JP2005067138A - Method for production of three-dimensionally shaped product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a three-dimensionally shaped product favorable in binder discharging property and excellent in curability. <P>SOLUTION: This production method for the three-dimensionally shaped product comprises sequentially repeating a process (layer-forming process) for charging a powdery material onto a support to form a layer having a predetermined thickness and a process (cross-sectional shape-forming process) for bonding a powdery material layer with a binder so as to become a cross-sectional shape obtained by cutting an object to be shaped in a parallel cross section. In this case, the viscosity of the binder is 5-100 mPa/s at 25°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a three-dimensional structure, and more particularly, to a method for manufacturing a three-dimensional structure by sequentially laminating cross-sectional shapes obtained by cutting a target three-dimensional structure with a plurality of parallel cross sections. .

  Conventionally, a thin layer of powder is bonded with a binder in correspondence with each cross-sectional shape obtained by cutting a three-dimensional modeling object on a plurality of parallel surfaces, and the cross-sectional shapes of the combined thin layers are sequentially laminated. Thus, a technique for creating a modeled object that becomes a three-dimensional model of a modeled object is known.

  Such a technique is called rapid prototyping, and can be used for parts trial production and design confirmation. In recent years, an inexpensive and high-speed method using an ink jet suitable for color modeling has been proposed. For example, there is one disclosed in Patent Document 1. The specific procedure of this three-dimensional modeling is demonstrated below.

  First, the blade mechanism spreads the powder into a thin layer having a uniform thickness on a flat surface, and an inkjet nozzle head is scanned over the thin layer surface of the powder, and the cross section of the object to be cut is cut in parallel cross sections. The binder is discharged according to the shape. The powder material in the region where the binder has been discharged is subjected to necessary operations to bring the powder into a bonded state, and also to the already formed lower layer cross-sectional shape. And the process of discharging a binder is repeated, laminating | stacking a powder thin layer sequentially on the upper part until the whole molded article is completed. Finally, since the areas where the binder was not discharged are in a state where the powders are not individually joined to each other, the powder can be easily removed when removing the shaped object from the apparatus. To be separated. By the above operation, a desired three-dimensional structure can be manufactured.

  Further, in the same manner, a colored three-dimensional structure is obtained by discharging a binder that is colored yellow (Y), magenta (M), or cyan (C). Is disclosed.

However, in the above-described method, the actual condition is that the characteristics (texture, color) of the modeled object do not reach a satisfactory level as compared with a desired object. In particular, it is impossible to obtain a three-dimensional structure that requires a transparent feeling by a conventional method because of the difference in properties between the powder and the binder. Furthermore, in order to impart smoothness to the surface, it is necessary to perform the overcoating and polishing treatments manually, which requires time and cost.
In addition, with manual coloring, it is generally difficult to reliably draw a desired pattern or the like at a predetermined position of a three-dimensional structure.

On the other hand, since the three-dimensional structure immediately after manufacture is formed only by the bonding force of the binder, the strength may be weak and may be broken depending on the method of handling the three-dimensional structure. Therefore, conventionally, the strength has been increased by impregnating the powder particles of the three-dimensional structure after manufacture with resin and wax. However, such a process requires labor and time.
In addition, conventionally used binders also have a problem of causing clogging in an ink jet nozzle.

Japanese Patent No. 2729110 JP 2001-150556 A

  The problem to be solved by the present invention is to provide a method for producing a three-dimensional structure that has good ejection properties and excellent curability.

The above object of the present invention has been achieved by the following means.
(1) A step of forming a powder material on a support in a layer having a predetermined thickness (layer formation step), and a binder of the powder material layer so as to have a cross-sectional shape obtained by cutting a modeling object in parallel cross sections In the manufacturing method of a three-dimensional structure including the step of sequentially repeating the bonding step (cross-sectional shape forming step), the viscosity of the binder at 25 ° C. is 5 to 100 mPa · s. Manufacturing method,
(2) The method for producing a three-dimensional structure according to (1), wherein the binder is cured by applying energy,
(3) The method for producing a three-dimensional structure according to (1) or (2), wherein the binder is cured by applying light energy,
(4) As the binder, two or more kinds of bonds selected from the group consisting of at least one colored binder, a white colored binder, and a colorless binder, preferably a colorless and transparent binder. (1)-(3) the manufacturing method of the three-dimensional structure as described in any one of using an agent,
(5) The three-dimensional structure according to any one of (1) to (4), wherein the colored binder comprises at least three binders of a yellow binder, a magenta binder, and a cyan binder. Method,
(6) The three-dimensional according to any one of (1) to (5), wherein the colored binder comprises at least four binders of a yellow binder, a magenta binder, a cyan binder, and a black binder. Manufacturing method of shaped objects,
(7) The binder comprises (a) at least one trifunctional or higher functional (meth) acrylate and (b) at least one monofunctional and / or bifunctional (meth) acrylate (1) to (6) A method for producing a three-dimensional structure according to any one of the above,
(8) The method for producing a three-dimensional structure according to (7), wherein the trifunctional or higher functional (meth) acrylate is a tetrafunctional, pentafunctional, or hexafunctional (meth) acrylate,
(9) The method for producing a three-dimensional structure according to any one of (1) to (8), wherein an organic solvent having a boiling point of 150 ° C. or lower is used as a viscosity modifier of the binder.

  According to the present invention, a three-dimensional structure can be manufactured without causing clogging of the binder at the print head nozzle. As a result, a high-quality three-dimensional structure that has been impossible until now can be manufactured easily, inexpensively and stably.

