 3D objects-
The bending strength of the three-dimensional model is preferably 50 MPa or more, more preferably 80 MPa or more. When the bending strength is 50 MPa or more, sufficient strength can be obtained in the three-dimensional modeled object. 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).

-Bending elastic modulus of three-dimensional model-
The flexural modulus of the three-dimensional model is preferably 1.5 GPa or more, more preferably 2.0 GPa or more. When the flexural modulus is 1.5 GPa or more, sufficient strength can be obtained in a three-dimensional model. 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 three-dimensional model-
The Vickers hardness of the three-dimensional model is preferably 10 HV 0.2 or higher, and more preferably 18 HV 0.2. When the Vickers hardness is 10 HV0.2 or more, sufficient hardness can be obtained in a three-dimensional model. The Vickers hardness can be measured in accordance with JIS-T-6501 using a Vickers hardness tester (device name: FV-800, manufactured by Future Tech Co., Ltd.). The Vickers hardness is a value when measured with a test force of 0.2 kg.

-Content of residual monomer in 3D model-
The content of the residual monomer in the three-dimensional model is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less, based on the total amount of the three-dimensional model. When the content is 10% by mass or less, impurities contained in the three-dimensional model can be reduced, and the strength and dimensional accuracy of the three-dimensional model can be improved. The content of the residual monomer in the three-dimensional model can be measured by using HPLC (device name: LC2010, manufactured by Shimadzu Corporation) in accordance with JIS-T6501.
In the present invention, as compared with the laminated model obtained by the conventional laminated model, each layer is cured, so that the residual monomer in the obtained three-dimensional model cannot be reduced to zero, but it can be extremely reduced. it can.

With the above-mentioned manufacturing method and manufacturing equipment for a three-dimensional model, a three-dimensional model having a complicated three-dimensional shape mainly composed of resin can be easily and efficiently modeled, and high strength can be exhibited immediately after the modeling. Obtainable. The three-dimensional model thus obtained has sufficient strength, is excellent in dimensional accuracy, and can reproduce fine irregularities, curved surfaces, etc., so that it has an excellent aesthetic appearance, is of high quality, and is suitably used for various purposes. be able to.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Further, 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 material are as follows. I asked for it.

-Volume average particle size (Dv) of organic particles and inorganic particles in the three-dimensional modeling material A-
Using Coulter Multisizer III (manufactured by Coulter Counter) as a measuring device, connect an interface (manufactured by Nikkaki Co., Ltd.) that outputs the number distribution and volume distribution, and a personal computer, and use primary sodium chloride as the electrolyte. A 1% by mass NaCl aqueous solution was prepared using. As a measuring method, 0.1 mL or more and 5 mL or less of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 mL or more and 150 mL or less of a 1 mass% NaCl aqueous solution as the electrolytic solution, and 2 mg or more of the three-dimensional modeling material A is added. 20 mg or less was added, and a dispersion treatment was carried out with an ultrasonic disperser for 1 minute or more and 3 minutes or less. Further, put 100 mL or more and 200 mL or less of the electrolytic aqueous solution in another beaker, add the sample dispersion liquid to a predetermined concentration, and use a 100 μm aperture as an aperture by the Coulter Multisizer III, and use 50,000 particles. The average value of the particles was measured. The measurement was carried out by dropping the dispersion liquid of the three-dimensional modeling material 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 3D model-
The content of the residual monomer in the three-dimensional model was measured by HPLC (device name: LC2010, manufactured by Shimadzu Corporation).

(Preparation Example 1 of Material A for Three-dimensional Modeling)
<Preparation of material A1 for 3D modeling>
100 parts by mass of polymethylmethacrylate (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 powdered three-dimensional modeling material A1.

(Preparation Example 2 of Material A for Three-dimensional Modeling)
<Preparation of material A2 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, polymethylmethacrylate (PMMA) was changed to polycarbonate (PC, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), but in the same manner as the preparation of the three-dimensional modeling material A1, powdered three-dimensional modeling Engineering plastic A2 was prepared.

(Preparation Example 3 of Material A for Three-dimensional Modeling)
<Preparation of material A3 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, the polymethylmethacrylate (PMMA) was changed to polyamide 12 (PA12, manufactured by Toray Industries, Inc.), but in the same manner as the preparation of the three-dimensional modeling material A1, for three-dimensional modeling in a powder state. Material A3 was prepared.

