JP2019084778A - Method of producing three-dimensional object and apparatus for producing three-dimensional object - Google Patents

Abstract

To provide a method for producing a three-dimensional object that can easily and efficiently produce a complex three-dimensional object in which a plurality of different resins are combined.SOLUTION: A method for producing a three-dimensional object repeatedly performs: a layer forming step of forming a three-dimensional molding material layer using a three-dimensional molding material; and a discharge step of discharging three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to a predetermined region of the three-dimensional molding material layer. Dots A to C formed by discharging three or more kinds of curing liquids on the three-dimensional molding material layer are adjacent to each other, and the dots formed by discharging one curing liquid are arranged such that there is at least one region D adjacent to the dots formed by discharging another curing liquid.SELECTED DRAWING: Figure 1B

Description

  The present invention relates to a method of manufacturing a three-dimensional object and a manufacturing apparatus of the three-dimensional object.

  Currently, there are a wide variety of products using resin, for example, parts requiring constant transparency such as displays and optical lenses, and parts as metal substitutes for weight reduction that are being considered in automobiles and aircraft Etc.

  These resins are more effective than metals and ceramics for weight reduction and function adjustment (physical property adjustment). From the high degree of freedom of function adjustment, for example, multi-materialization is performed in which resins exhibiting different physical properties such as resin parts exhibiting rubber elasticity and resin parts exhibiting high toughness are used in combination.

A problem in such multi-materialization is the joining of different resins, and examples of the joining method of the resins include a welding method, an adhesion method, a welding method and the like.
The welding process can realize strong bonding which can endure various applications if the same kind of resin is used.
The adhesion method includes adhesion by chemical reaction and adhesion by polymerization of monomers.
In the welding method, a solvent that dissolves the main material is used.

  An object of the present invention is to provide a method for producing a three-dimensional object which can easily and efficiently produce a complex three-dimensional object in which a plurality of different resins are combined.

The method for producing a three-dimensional object according to the present invention as a means for solving the above problems comprises a layer forming step of forming a three-dimensional modeling material layer using a three-dimensional modeling material;
A discharge step of discharging three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to predetermined regions of the three-dimensional structure forming material layer;
A method of producing a three-dimensional object which repeats the
The dots formed by discharging three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are discharging another curing liquid It arrange | positions so that the area | region adjacent to the dot formed by this may exist at least one place.

  According to the present invention, it is possible to provide a method for producing a three-dimensional object that can easily and efficiently produce a complex three-dimensional object in which a plurality of different resins are combined.

FIG. 1A is a view for explaining an example of the principle of the method for producing a three-dimensional object of the present invention. FIG. 1B is a view for explaining an example of the principle of the method for producing a three-dimensional object of the present invention. FIG. 2 is a schematic view showing an example of the three-dimensional object manufacturing apparatus of the present invention. FIG. 3 is a schematic view showing another example of the three-dimensional object manufacturing apparatus of the present invention.

(Method of manufacturing three-dimensional object and apparatus for manufacturing three-dimensional object)
The method for producing a three-dimensional object according to the present invention includes a layer forming step of forming a three-dimensional modeling material layer using a three-dimensional modeling material, and three or more different polymerizations with respect to a predetermined region of the three-dimensional modeling material layer. And a discharging step of discharging three or more kinds of curing liquids containing a hydrophobic compound.
The dots formed by discharging three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are discharging another curing liquid It is arranged such that there is at least one area adjacent to the dot formed in the above manner, and further including other steps as necessary.

The apparatus for producing a three-dimensional object according to the present invention comprises: layer forming means for forming a three-dimensional modeling material layer using a three-dimensional modeling material; and three or more different types of polymerization for predetermined regions of the three-dimensional modeling material layer. An apparatus for producing a three-dimensional object, comprising: discharge means for discharging three or more kinds of curing liquids containing a hydrophobic compound;
The dots formed by discharging three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are discharging another curing liquid It is arranged such that there is at least one area adjacent to the dot formed in the above-mentioned manner, and other means may be provided if necessary.

The method for producing a three-dimensional object of the present invention can be suitably carried out using the device for producing a three-dimensional object used in the present invention, and the layer forming step can be suitably carried out by the layer forming means. The step of discharging the curing liquid can be suitably carried out by means of discharging the curing liquid, and the other steps can be suitably carried out by other means.
In the present specification, "three-dimensional object" also includes "laminated object".

In the conventional welding process, in the case of resins having different basic molecular skeletons, since the respective resins are incompatible with each other, they do not mix even when they are melted. Therefore, in the method of manufacturing a three-dimensional object and the manufacturing apparatus of the three-dimensional object according to the present invention, in order to realize multi-materialization, it is necessary to select resins which are easily mixed with each other. It is based on the finding that it is difficult to combine
In the conventional adhesion method, as in the case of the welding process, when different types of resin moldings that are already present in bulk are adhered to each other, it is necessary to select an adhesive that is compatible with the respective moldings. In addition, when making parts that require dimensional accuracy, the presence of the adhesive tends to deteriorate the accuracy starting from the bonding site, and it is possible to freely combine resins having desired functions, and parts having the desired accuracy. It is based on the finding that there is also a problem with the adhesion method in terms of making
Further, the conventional welding method is based on the finding that welding is difficult when joining resins having high chemical resistance if a solvent that dissolves the main agent is used.

The method for producing a three-dimensional object and the production device for a three-dimensional object according to the present invention, as shown in FIGS. 1A and 1B, include three different polymer compounds A, B and C different from each other in the material layer for three-dimensional object. Eject a type of curing liquid. Then, dots A, B, and C formed by discharging three types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and dots formed by discharging one curing liquid and the like It is arrange | positioned so that it may have the area | region D which the dot formed by discharging the liquid for hardening of a. Adjoins.
As described above, in the present invention, materials and materials that can not be realized by the conventional material jetting method due to the compatibilization between the three-dimensional modeling material and the three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds. Multi-material modeling of physical three-dimensional objects.

  The method for producing a three-dimensional object and the production apparatus for a three-dimensional object according to the present invention form a three-dimensional object by repeating the curing reaction between the layer-forming material for three-dimensional object and the curing liquid containing a polymerizable compound. It is. Therefore, when the three-dimensional modeling material and the curing liquid are compatible with each other, the curing liquid can be alloyed with the three-dimensional modeling material by IPN (interpenetrating network), so that the desired physical properties can be controlled. . Furthermore, since the curing liquid is dot-arranged on the three-dimensional modeling material layer by the ink jet head, physical properties can be changed at the dot level. By doing so, various physical properties such as transparency and electrical properties as well as mechanical strength can be continuously changed in one part. This can realize multi-materialization combining different resins without bonding process, and therefore, deterioration in dimensional accuracy and improvement in productivity can be expected.