  The present invention combines a powder material layer so as to have a cross-sectional shape in which a powder material is formed on a support in a layer having a predetermined thickness (layer formation step) and a modeling object is cut in a parallel cross-section. 3D modeling characterized in that the viscosity of the binder at 25 ° C. is 5 to 100 mPa · s in the method of manufacturing a three-dimensional model including the step of sequentially repeating the step of bonding with the agent (cross-sectional shape forming step). It relates to the manufacturing method of goods.

  The binder used in the present invention is preferably cured by applying energy, and more preferably cured by applying light energy from the outside. The viscosity of the binder at 25 ° C. is 5 to 100 mPa · s, preferably 5 to 80 mPa · s, and more preferably 10 to 50 mPa · s. Detailed explanation will be given later.

  The powder material used in the present invention is preferably a fine powder having an average particle size of 0.1 to 1,000 μm, and more preferably a fine powder having an average particle size of 1 to 50 μm. The particle size distribution may be wide but is preferably narrow. The particle size distribution is preferably close to monodispersion, and the coefficient of variation of the particle size distribution is preferably 20% or less, and particularly preferably 15% or less. The powder material may be an organic material, an inorganic material, or an inorganic / organic composite material. Detailed explanation will be given later.

As the support for laying the powder material, a support having an arbitrary surface shape can be used, but a support having a smooth surface is preferable, and a support having a flat surface can be preferably used. In the manufacturing method of this invention, it is preferable to use the horizontal support body which has the flame | frame which can be extended | stretched more than the height of the three-dimensional structure to manufacture.
The predetermined thickness of the powder material layer is preferably a layer having a thickness of 10 to 500 μm per slice pitch, and more preferably a thickness of 50 to 150 μm. Each time the layer forming step and the colored cross-sectional shape forming step are repeated once, the lamination thickness of the entire powder material layer is increased by the slice pitch.
The colored cross-sectional shape means a shape having a completely cross-sectional shape obtained by cutting a modeling target object with a large number of parallel surfaces and accompanied by coloring corresponding to the shape. The cross-sectional shape may be a hollow shaped object particularly in the case of an opaque shaped object, and in this case, it is sufficient to reproduce the shape near the contour of the shape. It is only necessary to reproduce the color of the surface of the model, and it is important to reproduce the color of the contour of the shape.

The outline of the method for producing a three-dimensional structure of the present invention will be described with reference to the drawings.
Drawing 1 is a mimetic diagram showing a main process about one embodiment of a manufacturing method of a three-dimensional structure of the present invention.
In the manufacturing method of the present invention, a thin layer 1 of a powder material is formed on a support (modeling stage) 4 provided on a three-dimensional modeling unit 3. The support 4 is supported by the vertical movement unit 5 and is surrounded by a frame 6. By moving the blade 7 extending in the Y direction (direction perpendicular to the paper surface) in the X direction (from the left to the right on the paper surface) on the excess powder material supplied from the powder supply unit onto the support 4 A thin layer 1 is formed. On the thin layer 1 formed in this manner, the binder is supplied onto the thin layer 1 of the powder material from the inkjet head 8 of the binder application portion according to the cross-sectional shape data, thereby forming the binder application region 2. To do. When the binder is a two-component reactive epoxy resin or the like, these two reactive solutions are supplied to almost the same spot from different ink jet nozzles to form the binder application region 2. These reactive two liquids are cured by applying thermal energy at room temperature to bond the powder material. When the binder is an ultraviolet curable binder, the binder application region 2 bonds the powder material by being cured by the ultraviolet rays irradiated from the ultraviolet irradiation unit 9.
Subsequently, the vertical movement unit 5 is moved downward by one slice pitch to form a new powder material layer.
On the newly formed thin layer, the binder is supplied from the inkjet head of the binder application portion according to the next adjacent sectional shape data, and a new binder application region is formed. By irradiating this region with ultraviolet rays and curing it, the powder material is bonded over the entire thickness of the thin layer in the binder application region 2 to form a cross-sectional shape, and is also bonded to the cross-sectional shape immediately before.
It is possible to obtain the three-dimensional structure 10 by separating the powder material in the region to which the binder is not applied after the formation of the thin layer 1 of the powder material, the supply of the binder, and the curing are sequentially repeated as many times as necessary. it can.
FIG. 2 is a perspective view schematically showing cross-sectional shapes formed in adjacent layers in the manufacture of the three-dimensional structure as described above.

  A preferred embodiment of the method for producing a three-dimensional structure of the present invention will be described below. In the following five steps, prior to the (powder) layer forming step and the colored cross-sectional shape forming step, a three-dimensional shape color data creating step and a colored cross-sectional shape data creating step for each cross-section are performed.

  In the first step, the computer is made to create model data representing a three-dimensional modeling object having a colored pattern or the like on the surface. As the model data that is the basis for modeling, color three-dimensional model data created by general 3D-CAD modeling software can be used. It is also possible to use data and texture of the three-dimensional colored shape measured by the three-dimensional shape input device.

In the second step, the computer creates cross-section data for each cross-section obtained by slicing the modeling object in the horizontal direction from the model data. A cross-sectional body sliced at a pitch (layer thickness t) corresponding to the thickness of one layer of powder to be laminated is cut out from the model data, and shape data and coloring data indicating a region where the cross-section exists are created as cross-sectional data. In the present invention, “shape data” and “coloring data” are also collectively referred to as “colored (cross-sectional) shape data”.
Subsequently, information on the thickness of the powder layer (slice pitch when creating cross-sectional data) and the number of layers (the number of sets of colored shape data) when modeling the modeling object are obtained from the computer as a drive control unit of the pattern creation device. Is input.