(Preparation Example 4 of Material A for Three-dimensional Modeling)
<Preparation of material A4 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, the polymethylmethacrylate (PMMA) was changed to polyester (PES, manufactured by Toray Co., Ltd.), but the powdered three-dimensional modeling material was prepared in the same manner as the preparation of the three-dimensional modeling material A1. A4 was prepared.

(Preparation Example 5 of Material A for Three-dimensional Modeling)
<Preparation of material A5 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, except that polymethylmethacrylate (PMMA) was changed to polyetheretherketone (PEEK, manufactured by Victrex), the three-dimensional modeling in a powder state was the same as the preparation of the three-dimensional modeling material A1. Material A5 was prepared.

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

(Preparation Example 7 of Material A for Three-dimensional Modeling)
<Preparation of material A7 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, polymethylmethacrylate (PMMA) was changed to alumina (trade name: AHP200, manufactured by Nippon Light Metal Co., Ltd.), but in the same manner as the preparation of the three-dimensional modeling material A1, it was in a powder state. Material A7 for three-dimensional modeling was prepared.

(Preparation Example 8 of Material A for Three-dimensional Modeling)
<Preparation of 3D modeling material A8>
In the preparation of the three-dimensional modeling material A1, polymethylmethacrylate (PMMA) was changed to silica (trade name: H201, manufactured by Asahi Glass Co., Ltd.), except that the three-dimensional modeling material A1 was prepared in the same manner as the three-dimensional modeling material A1. A modeling material A8 was prepared.

(Preparation Example 9 of Material A for Three-dimensional Modeling)
<Preparation of material A9 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, polymethylmethacrylate (PMMA) was changed to lithium disilicate (prototype), but in the same manner as the preparation of the three-dimensional modeling material A1, the powdered three-dimensional modeling material A9 Was prepared.

(Preparation Example 10 of Material A for Three-dimensional Modeling)
<Preparation of 3D modeling material A10>
In the preparation of the three-dimensional modeling material A1, 1 part by mass of benzoyl peroxide (BPO) was changed to 5 parts by mass of benzoyl peroxide (BPO), but in the same manner as the preparation of the three-dimensional modeling material A1, the solid in a powder state. A modeling material A10 was prepared.

(Preparation Example 11 of Material A for Three-dimensional Modeling)
<Preparation of material A11 for 3D modeling>
In the preparation of the three-dimensional modeling material A1, the powdered 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 contained.

(Preparation Example 12 of Material A for Three-dimensional Modeling)
<Preparation of material A12 for 3D modeling>
40 parts by mass of polymethylmethacrylate (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 methylmethacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.) , Bisphenol A diglycidyl methacrylate (Bis-GMA, manufactured by Sigma Aldrich) was mixed by 30 parts by mass to prepare a liquid-state three-dimensional modeling material A12. The viscosity was 113 mPa · s.

(Preparation Example 13 of Material A for Three-dimensional Modeling)
<Preparation of material A13 for 3D modeling>
In the preparation of the three-dimensional modeling material A12, the polymethyl methacrylate was changed to polycarbonate (PC, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), but in the same manner as the preparation of the three-dimensional modeling material A12, the liquid state three-dimensional modeling material A13 Was prepared. The viscosity was 109 mPa · s.

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

The composition and content of the prepared three-dimensional modeling materials A1 to 14 are shown in Table 1 below.

(Preparation Example 1 of Material B for Three-dimensional Modeling)
<Preparation of material B1 for 3D modeling>
As a monofunctional polymerizable compound, 60 parts by mass of methyl methacrylate (MMA, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA, manufactured by Tokyo Kasei Kogyo Co., Ltd.), and as a polyfunctional polymerizable compound, 20 parts by mass of bisphenol A diglycidyl methacrylate (Biz-GMA, manufactured by Sigma Aldrich), and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a tertiary amine. Was mixed to prepare a three-dimensional modeling material B1.

(Preparation Example 2 of Material B for Three-dimensional Modeling)
<Preparation of material B2 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, 2-hydroxyethyl methacrylate (HEMA) was changed to hydroxypropyl methacrylate (HPMA, manufactured by Tokyo Chemical Industry Co., Ltd.) in the same manner as the preparation of the three-dimensional modeling material B1. The modeling material B2 was prepared.