  Although the hardening liquid discharged on the three-dimensional structure forming material layer is dot-arranged, it is essential that the dots be adjacent to each other. If these dots are not adjacent to each other, a portion which is not filled with the curing liquid will be present in the three-dimensional object, and cracks will form there from which a desired strength or shape can not be obtained. In addition, if the dots are not adjacent to the stacking direction (Z-axis direction) in the stacking direction (Z-axis direction), a region not filled with the curing liquid is present between the stackings, and the interlayer There is a risk of peeling.

Further, in the three-dimensional object obtained by repeating the layer forming step and the discharging step, adjacent to the dot formed by discharging three or more kinds of curing liquids containing three or more different polymerizable compounds. It is necessary for at least one region to exist. In the case where dots formed by discharging a curing liquid containing different types of polymerizable compounds are adjacent to each other, it is preferable to arrange the dots alternately. This is because, if dots are not arranged alternately, they do not show mutual compatibility, or if the molecular structures differ greatly even if they show compatibility, phase separation occurs at the interface between different resins, resulting in three-dimensional shaping It is because there is a risk of damage to things. In addition, when the number of types of the polymerizable compounds is two or less, even if dots are alternately arranged, engagement of different resins is small, and as a result, the bonding strength is weak, and it is difficult to obtain a desired effect.
Such arrangement of dots can be confirmed by, for example, printing out the dots on paper and observing the resulting dot image with an optical microscope to check how the dots are arranged. it can.

  When arranging a plurality of curing liquids in dots, it is important in what order the curing liquids are discharged. For example, in the case of ejecting different inks to the same place, it is preferable to eject the one with the slower reaction speed first. When the faster reaction rate is discharged earlier, the curing liquid having a slow reaction rate is accumulated on the cured area. For this reason, the penetration of the hardening liquid to the lower part than the area | region hardened | cured previously is inadequate, and there exists a possibility that delamination may arise and a desired uniform physical property will not be obtained.

  Further, also in the case where the penetration speed is different, it is preferable to discharge the one having the slower penetration speed first. By discharging the one having the slower penetration speed first, the curing liquid having a high penetration speed coming thereon is mixed in the layer, and it is easy to realize the gradation of physical properties. If the higher penetration speed is discharged earlier, the curing liquid with lower penetration speed will not be mixed with the previously discharged curing liquid, resulting in a phase separated structure in the layer, and the desired physical properties by alloying Can not be expressed.

  After the curing liquid is discharged, a new three-dimensional modeling material layer is formed by the layer forming step. When new layer formation is carried out, it is preferable that the curing liquid has not yet been sufficiently cured. When the curing liquid finishes curing at an early stage, when the new three-dimensional modeling material layer cures, the adhesion between the lower three-dimensional modeling material layer and the new three-dimensional modeling material layer becomes insufficient, and the interlayer There is a risk of peeling. These reaction rates can be adjusted by the amount of organic peroxide contained in the stereolithography material and the amount of tertiary amine contained in the curing liquid.

<Layer Forming Process and Layer Forming Means>
A layer formation process is a process of forming a material layer for three-dimensional modeling using three-dimensional modeling material, and can be implemented by layer formation means.

<< Material for 3D modeling >>
The stereolithography material contains organic particles and a polymerization initiator, and further contains other materials as required. The material for three-dimensional modeling may be in a liquid state or in a powder state, and can be appropriately selected as necessary. When the three-dimensional structure forming material is in a liquid state, it is preferable to further include a polymerizable compound.

-Organic particles-
There is no restriction | limiting in particular as a material of an organic particle, According to the objective, it can select suitably. For example, polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"), polyvinylidene fluoride, polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polyisoprene, polyethylene oxide, novolak, polyparavinyl phenol , Nitrocellulose, polyepichlorohydrin, copolymer containing methyl methacrylate, styrene / acrylonitrile copolymer, citraconic anhydride / styrene copolymer, vinyl chloride / vinylidene chloride copolymer, vinylidene fluoride / halogenation Ethylene copolymers, epichlorohydrin / ethylene oxide copolymers and the like can be mentioned. The weight average molecular weight of each polymer can be handled from high to low as needed. These may be used alone or in combination of two or more.

The volume average particle diameter (Dv) of the organic particles is preferably less than 1 μm when the three-dimensional structure forming material is in a liquid (dispersion) state. If the volume average particle size (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 material for three-dimensional modeling is a powder state, 1 micrometer or more and 100 micrometers or less are preferable. 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 ending without the hardening liquid soaking into the lower layer. In addition, the fluidity can be improved regardless of the type of the organic particles, the powder delivery is good, and the shaping accuracy can be improved as 100 μm or less.
The volume average particle diameter can be measured according to a known method using a known particle size measurement device such as Multisizer III (manufactured by Coulter Counter Co., Ltd.) or FPIA-3000 (manufactured by Sysmex Corporation).

-Polymerization initiator-
Examples of the polymerization initiator include peroxides and tertiary amines.
When the three-dimensional structure forming material contains a peroxide, the tertiary amine is preferably contained in the curing liquid. When the peroxide and the tertiary amine are separately contained in the stereolithography material and the curing liquid, the radical reaction is initiated when the stereolithography material and the curing liquid are mixed. Ru. Then, an alloy or a compound of the polymerized polymerizable compound and the organic particles is obtained. At this time, external energy such as light and heat is unnecessary, and an alloy or compound is obtained immediately after mixing the material for three-dimensional modeling and the liquid for curing, so a three-dimensional object is obtained easily and efficiently. Is advantageous in that

  Examples of peroxides 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 And 2,5-di (benzoylperoxy) hexane. These may be used alone or in combination of two or more. Among these, benzoyl peroxide (BPO) is preferable.

The method of adding the peroxide is not particularly limited, and it may be uniformly mixed with the organic particles and / or the inorganic particles, or dispersed in the organic particles and / or the inorganic particles. If the peroxide is a solid at normal temperature, it may be mixed with the organic particles and / or the inorganic particles, or may be dispersed in the organic particles and / or the inorganic particles. On the other hand, when mixing with organic particles and / or inorganic particles, mixing with a Henschel mixer or air blow is preferable. At that time, the material of the device is preferably stainless steel (SUS).
When organic particles are used, the organic particles can be synthesized by emulsion polymerization, and a proper amount of peroxide can be put therein to make a masterbatch. When the peroxide is a normal temperature liquid, it is necessary to soak it into the organic particles, but it is possible to prevent the powder transport from becoming impossible by suppressing the deterioration of the powder flowability by soaking the appropriate amount. .