In a 3rd step, the powder material used as the material which manufactures a three-dimensional structure in the modeling stage is supplied. Using a powder material counter rotation mechanism (hereinafter referred to as “counter roller”), the powder material is spread in a layer having a uniform thickness, and after the supply of a predetermined amount of powder is completed, the supply of the powder material is stopped. .
In the present invention, “sequentially repeating the layer forming step and the cross-sectional shape forming step” means (1) a step of forming a cross-sectional shape on the entire surface of the new layer after completing the new layer forming step. In addition to this, (2) forming a cross-sectional shape for a newly formed layer region before the formation of the new layer is completed while performing a new layer forming step. The latter example is exemplified in JP-A No. 2002-307562.

The fourth step is a step of forming a colored cross-sectional shape based on the colored shape data of the cut surface under the control of the drive control unit. This process preferably employs a non-contact method. As a representative example, an ink jet method will be described below as an example.
Based on the shape data and the color data created in the second step, the data is converted into bitmap information of each color of CMY subdivided into a grid, and the inkjet head is moved in the XY plane. Then, during the movement, the ultraviolet (UV) curable binder is appropriately discharged from each inkjet discharge nozzle based on the coloring data. As the binder, two or more kinds of binders selected from the group consisting of at least one colored binder, a white binder, and a colorless and transparent binder are used.
The colored binder is preferably a combination of three colors of yellow (Y), magenta (M), and cyan (C), which are the three primary colors of the subtractive color method. In the present invention, a binder colored yellow is called “yellow binder”, a binder colored magenta is called “magenta binder”, and a binder colored cyan is called “cyan binder”. M dye and C dye may be used as binders colored in two different shades. Colorless binders can be used to adjust the color density of CMY. In addition, a binder (white binder) containing a white pigment such as titanium white or a binder (black binder) colored with a black (black) dye can be used in combination to develop a desired effect.
The total discharge amount of the colored binder, the colorless binder and the white binder is preferably constant per unit area.
In addition, as another example of forming the colored cross-sectional shape, after discharging only a colorless UV curable binder to the powder material based on the shape data and curing by ultraviolet irradiation, the binder is based on the coloring data of the layer. It is also possible to use a two-stage process in which a normal CMY ink jet that does not contain is discharged onto a combined powder material layer.

By performing UV exposure on the surface of the binder discharged by the UV exposure apparatus simultaneously with or after the discharge of the ultraviolet curable binder, a bonded body of powder material is generated.
When the atmosphere of UV irradiation is an inert gas atmosphere such as nitrogen or argon, the delay effect due to oxygen of the radical polymerizable compound can be reduced.

The ink jet method used here mainly refers to an on-demand ink jet method, and examples thereof include a piezo on demand ink jet method, a thermal on demand ink jet method, and an electrostatic on demand ink jet method. Preferably, the UV curable binder is stable. From the viewpoint of properties, a piezo on-demand ink jet method and an electrostatic on-demand ink jet method can be mentioned.
Furthermore, the target three-dimensional structure is obtained by repeating the third step and the fourth step.
In addition, in the area | region of the powder material in which a binder is not apply | coated, the powder has hold | maintained the independent state.

In the fifth step, the powder material in the region to which the binder is not applied is separated, and the combined powder (three-dimensional structure) bonded by the binder is taken out. The unbound powder material can be collected and reused as a material.
By sequentially repeating the third step to the fourth step, a three-dimensional structure can be manufactured by sequentially laminating colored combinations of powder materials corresponding to the cut surfaces obtained by cutting the modeling object on a plurality of surfaces. it can.
A layer of a powder material having a refractive index n ₁ is bonded to a cross-sectional shape colored with a binder that gives a refractive index n ₂ (where −0.1 ≦ (n ₁ −n ₂ ) ≦ 0.1). ), A transparent or substantially transparent three-dimensional structure can be manufactured.

  You may perform post-processing processes, such as cleaning, heat processing, resin or wax penetration, and grinding | polishing, with respect to the obtained three-dimensional structure. The cleaning is performed by blowing the three-dimensional structure and by removing any powder left in the gap by brushing to remove excess powder. The heat treatment increases the strength and durability of the three-dimensional structure. Wax permeation reduces the porosity, makes the three-dimensional structure water-resistant, and makes it easier to polish. Abrasive finish improves surface smoothness.

Each component used in the present invention will be described below. However, the specific contents are not limited to the following explanation contents.
(Binder)
The binder used in the present invention is cured by applying energy. Binders that cure by “energy application” include resins that cure by a thermally activated chemical reaction. Such thermosetting resins include epoxy resins.
The epoxy resin is a resin having a three-membered ring called oxirane, and has a chain or cyclic aliphatic or aromatic ring as a reactive group. When treated with a curing agent, the epoxy resin is cured. Become. An example of the epoxy resin is diglycidyl ether of bisphenol A (DGEBA). Moreover, as a hardening | curing agent, polyamide (versamide type), a polyamine, an acid anhydride, and a polymercaptan can be illustrated.
In the present invention, when an epoxy resin is used as a binder, it is preferable that the epoxy resin and its curing agent be discharged from separate nozzles and mixed on the powder material to be cured.
Examples of thermosetting resins other than epoxy resins include vinyl urethane and cyanoacrylate.

  A suitable external heating source can be used to increase the cure rate of the thermosetting binder. The curing reaction can be accelerated by applying hot air to the binder application region or applying infrared energy or microwave energy.

  The thermally curable binder that can be used in the present invention may be a liquid that does not involve a chemical reaction. As a specific example, there is an example in which a starch-based powder material is supplied with a water-based binder, and starch particles are bonded together with water, Z Corporation (Z Corporation). In the three-dimensional modeling printer of No. 1, it is practically used in a system for binding powder particles made of starch / cellulose. Such a binder is also described in JP-A-6-218712 (Patent No. 2729110).