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

(Preparation Example 4 of Material B for Three-dimensional Modeling)
<Preparation of material B4 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) was changed to 10 parts by mass of 2-hydroxyethyl methacrylate (HEMA) in the same manner as in the preparation of the three-dimensional modeling material B1. Material B4 for three-dimensional modeling was prepared.

(Preparation Example 5 of Material B for Three-dimensional Modeling)
<Preparation of material B5 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, 20 parts by mass of 2-hydroxyethyl methacrylate (HEMA) was changed to 30 parts by mass of 2-hydroxyethyl methacrylate (HEMA) in the same manner as in the preparation of the three-dimensional modeling material B1. Material B5 for three-dimensional modeling was prepared.

(Preparation Example 6 of Material B for Three-dimensional Modeling)
<Preparation of material B6 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, bisphenol A diglycidyl methacrylate (Bis-GMA) was changed to tetraethylene glycol dimethacrylate (TEGDMA, manufactured by Kyoeisha Chemical Co., Ltd.) in the same manner as the preparation of the three-dimensional modeling material B1. The material B6 for three-dimensional modeling was prepared.

(Preparation Example 7 of Material B for Three-dimensional Modeling)
<Preparation of material B7 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, bisphenol A diglycidyl methacrylate (Bis-GMA) was changed to urethane dimethacrylate (UDMA, manufactured by Sigma Aldrich), except that the three-dimensional modeling material B1 was prepared in the same manner as the three-dimensional modeling material B1. The modeling material B7 was prepared.

(Preparation Example 8 of Material B for Three-dimensional Modeling)
<Preparation of material B8 for 3D modeling>
In the 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), the preparation of the three-dimensional modeling material B1 In the same manner, the three-dimensional modeling material B8 was prepared.

(Preparation Example 9 of Material B for Three-dimensional Modeling)
<Preparation of material B9 for 3D modeling>
In the 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), the preparation of the three-dimensional modeling material B1 In the same manner, the three-dimensional modeling material B9 was prepared.

(Preparation Example 10 of Material B for Three-dimensional Modeling)
<Preparation of material B10 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, N, N-dimethyl-p-toluidine (DMPT) was added to N. The three-dimensional modeling material B10 was prepared in the same manner as 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 of Material B for Three-dimensional Modeling)
<Preparation of 3D modeling material B11>
Three-dimensional modeling except that 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) in the preparation of the three-dimensional modeling material B1. The material B11 for three-dimensional modeling was prepared in the same manner as the preparation of the material B1.

(Preparation Example 12 of Material B for Three-dimensional Modeling)
<Preparation of material B12 for 3D modeling>
Three-dimensional modeling except that 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) in the preparation of the three-dimensional modeling material B1. The material B12 for three-dimensional modeling was prepared in the same manner as the preparation of the material B1.

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

(Preparation Example 14 of Material B for Three-dimensional Modeling)
<Preparation of 3D modeling material B14>
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) have a viscosity of 10 mPa · s and hydroxybutyl methacrylate (HBMA) 30. The three-dimensional modeling material B14 was prepared in the same manner as the preparation of the three-dimensional modeling material B1 except that the viscosity was changed to 20 mPa · s in parts by mass and 30 parts by mass of bisphenol A diglycidyl methacrylate (Bis-GMA). ..

(Preparation Example 15 of Material B for Three-dimensional Modeling)
<Preparation of material B15 for 3D modeling>
In the preparation of the three-dimensional modeling material B14, three-dimensional modeling was performed in the same manner as the preparation of the three-dimensional modeling material B14, except that N, N-dimethyl-p-toluidine (DMPT) was changed to N-methylethaneamine (MEA). Material B15 was prepared.

(Preparation Example 16 of Material B for Three-dimensional Modeling)
<Preparation of 3D modeling material B16>
In the preparation of the three-dimensional modeling material B14, the 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 contained.

(Preparation Example 17 of Material B for Three-dimensional Modeling)
<Preparation of material B17 for 3D modeling>
In the preparation of the three-dimensional modeling material B16, the three-dimensional modeling material B17 was prepared in the same manner as the preparation of the three-dimensional modeling material B16, except that the bisphenol A diglycidyl methacrylate (Bis-GMA) was not contained.

(Preparation Example 18 of Material B for Three-dimensional Modeling)
<Preparation of material B18 for 3D modeling>
In the preparation of the three-dimensional modeling material B1, 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 contained. Prepared the three-dimensional modeling material B18 in the same manner as the preparation of the three-dimensional modeling material B1.