  The content of the peroxide is preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to at least 100 parts by mass of at least one of the organic particles and the inorganic particles. A radical reaction is quick that content of a peroxide is 1 mass part or more, a three-dimensional object can be obtained at a desired speed | rate, and mechanical strength can also be improved. On the other hand, when the content of the peroxide is 5 parts by mass or less, the remaining of the mass of the peroxide can be suppressed, the peroxide can be uniformly dispersed in the particles, and burst noise and uneven strength occur during radical reaction. It can prevent the occurrence. In addition, yellowing can be suppressed.

  The content of the polymerization initiator is preferably 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the three-dimensional structure forming material. A radical reaction is quick that content of a polymerization initiator is 1 mass part or more, a three-dimensional object can be obtained at a desired speed | rate, and mechanical strength can also be improved. When the content of the polymerization initiator is 5 parts by mass or less, the remaining of the peroxide lump can be suppressed, the peroxide can be uniformly dispersed in the particles, and the generation of burst noise and strength unevenness at the time of radical reaction It can prevent. In addition, yellowing can be suppressed.

-Polymerizable compound-
The polymerizable compound is preferably contained in the three-dimensional structure material when the three-dimensional structure material is in a liquid state.
The polymerizable compound can be appropriately selected according to the purpose as long as it has a certain degree of viscosity, and examples thereof include a polymerizable compound having a vinyl group.
As a polymeric compound which has a vinyl group, a monofunctional polymeric compound, a polyfunctional polymeric compound, etc. are mentioned, for example. These may be used alone or in combination of two or more. Among these, in order to impart a thickening effect, it is preferable to use a monofunctional polymerizable compound and a multifunctional 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 alone or in combination of two or more. Among these, monofunctional methacrylic compounds are preferable, and monofunctional methacrylic compounds having a methyl methacrylate skeleton are more preferable.

  Examples of monofunctional methacrylic compounds having a methyl methacrylate skeleton 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. Methacrylate; 2-hydroxy ethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, hydroxyalkyl methacrylate (HAMA) such as hydroxypropyl methacrylate; tetrahydrofurfuryl methacrylate, glycidyl methacrylate, Ethylene glycol methacrylate, 2-methoxyethyl methacrylate DOO include benzyl methacrylate. These may be used alone or in combination of two or more. Among these, combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable in terms of balance such as fracture toughness, and combined use of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) Is more preferred.

--Multifunctional polymerizable compound--
As a polyfunctional polymerizable compound, a polyfunctional acryl compound, a polyfunctional methacryl compound etc. are mentioned, for example. Among these, polyfunctional methacrylic compounds are preferable, and polyfunctional methacrylic compounds having a methyl methacrylate skeleton are more preferable.

  Examples of multifunctional methacrylic compounds 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). And bisphenol A diglycidyl methacrylate (Bis-GMA). 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.

-Other ingredients-
There is no restriction | limiting in particular as another component, According to the objective, it can select suitably, For example, a fluidizer, a filler, etc. are mentioned. When the material for three-dimensional modeling is in a powder state, it is preferable in that it can easily and efficiently form a layer or the like by the material for three-dimensional modeling when it contains a fluidizing agent. It is preferable in that

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

-Formation of material layer for three-dimensional modeling-
There is no restriction | limiting in particular as a method to arrange | position the material for three-dimensional modeling on a support body, According to the objective, it can select suitably. For example, as a method of arranging in a thin layer, a method using a known counter rotation mechanism (counter roller) or the like used in the selective laser sintering method described in Japanese Patent No. 3607300, a brush for three-dimensional modeling material, A method of expanding into a thin layer using a member such as a roller or a blade, a method of pressing the surface of a material layer for three-dimensional modeling using a pressing member to expand into a thin layer, a method of using a known layered molding apparatus, etc. It can be mentioned.

-Support-
The support is not particularly limited as long as the material for three-dimensional modeling can be mounted, and can be appropriately selected according to the purpose, and a table having a mounting surface for the material for three-dimensional modeling, a diagram of JP-A-2000-328106. The base plate in the device described in 2, and the like. The mounting surface on which the material for three-dimensional modeling is mounted as the surface of the support may be, for example, a smooth surface, a rough surface, a flat surface, or a curved surface. It may be.

  In order to place the three-dimensional modeling material in a thin layer on the support using a counter rotation mechanism (counter roller), a brush or a blade, a pressing member or the like, for example, the following can be performed. That is, for example, in an outer frame (sometimes referred to as a “mold”, “hollow cylinder”, “cylindrical structure”, etc.), a support disposed so as to be able to move up and down while sliding on the inner wall of the outer frame. The material for three-dimensional modeling is placed on the body using a counter rotation mechanism (counter roller), a brush, a roller or a blade, a pressing member or the like. At this time, when using a support capable of moving up and down the inside of the outer frame, the support is disposed at a position slightly lower than the upper end opening of the outer frame, that is, the thickness of the three-dimensional modeling material layer The material for three-dimensional modeling is placed on the support while being positioned downward by a minute. By the above, the material for three-dimensional modeling can be placed in a thin layer on the support.

  In addition, when the liquid for hardening is made to act with respect to the material for three-dimensional modeling put on the thin layer in this way, hardening occurs. On the cured product of the thin layer obtained here, in the same manner as described above, the material for three-dimensional modeling is placed in a thin layer, and the three-dimensional modeling material (layer) placed in this thin layer is cured Curing occurs when the solution is applied. The curing at this time occurs not only in the three-dimensional modeling material (layer) placed in the thin layer, but also with the cured product of the thin layer obtained by curing previously present below. As a result, a cured product (three-dimensional object, layered object) having a thickness of about two layers of the three-dimensional structure forming material (layer) placed in a thin layer is obtained.

  Moreover, in order to place the material for three-dimensional modeling in a thin layer on a support, it can also be performed automatically and simply using a well-known lamination modeling apparatus. The lamination molding apparatus generally places a recoater for laminating a three-dimensional modeling material, a movable supply tank for supplying a three-dimensional modeling material onto a support, and a three-dimensional modeling material in a thin layer. And a movable forming tank for laminating. In the additive manufacturing device, the surface of the supply tank can always be slightly elevated above the surface of the forming tank by raising the supply tank, lowering the forming tank, or both. Furthermore, the layered modeling apparatus can arrange the material for three-dimensional modeling in a thin layer from the supply tank side using a recoater, and can repeatedly stack the three-dimensional modeling material in a thin layer by repeatedly moving the recoater. .