  The binder used in the present invention is preferably a binder that is cured by application of light energy, and more preferably a UV curable binder. The UV curable binder includes a photopolymerization initiator and at least one polymerizable compound as essential components, and has a function of binding almost all constituent materials by UV light and binding a powder material. As a ratio of each constituent material, the photopolymerization initiator is preferably contained in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the polymerizable compound and the photopolymerization initiator. . The content of the polymerizable compound is preferably 90 to 99.5% by weight, more preferably 95 to 99.9% by weight.

The viscosity of the binder at 25 ° C. is 5 to 100 mPa · s, preferably 5 to 80 mPa · s, and more preferably 10 to 50 mPa · s. In the present invention, the viscosity of the binder means a value measured at 25 ° C. with an E-type viscometer (Tokyo Keiki VISCONIC ELD).
It is preferable that a polyfunctional polymerizable compound having a high viscosity and a polymerizable compound having a low viscosity are appropriately mixed and used so that the viscosity of the binder at 25 ° C. falls within the above range.
The polyfunctional polymerizable compound having a high viscosity is preferably a trifunctional or higher functional (meth) acrylate. The trifunctional or higher functional (meth) acrylate is preferably tetrafunctional, pentafunctional or hexafunctional (meth) acrylate.
The polymerizable compound having a low viscosity is preferably monofunctional and / or bifunctional (meth) acrylate.
An organic solvent having a boiling point of 150 ° C. or lower can also be used as a viscosity modifier for the binder.

[Polymerizable compound]
The polymerizable compound that can be used in the UV curable binder is preferably a compound in which addition polymerization or ring-opening polymerization is initiated by irradiation with UV light due to radical species or cationic species generated from the photopolymerization initiator to generate a polymer. used. Examples of the polymerization mode of addition polymerization include radical, cation, anion, metathesis, and coordination polymerization. Examples of the ring-opening polymerization method include cation, anion, radical, metathesis, and coordination polymerization.
Examples of the addition polymerizable compound include compounds having at least one ethylenically unsaturated double bond. As the addition polymerizable compound, a compound having at least one, preferably two or more terminal ethylenically unsaturated bonds can be preferably used. Such terminal ethylenically unsaturated compounds are widely known in the industrial field. In the present invention, the binder composition can be used without particular limitation as long as it can be stably ejected from an inkjet nozzle.
The ethylenically unsaturated polymerizable compound has a chemical form of a monofunctional polymerizable compound and a polyfunctional polymerizable compound (ie, bifunctional, trifunctional and 4-6 functional), or a mixture thereof. Examples of the monofunctional polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. As the polyfunctional polymerizable compound, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

  Also, addition reaction products, monofunctional or polyfunctional unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates and epoxies. A dehydration condensation reaction product with a functional carboxylic acid can also be used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol can also be used.

  As a specific example of the radical polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, a (meth) acrylic acid ester is representative, and at least one kind of a trifunctional or higher functional (meth) acrylate is used. It is preferable to use at least one of monofunctional and / or bifunctional (meth) acrylates.

  Specific examples of monofunctional (meth) acrylates include tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (meth) Examples thereof include acrylate and tetrahydrofurfuryl (meth) acrylate.

  Specific examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol di ( Mention may be made of (meth) acrylate and dipentaerythritol di (meth) acrylate.

  Specific examples of trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate Mention may be made of the rate.

  Specific examples of tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, ethoxylated penta Mention may be made of erythritol tetra (meth) acrylate.

Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Specific examples of hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa (meth) acrylate Can be mentioned.

  Here, the above notation of (meth) acrylate is an abbreviated notation indicating that it can have both a methacrylate structure and an acrylate structure.

In addition to (meth) acrylate, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester and the like can also be used as the polymerizable compound.
Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 can be used.

  Specific examples of amide monomers of unsaturated carboxylic acid and aliphatic polyvalent amine compound include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (I) to a polyisocyanate compound having two or more isocyanate groups. Etc.
Formula (I)
^{_{CH 2 = C (R 1)}} COOCH 2 CH (R 2) OH
(However, R ¹ and R ² represent H or CH _3. )

  In the present invention, a cationic ring-opening polymerizable compound having at least one cyclic ether group such as an epoxy group and / or an oxetane group in the molecule can be used as a UV curable binder together with a UV cationic polymerization initiator. .

The general cationic polymerizable compounds preferably used in the present invention will be described below. Examples of the cationic polymerizable compound include curable compounds containing a ring-opening polymerizable group, and among them, a heterocyclic group-containing curable compound is preferable. Examples of such a curable compound include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, vinyl ethers, etc., and particularly epoxy derivatives, oxetane derivatives, and vinyl ethers. preferable.
Examples of preferable epoxy derivatives are roughly classified into monofunctional glycidyl ethers, polyfunctional glycidyl ethers, monofunctional alicyclic epoxies, polyfunctional alicyclic epoxies, and the like.

  Specific examples of monofunctional and polyfunctional glycidyl ethers include diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether), trifunctional or higher glycidyl ethers (trimethylolethane triglycidyl ether) , Trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, Phenol novolac resin polyglycidyl ether, etc.), alicyclic epoxies (Celoxide 2021P, Celoxy Id 2081, epolide GT-301, epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (OX-SQ, PNOX-1009 (manufactured by Toagosei Co., Ltd.)) and the like are included, but the present invention is not limited to these.

In the present invention, an alicyclic epoxy derivative can be preferably used. The “alicyclic epoxy group” refers to a partial structure obtained by epoxidizing a double bond of a cycloalkene ring such as a cyclopentene group or a cyclohexene group with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
The alicyclic epoxy compound is preferably a polyfunctional alicyclic epoxy having two or more cyclohexene oxide groups or cyclopentene oxide groups in one molecule. Specific examples of the monofunctional or polyfunctional alicyclic epoxy compound include 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, and di (3,4-epoxy). Cyclohexyl) adipate, di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide Can be mentioned.
One type of alicyclic epoxy compound may be used, or a mixture of two or more types may be used.
Various alicyclic epoxy compounds are commercially available and can be obtained from Union Carbide Japan Co., Ltd., Daicel Chemical Industries, Ltd., and the like.