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

In Table 2, "HAMA" is a 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 (laminated modeling material set) of Example 1. Using the three-dimensional modeling material set, the three-dimensional modeling object 1 was manufactured as follows by a shape printing pattern of a size (length 70 mm × width 12 mm).

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

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

(3) Next, the operations of (1) and (2) are repeated until a predetermined total average thickness of 3 mm is obtained, and thin layers made of the cured three-dimensional modeling material A1 are sequentially laminated to form a three-dimensional object. Model 1 was manufactured. When the excess material A for three-dimensional modeling was removed from the obtained three-dimensional modeling object 1 by air blowing, the shape was not lost. The three-dimensional model 1 was excellent in strength and dimensional accuracy.

Next, the bending strength, flexural modulus, Vickers hardness, curing speed, and dimensional accuracy of the obtained three-dimensional model 1 were evaluated according to the following criteria. The results are shown in Table 3 below.

<Bending strength and flexural modulus>
The obtained three-dimensional model 1 was measured by a three-point bending strength test based on JIS-T-6501 using a desktop precision universal testing machine (device name: AUTOGRAPPH-AGS-J, manufactured by Shimadzu Corporation). , Bending strength and flexural modulus were evaluated based on the following evaluation criteria.
-Evaluation criteria for bending strength-
◯: Bending strength is 80 MPa or more Δ: Bending strength is 50 MPa or more and less than 80 MPa ×: Bending strength is less than 50 MPa-Evaluation standard of bending elastic modulus-
◯: Bending elastic modulus of 2.0 GPa or more Δ: Bending elastic modulus of 1.5 GPa or more and less than 2.0 GPa ×: Bending elastic modulus of less than 1.5 GPa

<Vickers hardness>
The obtained three-dimensional model 1 was measured using a Vickers hardness tester (device name: FV-800, manufactured by Future Tech Co., Ltd.) with a test force of 0.2 kg in accordance with JIS-T-6501. The Vickers hardness was evaluated based on the evaluation criteria.
-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 model 1 was evaluated according to the following criteria.
-Evaluation criteria-
◯: A state in which the modeled object can be taken out by hand even if only 10 seconds have passed after the three-dimensional modeling △: A state in which the modeled object can be taken out by hand 10 minutes after the three-dimensional modeling ×: Modeling even one hour after the three-dimensional modeling The state where the object is fragile and cannot be taken out

<Dimensional accuracy>
The dimensional accuracy of the three-dimensional model 1 was evaluated according to the following criteria.
-Evaluation criteria-
◯: The surface of the obtained three-dimensional model is smooth and beautiful, and there is no warpage. Δ: The surface of the obtained three-dimensional model is slightly distorted and slightly warped. ×: Obtained The surface of the three-dimensional model is distorted and warped violently.

(Examples 2-26 and Comparative Examples 1-2)
<Making a 3D modeling material set>
In Example 1, each three-dimensional model (laminated model) was created in the same manner as in Example 1 except that the combination of the three-dimensional modeling material A and the three-dimensional modeling material B was changed as shown in Table 3 below. It was prepared and evaluated. The results are shown in Table 3 below. In addition, Comparative Examples 1 and 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 (laminated modeling material set) of Example 27.
In Example 1, each three-dimensional model (laminated model) was produced and evaluated in the same manner as in Example 1 except that the modeling step (1) was changed to the following (1'). The results are shown in Table 3 below.

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

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

In Table 3, the values in parentheses next to the evaluation are the values of bending strength, flexural modulus, and Vickers hardness, respectively.