  There is no restriction | limiting in particular as thickness of the material layer for three-dimensional modeling, Although it can select suitably according to the objective, If the material for three-dimensional modeling is a liquid state, For example, 10 micrometers-70 micrometers by average thickness per one layer The following are preferable, and 20 micrometers or more and 50 micrometers or less are more preferable. When the average thickness is 10 μm or more, an enormous amount of time is not required to obtain a three-dimensional object, and when it is 70 μm or less, the dimensional accuracy of the three-dimensional object can be improved. On the other hand, when the material for three-dimensional modeling 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. When the average thickness is 10 μm or more, an enormous amount of time is not required to obtain a three-dimensional object, and when it is 200 μm or less, the dimensional accuracy of the three-dimensional object can be improved. In addition, average thickness can be measured according to a well-known method.

<Discharge process and discharge means>
The discharge step is a step of discharging three or more types of curing liquids containing three or more types of different polymerizable compounds to a predetermined region of the three-dimensional structure forming material layer, and is performed by the discharge unit.

<< Curing liquid >>
The three or more kinds of curing liquids contain three or more kinds of different polymerizable compounds, and further contain, as necessary, a polymerization initiator and other materials.
The curing liquid exhibits reactivity with the three-dimensional modeling material, and is preferably cured by energy ray irradiation.
It is preferable that the three-dimensional modeling material layer from which the curing liquid is discharged is not cured until the next layer forming step.

-Polymerizable compound-
There is no restriction | limiting in particular as a polymeric compound, 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 monofunctional polymerizable compounds and multifunctional polymerizable compounds. Among these, it is preferable to use a monofunctional polymerizable compound and a multifunctional 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.
The polymerizable compound is preferably at least one selected from acrylic / methacrylic compounds, styrene compounds, isoprene compounds, vinyl halide compounds, vinylidene halide compounds, and copolymers of these compounds.

--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 monofunctional polymerizable compounds include alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butoxyethyl methacrylate, 2-ethylhexyl methacrylate and the like; 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, combined use of methyl methacrylate (MMA) and hydroxyalkyl methacrylate (HAMA) is preferable in terms of balance such as fracture toughness, and combined use of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) Is more preferred.

--Multifunctional polymerizable compound--
As a polyfunctional polymerizable compound, a polyfunctional acryl compound, a polyfunctional methacryl compound etc. are mentioned, for example. Among these, polyfunctional methacrylic compounds are preferable, and polyfunctional methacrylic compounds having a methyl methacrylate skeleton are more preferable.

  As a polyfunctional polymerizable compound, for example, 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), 2-hydroxy-1,3-dimethacryloxypropane and the like can be mentioned. 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.

-Polymerization initiator-
As a polymerization initiator, the thing similar to the material for three-dimensional modeling can be used.
When the three-dimensional structure forming material contains a peroxide as a polymerization initiator, the curing liquid 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 a toluidine skeleton.
As a tertiary amine having a toluidine skeleton, for example, N, N-dimethyl-p-toluidine (DMPT), N, N-diethyl-p-toluidine (DEPT), N, N-di (β-hydroxyethyl) P-toluidine, N, N-di (β-hydroxypropyl) -p-toluidine and the like. 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.

-Colorant-
The curing liquid preferably further contains a colorant. When the curing liquid further contains a colorant, in the conventional binder jetting method using ultraviolet light, if the colorant is contained, absorption and irregular reflection of the ultraviolet light occur, and it can not be shaped. On the other hand, in the present invention, it can be shaped without any problem.

There is no restriction | limiting in particular as a coloring agent, According to the objective, it can select suitably, For example, dye, a pigment, etc. are mentioned.
As a pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Also, mixed crystals may be used.
As the pigment, for example, black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, metallic pigments and the like can be used.
In addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red and chromium yellow as inorganic pigments, carbon black manufactured by known methods such as contact method, furnace method and thermal method Can be used.
As organic pigments, azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dyes Chelates (eg, basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used. Among these pigments, those having good affinity to the solvent are preferably used. In addition, use of resin hollow particles and inorganic hollow particles is also possible.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone, or two or more types may be used in combination.

-Other ingredients-
The other components can be appropriately selected in consideration of various conditions such as the type of means for discharging the curing liquid, the frequency of use, and the content thereof. For example, clogging of the liquid discharge head in an ink jet printer etc. And the organic solvent, a viscosity modifier, a stabilizer and the like.
Examples of the organic solvent include alcohols such as ethanol, ethers, and ketones. Among these, ethanol is preferred.

The curing liquid is composed of at least four types, and when the reaction rates of the respective curing liquids are different, it is preferable to discharge the curing liquid having a slow reaction rate first.
In the case where at least four different types of curing liquids different from each other are discharged to the same place, it is more difficult to delaminate if the slower reaction speed is discharged first. In the case where the faster reaction rate is discharged earlier, the infiltration of another curing liquid below the region where the reaction has occurred becomes insufficient, and a layer exhibiting uniform physical properties can not be formed.
The reaction rate of the curing liquid can be measured, for example, using a Fourier transform far-infrared to mid-infrared spectrometer. Specifically, immediately after mixing a material for three-dimensional modeling and a curing liquid to prepare a sample, the sample is placed on the apparatus and the area of the peak generated or lost by reacting is traced over time. The reaction rate can be quantified and measured.

The curing liquid is composed of at least four types, and it is preferable to discharge the curing liquid having a low penetration speed first, when the penetration speed of each curing liquid to the three-dimensional modeling material layer is different.
When discharging at least four different curing liquids to the same location, it is easier to mix in the layer with the curing liquid with higher penetration speed, if the one with the slower penetration speed is discharged first. Although physical gradation is easy to realize, if the higher penetration speed is discharged first, it can not be well mixed in the layer with the low penetration speed curing liquid, which may cause unevenness.
The penetration rate of the curing liquid can be measured, for example, by transmission X-rays. Specifically, it is possible to measure the permeation rate by irradiating X-rays from the side of the tank on which the material for three-dimensional modeling is applied and tracking the behavior of the curing liquid from the moment of applying the curing liquid over time. The penetration speed can be quantified by the penetration depth of the hardening liquid in the Z-axis direction when a predetermined time has elapsed.

-Physical properties of liquid for curing-
The viscosity of the curing liquid at 25 ° C. is preferably 4 mPa · s to 20 mPa · s, and more preferably 5 mPa · s to 8 mPa · s. When the viscosity is 4 mPa · s or more and 20 mPa · s or less, stable discharge of the curing liquid becomes possible, and the dimensional accuracy and mechanical strength of the shaped article can be improved. The viscosity can be measured, for example, in accordance with JIS-K7117, and can be measured at 25 ° C. using a B-type rotational viscometer (device name: TVB-10M, manufactured by Toki Sangyo Co., Ltd.).