The glycidyl compound which has a normal epoxy group which does not have an alicyclic structure in a molecule | numerator can be used independently, or it can also use together with said alicyclic epoxy compound.
Examples of such normal glycidyl compounds include glycidyl ether compounds and glycidyl ester compounds, but it is preferable to use glycidyl ether compounds in combination.
Specific examples of the glycidyl ether compound include 1,3-bis (2,3-epoxypropyloxy) benzene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy. Resin, aromatic glycidyl ether compound such as trisphenol methane type epoxy resin, aliphatic glycidyl ether compound such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane tritriglycidyl ether Can be mentioned. Examples of the glycidyl ester include glycidyl ester of linolenic acid dimer.
Glycidyl ethers can be obtained commercially from Yuka Shell Epoxy Co., Ltd.

  In the present invention, a compound having an oxetanyl group which is a 4-membered cyclic ether (hereinafter, also simply referred to as “oxetane compound”) can be used. An oxetanyl group-containing compound is a compound having one or more oxetanyl groups in one molecule. This oxetanyl group-containing compound is roughly classified into a monofunctional oxetane compound having one oxetanyl group in one molecule and a polyfunctional oxetane compound having two or more oxetanyl groups in one molecule.

  As the monofunctional oxetane compound, a compound represented by the following general formula (1) is preferable.

式（１）中、Ｒ₁はメチル基又はエチル基を示す。Ｒ₂は、炭素数６ないし１２の炭化水素基を示す。
Ｒ₂の炭化水素基としては、フェニル基やベンジル基も採りうるが、炭素数６ないし８のアルキル基が好ましく、２−エチルへキシル基等の分岐アルキル基が特に好ましい。Ｒ₂がフェニル基であるオキセタン化合物の例は、特開平１１−１４０２７９号公報に記載されている。Ｒ₂が置換されていても良い、ベンジル基であるオキセタン化合物の例は、特開平６−１６８０４号公報に記載されている。

In formula (1), R ₁ represents a methyl group or an ethyl group. R ₂ represents a hydrocarbon group having 6 to 12 carbon atoms.
The hydrocarbon group for R ₂ may be a phenyl group or a benzyl group, but is preferably an alkyl group having 6 to 8 carbon atoms, particularly preferably a branched alkyl group such as a 2-ethylhexyl group. Examples of oxetane compounds in which R ₂ is a phenyl group are described in JP-A No. 11-140279. An example of an oxetane compound which is a benzyl group, in which R ₂ may be substituted, is described in JP-A-6-16804.

  In this invention, although a polyfunctional oxetane compound can be used, a preferable compound group is represented by following General formula (2).

式（２）中、ｍは２、３又は４の自然数を示し、Ｚは酸素原子、硫黄原子、又はセレン原子を表す。Ｒ₃は水素原子、フッ素原子、炭素数が１ないし６の直鎖もしくは分岐状のアルキル基、炭素数が１ないし６のフルオロアルキル、アリル基、フェニル基又はフリル基である。Ｒ₄は、ｍ価の連結基であり、炭素数が１ないし２０の基であることが好ましく、１個以上の酸素原子、硫黄原子を含んでいても良い。
Ｚは酸素原子が好ましく、Ｒ₃はエチル基が好ましく、ｍは２が好ましく、Ｒ₄としては、炭素数が１ないし１６の線形又は分岐アルキレン基、線形又は分岐ポリ（アルキレンオキシ）基が好ましく、Ｒ₃、Ｒ₄、Ｚ、及びｍに対する好ましい例の内から任意の２つ以上を組み合わせた化合物は更に好ましい。

In formula (2), m represents a natural number of 2, 3 or 4, and Z represents an oxygen atom, a sulfur atom or a selenium atom. R ₃ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluoroalkyl having 1 to 6 carbon atoms, an allyl group, a phenyl group or a furyl group. R ₄ is an m-valent linking group, preferably a group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms and sulfur atoms.
Z is preferably an oxygen atom, R ₃ is preferably an ethyl group, m is preferably 2, and R ₄ is preferably a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched poly (alkyleneoxy) group. , R ₃ , R ₄ , Z, and m are more preferably compounds obtained by combining any two or more of the preferred examples.

  As the UV curable binder of the present invention, it is also preferable to use a radical polymerizable ethylenically unsaturated compound and a cationic polymerizable cyclic ether (epoxy derivative and / or oxetane derivative) in combination. There is an advantage that a bonded body having a balanced physical property can be obtained due to the structure of an interpenetrating polymer network (IPN). In this case, it is preferable to use a radical photopolymerization initiator and a cationic photopolymerization initiator (such as an onium salt) in combination as the photopolymerization initiator.

[Photopolymerization initiator]
The curable binder used in the present invention can be cured by a thermal polymerization initiator, but is preferably cured using a photopolymerization initiator.
The photopolymerization initiator used in the present invention refers to a compound that generates active radical species or cationic species by active energy rays and initiates and accelerates the polymerization reaction of the binder. As active energy rays, radiation, gamma rays, alpha rays, electron rays, ultraviolet rays and the like are used. Among these, the method of curing with ultraviolet rays is particularly preferable.

  As the thermal polymerization initiator that can be used in the present invention, a compound that is known and has a bond having a small bond dissociation energy can be used. The thermal polymerization initiators can be used alone or in combination of two or more.

  Examples of the thermal polymerization initiator include organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oniums. A salt compound is mentioned.