Examples of aspects of the present invention are as follows.
<1> A three-dimensional 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 polymethylmethacrylate, polycarbonate, polyester, polyamide, and polyetheretherketone.
<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 diameter of at least one of the organic particles and the inorganic particles is less than 1 μm.
The three-dimensional modeling material according to any one of <1> to <4>, wherein when the three-dimensional modeling material A is in a powder state, the volume average particle diameter of at least one of the organic particles and the inorganic particles is 1 μm or more. It 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 contains a polymerizable compound A.
<7> The three-dimensional modeling material set according to any one of <1> to <6>, wherein both the three-dimensional modeling material A and the three-dimensional modeling material B are 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 contains a tertiary amine as the polymerization initiator B.
<10> The three-dimensional modeling material set according to any one of <6> to <9>, wherein the polymerizable compound A or the polymerizable compound B contains a monofunctional polymerizable compound and a polyfunctional polymerizable compound.
<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 modeling material A layer using the three-dimensional modeling material A in the three-dimensional modeling material set according to any one of <1> to <12>.
An imparting 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.
This is a method for manufacturing a three-dimensional model, which is characterized by repeating the above steps a plurality of times.
<14> A layer forming step of 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 <1> to <12>.
An imparting 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 manufacturing a dental prosthesis, which is characterized by repeating the above steps a plurality of times.
<15> A 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 <1> to <12>.
An imparting means for imparting 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 a three-dimensional model manufacturing apparatus characterized by having.

The three-dimensional modeling material set according to any one of <1> to <12>, the method for producing a three-dimensional model according to <13>, the method for producing a dental prosthesis according to <14>, and the above. The three-dimensional model manufacturing apparatus according to <15> can solve the above-mentioned problems in the prior art and achieve the object of the present invention.

Japanese Unexamined Patent Publication No. 2004-330743

4 Material B for 3D modeling

Claims (15)

A three-dimensional modeling material A containing at least one of organic particles and inorganic particles, and a polymerization initiator A,
Look containing a polymerizable compound B, and a stereolithography material set having allowed to act against for stereolithography material A and material for stereolithography cure occurs of the stereolithography material A B, and
When the three-dimensional modeling material A is in a liquid state, the volume average particle diameter 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 set is characterized in that the volume average particle diameter of at least one of the organic particles and the inorganic particles is 1 μm or more . A 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 containing a polymerizable compound B and having a three-dimensional modeling material B in which the three-dimensional modeling material A is cured when acted on the three-dimensional modeling material A.
A three-dimensional modeling material set characterized in that 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 2, wherein the organic particles are at least one selected from polymethylmethacrylate, polycarbonate, polyester, polyamide, and polyetheretherketone. The three-dimensional modeling material set according to any one of claims 1 to 3 , 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 4 , wherein the polymerization initiator A is a peroxide. The three-dimensional modeling material set according to any one of claims 1 to 5, wherein the three-dimensional modeling material A further contains a polymerizable compound A. The three-dimensional modeling material set according to claim 1 , 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 7 , wherein the three-dimensional modeling material B further contains a tertiary amine as the polymerization initiator B. The three-dimensional modeling material set according to claim 6 , wherein the polymerizable compound A or the polymerizable compound B contains a monofunctional polymerizable compound and a polyfunctional polymerizable compound. The three-dimensional modeling material set according to claim 9 , 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 any one of claims 8 to 10 , wherein the tertiary amine has a toluidine skeleton. A layer forming step of 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 11 .
A step of imparting the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 11 to a predetermined region of the three-dimensional modeling material A layer.
A method for manufacturing a three-dimensional model, which comprises repeating the above steps a plurality of times. A layer forming step of 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 11 .
A step of imparting the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 11 to a predetermined region of the three-dimensional modeling material A layer.
A method for manufacturing a dental prosthesis, which comprises repeating the above steps a plurality of times. A 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 11 .
An imparting means for imparting the three-dimensional modeling material B in the three-dimensional modeling material set according to any one of claims 1 to 11 to a predetermined region of the three-dimensional modeling material A layer.
A device for manufacturing a three-dimensional object, which is characterized by having. A layer forming step of forming a three-dimensional modeling material A layer using at least one of organic particles and inorganic particles, and a three-dimensional modeling material A containing a polymerization initiator A.
A step of imparting a three-dimensional modeling material B which contains a polymerizable compound B in a predetermined region of the three-dimensional modeling material A layer and causes the three-dimensional modeling material A to cure when acted on the three-dimensional modeling material A. ,
This is a method for manufacturing a three-dimensional model that repeats the above steps multiple times.
A method for manufacturing a three-dimensional model, which satisfies any of the following 1) to 3).
1) The three-dimensional modeling material A is in a liquid state, and the volume average particle diameter of at least one of the organic particles and the inorganic particles is less than 1 μm.
2) The three-dimensional modeling material A is in a powder state, and the volume average particle diameter of at least one of the organic particles and the inorganic particles is 1 μm or more.
3) The three-dimensional modeling material A and the three-dimensional modeling material B are both in a liquid state.