  The surface tension of the curing liquid is preferably 50 mN / m or less, more preferably 30 mN / m or less. When the surface tension is 50 mN / m or less, stable discharge of the curing liquid becomes possible, the dimensional accuracy of the formed article is good, and the mechanical strength is also improved.

  There is no restriction | limiting in particular as a discharge method with respect to the predetermined area | region of the material layer for three-dimensional modeling of the hardening liquid, According to the objective, it can select suitably, For example, the inkjet method, a dispenser, etc. are mentioned. Among these, the ink jet method is preferable from the viewpoint that high resolution dot control is possible.

Here, an example of the manufacturing apparatus of the three-dimensional model of this invention is shown in FIG. The manufacturing apparatus of the three-dimensional object of FIG. 2 includes the shaping side material storage tank 1 and the supply side material storage tank 2. Each of these material storage tanks stores a material for three-dimensional modeling, has a stage 3 movable up and down, and forms a layer made of the material for three-dimensional modeling on the stage.
An ink jet head 5 for discharging the hardening liquid 4 toward the three-dimensional modeling material in the material storage tank is provided on the modeling side material storage tank 1, and further, the modeling side material storage from the supply side material storage tank 2 While supplying the material for three-dimensional shaping | molding to the tank 1, it has a leveling mechanism 6 (Hereafter, it may be called a "recoater.") Which levels the material layer surface for three-dimensional shaping of the modeling side material storage tank 1.

The curing liquid 4 is dropped from the ink jet head 5 onto the three-dimensional modeling material of the modeling-side material storage tank 1. At this time, the position at which the hardening liquid 4 is dropped is determined by two-dimensional image data (slice data) obtained by slicing a three-dimensional shape which is finally desired to be shaped into a plurality of plane layers.
After drawing of 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 material for three-dimensional shaping is moved to the shaping side material storage tank 1 by the leveling mechanism 6.

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

FIG. 3 shows another example of the three-dimensional object manufacturing apparatus of the present invention. Although the manufacturing apparatus of the three-dimensional object of FIG. 3 is the same as that of FIG. 2 in principle, the supply mechanism of the material for three-dimensional modeling is different. That is, the supply side material storage tank 2 is disposed above the modeling side material storage tank 1. When drawing of the first layer is completed, the stage 3 of the modeling side material storage tank 1 descends by a predetermined amount, and while the supply side material storage tank 2 moves, a predetermined amount of three-dimensional modeling material is transferred to the modeling side material storage tank 1 The material is dropped to form a new three-dimensional modeling material layer. Thereafter, the leveling mechanism 6 compresses the three-dimensional modeling material layer to increase the bulk density, and uniformizes the height of the three-dimensional modeling material layer.
According to the layered modeling apparatus having the configuration shown in FIG. 3, the apparatus can be made compact as compared with the configuration of FIG. 2 in which two material storage tanks are arranged in plan.

  According to the method for manufacturing a three-dimensional object and the manufacturing apparatus for a three-dimensional object, a complex three-dimensional object having a plurality of different resins combined can be formed simply and efficiently, and desired physical properties are developed immediately after formation. Can be obtained. The three-dimensional object thus obtained has sufficient bonding strength between different resins, is excellent in dimensional accuracy, and can reproduce fine asperities, curved surfaces, etc., so it is excellent in aesthetic appearance and high in quality. It can be suitably used for applications.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Preparation Example 1 of Material for Three-Dimensional Sculpting)
-Preparation of material 1 for three-dimensional shaping-
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 blowing to prepare a three-dimensional modeling material 1 in powder form.

(Preparation example 2 of material for three-dimensional modeling)
-Preparation of material 2 for three-dimensional shaping-
In the same manner as in Preparation Example 1 of the material for three-dimensional modeling except that polymethyl methacrylate was replaced with polyvinylidene fluoride (Solvey, Solef 9007) in Preparation Example 1 of the material for three-dimensional modeling, the material 2 for three-dimensional modeling was prepared. Prepared.

(Preparation Example 3 of Material for Three-Dimensional Sculpting)
-Preparation of material 3 for three-dimensional shaping-
A material for three-dimensional shaping, in the same manner as in the preparation example 1 for three-dimensional shaping material, except that polymethyl methacrylate is replaced by polyvinyl chloride (K75Z manufactured by Tosoh Corporation) in preparation example 1 for three-dimensional shaping material 3 was prepared.

(Preparation Example 4 of Material for Three-Dimensional Sculpting)
-Preparation of material 4 for three-dimensional shaping-
The same procedure as in Preparation Example 1 of the material for three-dimensional shaping is repeated except that polymethyl methacrylate is replaced by chlorinated polyvinyl chloride (CPVC-HA, manufactured by Sekisui Chemical Co., Ltd.) in the preparation example 1 of the material for three-dimensional shaping The material 4 for three-dimensional modeling was prepared.

(Preparation Example 5 of Material for Three-Dimensional Sculpting)
-Preparation of material 5 for three-dimensional shaping-
In the same manner as in Preparation Example 1 of the material for three-dimensional modeling except that polymethyl methacrylate was replaced with chlorinated polyisoprene (in-house polymerized product) in Preparation Example 1 of the material for three-dimensional modeling, material 5 for three-dimensional modeling was prepared did.

(Preparation Example 6 of Material for Three-Dimensional Sculpting)
-Preparation of material 6 for three-dimensional shaping-
In Preparation Example 1 of the material for three-dimensional shaping, the same as preparation example 1 of the material for three-dimensional shaping except that polymethyl methacrylate is replaced by polyethylene oxide (Alcox R-150, manufactured by Meisei Chemical Industry Co., Ltd.), A three-dimensional modeling material 6 was prepared.

(Preparation example 7 of material for three-dimensional modeling)
-Preparation of material 7 for three-dimensional shaping-
In the same manner as in Preparation Example 1 of the material for three-dimensional shaping, except that polymethyl methacrylate was replaced by polyparavinylphenol (Marca Linker M, manufactured by Maruzen Petroleum Co., Ltd.) in the preparation example 1 of the material for three-dimensional shaping, A shaping material 7 was prepared.

(Preparation Example 8 of Material for Three-Dimensional Sculpting)
-Preparation of material 8 for three-dimensional shaping-
In the same manner as in Preparation Example 1 of the material for three-dimensional shaping, except that polymethyl methacrylate was replaced by nitrocellulose (DHX-120-170, manufactured by Inabata Sangyo Co., Ltd.) in Preparation Example 1 of the material for three-dimensional shaping, A shaping material 8 was prepared.