Preferred examples of the polymerization initiator that generates radicals by the action of light include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and benzyl compounds. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy -2-methyl-propiophenone, p-dimethylaminoacetone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and benzyldimethyl ketal. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. Examples of the benzyl compound include benzyl and benzyl-β-methoxyethyl acetal.
As mentioned above, since sulfonium salts and iodonium salts that are usually used as photocation generators act as radical generators upon irradiation with ultraviolet rays, these may be used alone in the present invention. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.

  As a photopolymerization initiator that generates an active cationic species by ultraviolet rays, an onium salt initiator such as an aromatic iodonium salt such as a triarylsulfonium salt or an aromatic iodonium salt such as a diaryliodonium salt is useful. Nonionic initiators such as nitrobenzyl esters can also be used. In addition, known photopolymerization initiators described in “Organic Materials for Imaging” published by Organic Electronics Materials Research Group (published in 1997), etc. can also be used.

As the photoreaction initiator, an aromatic sulfonium salt or the like is preferable because it is relatively thermally stable.
When an aromatic sulfonium salt and an aromatic iodonium salt are used as an onium salt photoinitiator, the counter anions include BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , PF ₆ ⁻ , B (C ₆ F ₅ ) _4- ^{and the} like. As the initiator, PF ₆ salt or SbF ₆ salt of aromatic sulfonium can be preferably used since it has solubility and moderate polymerization activity. In order to improve solubility, one or more alkyl groups or alkoxy groups having 1 to 10 carbon atoms are introduced into the aromatic group, usually phenyl group, of the aromatic group iodonium salt or aromatic sulfonium salt. A chemical structure is preferred.
PF ₆ salt or SbF ₆ salt of aromatic sulfonium salt is commercially available from Union Carbide Japan Co., Ltd. Asahi Denka Kogyo Co., Ltd. also sells PF ₆ salt of aromatic sulfonium under the trade name of Adekaoptomer SP series.
The aromatic sulfonium salt has an absorption up to about 360 nm, and the aromatic iodonium salt has an absorption up to about 320 nm. Therefore, for curing, it is preferable to irradiate ultraviolet rays including the spectral energy in this region.

[Organic solvent]
In the present invention, an organic solvent having a boiling point of 150 ° C. or lower can be used as a viscosity modifier for the binder. Examples of organic solvents having a boiling point of 150 ° C. or lower include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl acetate, and n-propyl acetate. , Acetate esters such as iso-propyl acetate, n-butyl acetate, iso-butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl n-butyl ketone, diisopropyl ketone And ketones such as acetylacetone, and alcohols such as ethanol, propanol, and butanol.
The amount of the organic solvent used is preferably 2 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably not used, based on the total amount of the binder.

The volatile component after curing of the UV curable binder is preferably 5% by weight or less. For this reason, it is more preferable to use a solvent-free formulation that does not use an organic solvent for the binder.
In order to reduce the volatile components after curing, the residual monomer can be post-polymerized by UV light irradiation or heating after the three-dimensional structure is manufactured.

(Powder material)
As the powder material, inorganic powders and organic powders, and all inorganic / organic composite powders can be used. Examples of inorganic powders include metals, oxides, composite oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbide sulfides, and composites of at least two of these. Can be mentioned. Specifically, magnesium hydroxide, silica gel, alumina, aluminum hydroxide, glass, titanium oxide, zinc oxide, zircon oxide, tin oxide, potassium titanate, aluminum borate, magnesium oxide, magnesium borate, calcium hydroxide, basic Magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide, zinc sulfide and at least two of these Examples include composites. Preferably, magnesium hydroxide, silica gel, alumina, aluminum hydroxide, glass, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate and the like can be mentioned.

  Examples of the organic powder include synthetic resin particles and natural polymer particles. Specifically, acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide Carboxymethylcellulose, gelatin, starch, chitin, chitosan and the like, preferably acrylic resin, polyurethane, gelatin, polystyrene and the like.

As the organic powder material, powder particles obtained by bulk polymerization of a polymerizable compound used for the binder and pulverization can be used. The polymerizable compound used for the binder can be suspension-polymerized or pearl-polymerized to obtain a powder material having a desired particle size. In this case, the refractive indexes given by both the powder material and the binder can be made equal.
Examples of the inorganic / organic composite powder include composites of the organic powder and the inorganic powder.
The average particle diameter of the powder material is 0.1 to 1,000 μm, preferably 0.1 to 500 μm, more preferably 0.5 to 300 μm.
As the shape of the powder material, any shape such as an amorphous shape, a spherical shape, a flat plate shape, a needle shape, and a porous shape can be used.

The range of the refractive index n ₁ of the powder material is preferably 1.4 to 1.7.
Let n _{2 be} the refractive index of the bonding agent in a state in which the powder materials are bonded to each other. When using an ethylenically unsaturated compound as the binder, the refractive index of the bonding agent the compound can be polymerized with n _2. As (n ₁ −n ₂ ) is smaller, the transparency of the resulting molded article is higher as the absolute value is smaller. When the absolute value of the difference in refractive index is 0.1 or less, the sense of transparency becomes high, and when it is 0.06 or less, a molded article that is nearly transparent is obtained. Here, in the present invention, “nearly transparent” means that the transmittance is 50% or more per 1 cm of the optical path.

(Coloring agent)
Colorants that can be used in the production method of the present invention are roughly classified into dyes and pigments, and dyes can be preferably used.
By using yellow (Y), magenta (M) and cyan (C) dyes, which are the three primary colors of the subtractive color method, a wide range of hues can be reproduced with different saturations. In this invention, it is preferable to use the dye utilized for the color print of a color photograph. Details are described below.

  As yellow dyes, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, JP-B 58- 10739, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649, European Patent 249,473A No., couplers represented by formulas (I) and (II) of No. 502,424A, couplers represented by formulas (1) and (2) of No. 513,496A (particularly Y-28 on page 18) A coupler represented by formula (I) in claim 1 of US Pat. No. 568,037A, a coupler represented by general formula (I) on lines 45 to 55 of column 1 of US Pat. No. 5,066,576, The general formula (I A coupler described in claim 1 on page 40 of European Patent No. 498,381A1 (particularly D-35 on page 18), a coupler represented by formula (Y) on page 4 of 447,969A1 (Especially Y-1 (page 17), Y-54 (page 41)), couplers represented by formulas (II) to (IV) in columns 7 to 58 of US Pat. No. 4,476,219, column 7. And ketimine type dyes obtained from (particularly II-17, 19 (column 17), II-24 (column 19)). Preferably, dyes described in JP 2001-294773 A, JP 2002-121414 A, JP 2002-105370 A, JP 2003-26974 A, JP 2003-73598 A, and the like are mentioned. Especially, the pyrazole compound represented by general formula (Y-II) described in Unexamined-Japanese-Patent No. 2003-73598 is used more preferably, and Y-1 shown below can be illustrated.

(Y-1)

Examples of the magenta dye include dyes described in JP-A Nos. 2001-181549, 2002-121414, 2002-105370, 2003-12981, and 2003-26974. It is done.
Of these, a pyrazolotriazole azomethine compound represented by the general formula (III) described in JP-A No. 2002-121414 is preferably used, and M-1 shown below can be exemplified.

Examples of the cyan dye include dyes described in JP-A Nos. 2002-121414, 2002-105370, 2003-3109, and 2003-26974.
A pyrrolotriazole azomethine compound represented by the general formula (IV-1a) described in JP-A No. 2002-121414 and a phthalocyanine compound represented by the general formulas (C-II-1) and (C-II-2) Preferably used, C-1 and C-101 shown below can be exemplified.

  If necessary, a black (black) dye may be used in combination with the three primary colors of CMY. The black dye can be made by mixing CMY3 dye.

As dyes other than those described above, those generally used in the technical field of printing (for example, color materials for copying or color proofing plates such as printing ink, thermal ink jet recording, and electrophotographic recording) can be used.
For example, “Organization of Organic Synthetic Chemistry” “Dye Handbook” Maruzen Co., Ltd. (published in 1970), Sadaharu Abeda, Kunihiko Imada “Commentary Dye Chemistry” Co., Ltd. Examples include dyes described in Kodansha (1986), Chemicals for Inkjet Printers-Material Development Trends and Perspective Survey-"CMC Co., Ltd. (1997), Takeshi Amari" Inkjet Printers-Technology and Materials ", etc. It is done.

(Pigment)
The pigment is not particularly limited, and all commercially available organic and inorganic pigments or pigments dispersed in an insoluble resin or the like as a dispersion medium, or the resin is grafted onto the pigment surface Can be used. Moreover, what dye | stained the resin particle with dye can be used.

In order to color the outer surface of the modeled object in the present invention, it is preferable to form a colored image with the YMC binder on the contour of the cross-sectional shape and to provide a white reflective layer immediately below the colored image. The white reflective layer has a role corresponding to, for example, a base in color printing, and it is preferable to use a binder containing a white pigment (white binder) immediately inside the wearing image.
Specific examples of the white pigment include basic lead carbonate (2PbCO ₃ Pb (OH) ₂ , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO ₂ , so-called titanium white), Strontium titanate (SrTiO ₃ , so-called titanium strontium white) or the like can be used.

  Here, titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable. Therefore, it has a high hiding power and coloring power as a pigment, and further, acid and alkali. Excellent durability against other environments. Therefore, it is preferable to use titanium oxide as the white pigment. Of course, other white pigments (may be other than the listed white pigments) may be used depending on the type of powder material and binder component.

In the present invention, CMY pigments may be used instead of CMY dyes.
Specific examples of organic pigments and inorganic pigments include, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G etc.), C.I. I. A monoazo pigment such as C.I. Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Yellow 115 (such as quinoline yellow lake); I. Basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavantron Yellow (Y-24), isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110), and quinophthalone yellow Quinophthalone pigments such as (Y-138), isoindoline pigments such as isoindoline yellow (Y-139), C.I. I. Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.); I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).

  As a magenta color, C.I. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I. I. Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.).

  As a pigment exhibiting a cyan color, C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (Peacock Blue Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkali blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).

(UV exposure)
For UV exposure for curing the UV curable binder, generally used high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps and the like can be used, and the exposure wavelength is 450 to 250 nm, preferably 400 to It can be 300 nm. Exposure energy is preferably 500 mJ / cm ² or less, 10 to 400 mJ / cm ² is more preferable. UV light can be guided from the UV light source to the powder material surface using a UV transmissive optical fiber.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
<Example 1>
(Preparation of UV curable binder "colorless transparent binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
(Captolactone-modified dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd., hereinafter the same)
Polymerizable compound: HDDA 14.8 g
(1,6-hexanediol diacrylate: manufactured by Daicel UCB) The same applies hereinafter.
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
(The same applies hereinafter, manufactured by Ciba Specialty Chemicals (Ciba S.C.).)
The above components were mixed by stirring to obtain a colorless and transparent binder having a viscosity at 25 ° C. of about 20 mPa · s.

(Preparation of UV curable binder "white binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
White pigment: Titanium oxide 3g
(KRONOS KA-15 manufactured by Titanium Industry; particle size 0.4 μm)
The above components were kneaded with a three-roll mill to obtain a white binder having a viscosity at 25 ° C. of about 25 mPa · s.