(Preparation Example 9 of Material for Three-Dimensional Sculpting)
-Preparation of material 9 for three-dimensional shaping-
In the same manner as in Preparation Example 1 of the material for three-dimensional modeling except that polymethyl methacrylate was replaced with polyepichlorohydrin (in-house polymerized product) in Preparation Example 1 of the material for three-dimensional modeling, the material 9 for three-dimensional modeling was used. Prepared.

(Preparation Example 10 of Material for Three-Dimensional Sculpting)
-Preparation of material 10 for three-dimensional shaping-
A preparation for stereolithography was carried out in the same manner as in the preparation 1 of the stereolithography material except that polymethyl methacrylate was replaced by a vinylidene fluoride / trichloroethylene copolymer (in-house polymerized product) in the preparation 1 of the stereolithography material. Material 10 was prepared.

(Preparation Example 11 of Material for Three-Dimensional Sculpting)
-Preparation of material 11 for three-dimensional shaping-
A three-dimensional modeling material 11 was prepared in the same manner as in the three-dimensional modeling material preparation example 1 except that no benzoyl peroxide was added in the three-dimensional modeling material preparation example 1.

(Preparation Example 12 of Material for Three-Dimensional Sculpting)
-Preparation of material 12 for three-dimensional shaping-
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 flow to prepare a three-dimensional modeling material 12 in a slurry state.

  Next, the compositions of the prepared three-dimensional modeling materials 1 to 12 are summarized in Table 1 and shown.

Preparation Example 1 of Hardening Liquid
-Preparation of curing liquid 1-
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 bisphenol A diglycidyl methacrylate (Bis-) as a polyfunctional polymerizable compound 20 parts by mass of GMA, manufactured by Sigma Aldrich Co., and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Chemical Industry Co., Ltd.) as a tertiary amine are mixed, and liquid 1 for curing is mixed. Prepared.

Preparation Example 2 of Hardening Liquid
-Preparation of curing liquid 2-
100 parts by mass of vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Chemical Industry Co., Ltd.) as a tertiary amine are mixed and cured Liquid 2 was prepared.

Preparation Example 3 of Hardening Liquid
-Preparation of hardening liquid 3-
100 parts by mass of vinyl lauryl acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Chemical Industry Co., Ltd.) as a tertiary amine are mixed and cured. Liquid 3 was prepared.

Preparation Example 4 of Hardening Liquid
-Preparation of curing liquid 4-
100 parts by mass of styrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a tertiary amine are mixed to obtain a curing liquid 4 was prepared.

Preparation Example 5 of Hardening Liquid
-Preparation of curing liquid 5-
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.), bisphenol A diglycidyl methacrylate (Bis-GMA as a polyfunctional polymerizable compound , 20 parts by mass of Sigma Aldrich, 1.5 parts by mass of N, N-dimethyl-p-toluidine (DMPT, manufactured by Tokyo Chemical Industry Co., Ltd.) as a tertiary amine, and Rhodamine (Fuji Film Co., Ltd.) as a colorant 0.5 parts by mass were mixed to prepare a curing liquid 5.

Next, Table 2 shows the production conditions of the three-dimensional object, Table 3 shows the material for three-dimensional formation, Tables 4 to 8 show the compositions of the liquids 1 to 5 for curing, the reaction speed to the three-dimensional material to be combined, permeation The speed, the presence or absence of the colorant, and the order of discharge are shown.
The reaction rate and penetration rate of the curing liquid were measured as follows.

-Reaction rate-
The reaction rate of the curing liquid is determined by mixing the three-dimensional modeling material and the curing liquid with a Fourier transform far-infrared to mid-infrared spectrometer and immediately setting the sample on the apparatus, The reaction rate was quantified by measuring the area of the peak generated or eliminated by the passage of time.
The reaction rates in Tables 4 to 8 are evaluated in 5 steps of 1 to 5, 1 represents extremely slow, 2 is slow, 3 is ordinary, 4 is fast, 5 is extremely fast, respectively.

-Penetration rate-
The permeation rate of the curing liquid is determined by irradiating the X-ray from the side of the tank on which the material for three-dimensional modeling is spread using a transmission X-ray apparatus, and behavior of the curing liquid from the moment of applying the curing liquid over time. The permeation rate was measured by following. The penetration speed was quantified from the penetration depth of the hardening liquid in the Z-axis direction when a predetermined time has elapsed.
The penetration rates in Tables 4 to 8 are evaluated in 5 steps of 1 to 5, and 1 represents extremely slow, 2 is slow, 3 is ordinary, 4 is fast, 5 is extremely fast, respectively.

Example 1
Using the obtained material 1 for three-dimensional modeling and the curing liquids 1 to 4 shown in Tables 4 to 7, the three-dimensional article 1 is obtained by the shape printing pattern of size (length 70 mm × width 12 mm): It was manufactured in the same way.

(1) First, using the apparatus for manufacturing a three-dimensional object shown in FIG. 2 (Nigata Co., Ltd., powder jig), the material 1 for three-dimensional modeling is transferred from the supply-side material reservoir to the modeling-side material reservoir. Then, on the support, a thin layer made of the three-dimensional structure forming material 1 having an average thickness of 100 μm was formed.

(2) Next, on the surface of the thin layer made of the three-dimensional structure forming material 1 formed, the curing liquids 1 to 4 are applied in the order of ejection shown in Tables 4 to 7 as an inkjet printer (SG7100, manufactured by Ricoh Co., Ltd.) The material was applied (discharged) from the nozzles and used to cure the three-dimensional structure forming material 1.

(3) Next, repeat the operations of (1) and (2) until the total average thickness of the predetermined 3 mm is reached, sequentially laminating thin layers of the hardened material 3 for three-dimensional modeling, Manufactured. When excess material for three-dimensional modeling was removed by air blow to the three-dimensional object 1 obtained, no shape loss occurred. The three-dimensional object 1 obtained was excellent in bonding strength at the resin interface and dimensional accuracy.

  Next, the bonding strength, dimensional accuracy, productivity, and multimaterialization were evaluated for the three-dimensional object 1 obtained as follows. The results are shown in Table 9.

<Joint strength>
The obtained three-dimensional object 1 was measured by a three-point bending strength test according to JIS-T-6501 using a table-top precision universal testing machine (apparatus name: AUTOGRAPH-AGS-J, manufactured by Shimadzu Corporation). The bonding strength was evaluated based on the following evaluation criteria. Here, the load cell of the universal testing machine was set to hit the boundary between different resins, and it was defined and evaluated that the bonding strength was strong if the bending strength was strong.
[Evaluation criteria]
○: 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

<Dimensional accuracy>
The dimensional accuracy of the three-dimensional object 1 was evaluated according to the following criteria.
[Evaluation criteria]
○: The surface of the obtained three-dimensional object is smooth and beautiful, and no warpage occurs. Δ: The surface of the obtained three-dimensional object has some distortion and slight warpage. ×: obtained Distortion occurs on the surface of the three-dimensional object that is being

<Productivity>
The productivity of the three-dimensional object 1 was evaluated according to the following criteria.
[Evaluation criteria]
○: A state in which the multi-materialized object can be taken out by hand after 10 minutes of shaping Δ: A state in which the multi-materialized object can be removed by hand after 1 hour of formation ×: The object even if 2 hours have passed after solid formation Is soft and can not be taken out

<Multi-materialization (physical property gradient)>
Based on the following criteria, the degree of completion of multi-materialization of the three-dimensional structure 1 was evaluated.
[Evaluation criteria]
○: A state in which the physical properties are obviously different at one end and the other end ×: A state in which no physical difference is observed over the entire surface

(Examples 2 to 20 and Comparative Example 1)
Example 1 and Example 1 except that the combination of the manufacturing conditions of the three-dimensional object shown in Table 2, the material for three-dimensional formation shown in Table 3, and the liquid for curing shown in Table 4 to Table 8 Similarly, a three-dimensional object was produced and evaluated. The results are shown in Table 9.

(Comparative example 2)
A three-dimensional object is produced by a welding process in which three-dimensional objects of different physical properties are mutually melted with hot air and welded using the three-dimensional modeling material shown in Table 3 and the curing liquid shown in Table 4, Example 1 It evaluated similarly to. The results are shown in Table 9.

(Comparative example 3)
A three-dimensional object is produced by an adhesion method in which three-dimensional objects of different physical properties are adhered to each other with an adhesive using the three-dimensional structure forming material shown in Table 3 and the curing liquid shown in Table 4. It evaluated. The results are shown in Table 9.

(Comparative example 4)
A three-dimensional object is produced by a welding method in which three-dimensional objects of different physical properties are mutually ultrasonically welded using the three-dimensional modeling material shown in Table 3 and the curing liquid shown in Table 4, and are the same as Example 1. It evaluated. The results are shown in Table 9.

* IJ as discharge means: Ink jet printer (manufactured by Ricoh Co., Ltd., SG7100)
* In Example 3, ultraviolet light was applied under the condition of 200 mJ / cm ² of integrated light quantity.
* As a dispenser of Example 7, SUPER-JET dispenser (made by Musashi engineering Co., Ltd.) was used.
* The number of adjacent dots of different composition gives different colors to each curing liquid, and the surface of the material layer for three-dimensional modeling when discharged onto the material layer for three-dimensional modeling formed using the material for three-dimensional modeling is optical It measured by observing with a microscope.
* The presence or absence of adjacent dots in the stacking direction (Z-axis direction) was confirmed by giving different colors to the respective curing liquids, and observing the cross section of the obtained shaped article with an optical microscope.

As an aspect of this invention, it is as follows, for example.
The layer formation process of forming the material layer for three-dimensional modeling using <1> three-dimensional modeling material,
A discharge step of discharging three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to a predetermined region of the three-dimensional structure forming material layer;
A method of producing a three-dimensional object which repeats the
The dots formed by discharging the three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are the other curing liquid It is arranged such that at least one region adjacent to the dot formed by discharging the ink is present.
<2> The method according to <1>, wherein the dots formed by discharging the curing liquid are adjacent to each other also in the stacking direction (Z-axis direction).
<3> The method for producing a three-dimensional object according to any one of <1> to <2>, wherein the curing liquid exhibits reactivity with the three-dimensional structure forming material.
<4> The method for producing a three-dimensional object according to any one of <1> to <3>, wherein the curing liquid is cured by energy beam irradiation.
Any one of the said <1> to <4> discharged previously from the said liquid for hardening with a slow reaction rate, when the liquid for hardening consists of at least 4 types, and each reaction liquid for hardening differs. It is a manufacturing method of the three-dimensional molded item as described in these.
&Lt; 6 &gt; When the curing liquid is at least four types, and the penetration speed of each of the curing liquids with respect to the three-dimensional modeling material layer is different, the above-mentioned <1 It is a manufacturing method of the three-dimensional molded item in any one of <><4>.
<7> The method for producing a three-dimensional object according to any one of <1> to <6>, wherein the three-dimensional modeling material layer from which the curing liquid is discharged is not cured until the next layer forming step.
<8> The method for producing a three-dimensional object according to any one of <1> to <7>, wherein the curing liquid is discharged from an inkjet head.
<9> The method for producing a three-dimensional object according to any one of <1> to <8>, wherein the polymerizable compound has a vinyl group.
<10> The <1>, wherein the polymerizable compound is at least one selected from an acryl / methacryl compound, a styrene compound, an isoprene compound, a halogenated vinyl compound, a vinylidene halide compound, and a copolymer of the compound It is a manufacturing method of the three-dimensional molded item in any one of <9>.
<11> The method for producing a three-dimensional object according to any one of <1> to <10>, wherein the curing liquid further contains a colorant.
<12> The method for producing a three-dimensional object according to any one of <1> to <11>, wherein the three-dimensional structure forming material contains organic particles.
<13> The method for producing a three-dimensional object according to <12>, wherein the polymerizable compound exhibits compatibility with the organic particles.
<14> The organic particles are polymethyl methacrylate, polyvinylidene fluoride, polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polyisoprene, polyethylene oxide, novolac, polyparavinyl phenol, nitrocellulose, polyepi Chlorohydrin, copolymer containing methyl methacrylate, styrene / acrylonitrile copolymer, citraconic anhydride / styrene copolymer, vinyl chloride / vinylidene chloride copolymer, vinylidene fluoride / halogenated ethylene copolymer, It is a manufacturing method of the three-dimensional object in any one of said <12> to <13> which is at least 1 sort (s) selected from an epichlorohydrin ethylene oxide copolymer.
<15> The method for producing a three-dimensional object according to any one of <12> to <14>, wherein the three-dimensional structure forming material further contains an organic peroxide.
<16> Layer forming means for forming a three-dimensional modeling material layer using a three-dimensional modeling material;
Ejecting means for ejecting three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to a predetermined region of the three-dimensional structure forming material layer,
An apparatus for producing a three-dimensional object having
The dots formed by discharging the three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are the other curing liquid It is arranged such that at least one region adjacent to the dot formed by discharging the ink is present.
<17> The apparatus for producing a three-dimensional object according to <16>, wherein the dots formed by discharging the curing liquid are adjacent to each other also in the stacking direction (Z-axis direction).
<18> The apparatus for producing a three-dimensional object according to any one of <16> to <17>, wherein the curing liquid exhibits reactivity with the three-dimensional structure forming material.
<19> The manufacturing apparatus of a three-dimensional object according to any one of <16> to <18>, wherein the curing liquid is cured by energy beam irradiation.
<20> Any one of the above <16> to <19> discharged first from the curing liquid having a slow reaction rate when the curing liquid consists of at least four types and the reaction speeds of the respective curing liquids are different. It is a manufacturing apparatus of the three-dimensional molded item described in.
&Lt; 21 &gt; When the curing liquid is at least four types, and the penetration speed of each of the curing liquids with respect to the three-dimensional modeling material layer is different, the curing liquid having a slow penetration speed is discharged first. It is a manufacturing apparatus of the three-dimensional object in any one of <><19>.
<22> The manufacturing apparatus for a three-dimensional object according to any one of <16> to <21>, wherein the three-dimensional modeling material layer from which the curing liquid is discharged is not cured until the next layer forming step.
<23> The manufacturing apparatus of a three-dimensional object according to any one of <16> to <22>, wherein the curing liquid is discharged from an inkjet head.
<24> The manufacturing apparatus of a three-dimensional object according to any one of <16> to <23>, wherein the polymerizable compound has a vinyl group.
<25> The <16>, wherein the polymerizable compound is at least one selected from an acryl / methacryl compound, a styrene compound, an isoprene compound, a halogenated vinyl compound, a vinylidene halide compound, and a copolymer of the compound It is a manufacturing apparatus of the three-dimensional object in any one of <24>.
<26> The apparatus for producing a three-dimensional object according to any one of <16> to <25>, wherein the curing liquid further contains a colorant.
<27> The device for producing a three-dimensional object according to any one of <16> to <26>, wherein the three-dimensional structure forming material contains organic particles.
<28> The manufacturing apparatus of a three-dimensional object according to <27>, wherein the polymerizable compound exhibits compatibility with the organic particles.
<29> The organic particles are polymethyl methacrylate, polyvinylidene fluoride, polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polyisoprene, polyethylene oxide, novolac, polyparavinyl phenol, nitrocellulose, polyepi Chlorohydrin, copolymer containing methyl methacrylate, styrene / acrylonitrile copolymer, citraconic anhydride / styrene copolymer, vinyl chloride / vinylidene chloride copolymer, vinylidene fluoride / halogenated ethylene copolymer, It is a manufacturing apparatus of the three-dimensional object in any one of said <27> to <28> which is at least 1 sort (s) selected from an epichlorohydrin ethylene oxide copolymer.
<30> The apparatus for producing a three-dimensional object according to any one of <27> to <29>, wherein the three-dimensional structure forming material further contains an organic peroxide.

  The method for producing a three-dimensional object according to any one of <1> to <15> and the device for producing a three-dimensional object according to any one of <16> to <30> solve the above-mentioned various problems in the related art And the object of the present invention can be achieved.

      4 Liquid for curing

Claims (16)

A layer forming step of forming a three-dimensional modeling material layer using a three-dimensional modeling material;
A discharge step of discharging three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to a predetermined region of the three-dimensional structure forming material layer;
A method of producing a three-dimensional object which repeats the
The dots formed by discharging the three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are the other curing liquid The method for manufacturing a three-dimensional object, wherein an area adjacent to the dot formed by discharging the ink is arranged in at least one place.   The method for producing a three-dimensional object according to claim 1, wherein the dots formed by discharging the curing liquid are adjacent to each other also in the stacking direction (Z-axis direction).   The method for producing a three-dimensional object according to any one of claims 1 to 2, wherein the curing liquid exhibits reactivity with the three-dimensional structure material.   The method for producing a three-dimensional object according to any one of claims 1 to 3, wherein the curing liquid is cured by energy beam irradiation.   The three-dimensional structure according to any one of claims 1 to 4, wherein the curing liquid is discharged first from the curing liquid having a slow reaction speed when the curing liquid consists of at least four types and the reaction speeds of the respective curing liquids are different. Method of manufacturing objects.   The liquid for curing according to any one of claims 1 to 4, wherein the liquid for curing is discharged first from the liquid for curing having a low permeation rate when the liquid for curing comprises at least four types and the permeation speeds of the respective liquids for curing to the three-dimensional modeling material layer differ. The manufacturing method of the three-dimensional molded article in any one.   The method for producing a three-dimensional object according to any one of claims 1 to 6, wherein the three-dimensional structure forming material layer from which the curing liquid is discharged is not cured until the next layer forming step.   The method for producing a three-dimensional object according to any one of claims 1 to 7, wherein the curing liquid is discharged from an ink jet head.   The method for producing a three-dimensional object according to any one of claims 1 to 8, wherein the polymerizable compound has a vinyl group.   10. The method according to claim 1, wherein the polymerizable compound is at least one selected from an acryl / methacryl compound, a styrene compound, an isoprene compound, a vinyl halide compound, a vinylidene halide compound, and a copolymer of the compound. The manufacturing method of the three-dimensional molded item as described in.   The method for producing a three-dimensional object according to any one of claims 1 to 10, wherein the curing liquid further contains a colorant.   The method for producing a three-dimensional object according to any one of claims 1 to 11, wherein the material for three-dimensional structure comprises organic particles.   The method for producing a three-dimensional object according to claim 12, wherein the polymerizable compound exhibits compatibility with the organic particles.   The organic particles are polymethyl methacrylate, polyvinylidene fluoride, polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polyisoprene, polyethylene oxide, novolak, polyparavinyl phenol, nitrocellulose, polyepichlorohydrin. , Copolymers containing methyl methacrylate, styrene / acrylonitrile copolymer, citraconic anhydride / styrene copolymer, vinyl chloride / vinylidene chloride copolymer, vinylidene fluoride / halogenated ethylene copolymer, and epichlorohydric acid The method for producing a three-dimensional object according to any one of claims 12 to 13, which is at least one selected from phosphorus-ethylene oxide copolymers.   The method for producing a three-dimensional object according to any one of claims 12 to 14, wherein the three-dimensional material further contains an organic peroxide. Layer forming means for forming a three-dimensional modeling material layer using a three-dimensional modeling material;
Ejecting means for ejecting three or more kinds of curing liquids containing three or more kinds of different polymerizable compounds to a predetermined region of the three-dimensional structure forming material layer,
An apparatus for producing a three-dimensional object having
The dots formed by discharging the three or more types of curing liquids on the three-dimensional modeling material layer are adjacent to each other, and the dots formed by discharging one curing liquid are the other curing liquid An apparatus for manufacturing a three-dimensional object, which is arranged such that at least one region adjacent to a dot formed by discharging the ink is present.