(Preparation of UV curable binder "yellow binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone 0.5 g
(Ciba S.C., hereinafter the same)
Colorant: Y-1 0.8g
Y-1, the following M-1, and the following C-1 are as described in the disclosure section of the invention.
The above ingredients were mixed with stirring, and the viscosity at 25 ° C was about 20 mPa.s. A yellow binder of s was obtained.

(Preparation of UV curable binder "Magenta binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone 0.5 g
Colorant: M-1 0.8g
The above components were mixed by stirring to obtain a magenta binder having a viscosity at 25 ° C. of about 20 mPa · s.

(Preparation of UV curable binder "Cyan binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone 0.5 g
Colorant: C-1 0.8g
The above components were mixed with stirring to obtain a cyan binder having a viscosity at 25 ° C. of about 20 mPa · s.

(Preparation of UV curable binder "Black Binder")
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone 0.5 g
Coloring agent: Y-1 0.3 g
M-1 0.2g
C-1 0.4g
The above components were mixed by stirring to obtain a black binder having a viscosity at 25 ° C. of about 20 mPa · s.

(Create 3D model)
After laying a powder material layer for one layer with a rod of polymethyl methacrylate (MB20X-5 manufactured by Sekisui Chemical Co., Ltd .; average particle size 5 μm) as a powder material to a thickness of about 100 μm, each ink jet is based on coloring data A colored binder (yellow, magenta, cyan, black), a white binder, and a colorless transparent binder are appropriately discharged from the discharge nozzle.
The inkjet method using the UV curable binder as an ink makes each dot a continuous line at a resolution of 600 dpi (dot spacing of about 42 μm) while adjusting the amount of ink as necessary in areas where strength is required. Droplets were discharged so that Next, a powder material layer having a thickness corresponding to one slice pitch was formed and a binder corresponding to the cross-sectional shape corresponding to the cross-section was repeatedly supplied to create a three-dimensional structure.

<Example 2>
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
8.4 g of polymerizable compound: ethoxylated pentaerythritol tetraacrylate
Polymerizable compound: HDDA 11.6 g
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Example 3>
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
In place of polymerizable compound: trimethylolpropane EO-modified triacrylate 10.0 g
(M350: manufactured by Toagosei Co., Ltd. Hereinafter, the same applies in the present invention.)
Monomer: Isobornyl acrylate 10.0 g
(Manufactured by IBOA Daicel UCB, hereinafter the same in the present invention)
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Example 4>
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
Instead of polymerizable compound: M350 5.0 g
Polymerizable compound: trimethylolpropane PO-modified triacrylate 5.0 g
(M310: manufactured by Toagosei Co., Ltd.)
Polymerizable compound: trimethylolpropane triacrylate 5.0 g
(M309: manufactured by Toagosei Co., Ltd.)
Polymerizable compound: IBOA 5.0 g
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Example 5>
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
In place of polymerizable compound: dipentaerythritol hexaacrylate 5.0 g
(KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd. Hereinafter, the same applies in the present invention.)
Polymerizable compound: trimethylolpropane trimethacrylate 15.0 g
(TMPTMA manufactured by Daicel UCB) Hereinafter, the same applies in the present invention.)
Methyl isobutyl ketone 2.0g
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Comparative Example 1>
Polymerizable compound: KAYARAD DPCA60 5.2 g
Polymerizable compound: HDDA 14.8 g
In place of polymerizable compound: KAYARAD DPCA60 20.0 g
Was used to stir and mix the binder component to obtain a colorless and transparent binder having a viscosity at 25 ° C. of about 1,000 mPa · s.
However, the ink jet head could not be discharged normally, and a three-dimensional structure was not obtained.

<Comparative example 2>
In Example 5, Polymerizable compound: KAYARAD DPHA 5.0 g
Polymerizable compound: TMPTMA 15.0 g
Methyl isobutyl ketone 2.0g
The binder component was stirred and mixed in the same manner as in Example 5 except that methyl isobutyl ketone was not used to obtain a colorless and transparent binder having a viscosity at 25 ° C. of about 160 mPa · s.
However, the ink jet head could not be discharged normally, and a three-dimensional structure was not obtained.
The above results are summarized in Table 1 below.

Inkjet ejection properties were divided into the following ranks.
(Inkjet ejection)
○: Normal ejection ×: Clogging occurred and the material could not be ejected The texture was classified into the following ranks for sensory evaluation.
(Texture)
○ ・ ・ ・ Good △ ・ ・ ・ Slightly good ・ ・ ・ Defective

<Viscosity measurement>
The viscosity of the binder used in the examples was measured at 25 ° C. and 10 rpm using an E-type viscometer (Tokyo Keiki VISCONIC ELD).
The binder used in the comparative example was measured in the same manner as the binder used in the example except that the rotation speed was changed to Comparative Example 1: 0.5 rpm and Comparative Example 2: 2.5 rpm, respectively.

It is a schematic diagram which shows each process about one embodiment of the manufacturing method of the three-dimensional structure according to the present invention. It is a perspective view which shows typically the cross-sectional shape of several layers formed in manufacture of the three-dimensional structure shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thin layer 2 Binder provision area 3 Three-dimensional modeling part 4 Support body (modeling stage)
5 Vertical moving part 6 Frame 7 Blade 8 Inkjet head 9 Ultraviolet irradiation part 10 Three-dimensional structure

Claims (9)

A step of sequentially repeating a step of forming a powder material on a support in a layer having a predetermined thickness, and a step of bonding the powder material layer with a binder so as to obtain a cross-sectional shape obtained by cutting a modeling object in a parallel cross section. In a manufacturing method of a three-dimensional structure including
The method for producing a three-dimensional structure, wherein the binder has a viscosity of 5 to 100 mPa · s at 25 ° C. The method for producing a three-dimensional structure according to claim 1, wherein the binder is cured by applying energy. The manufacturing method of the three-dimensional structure according to claim 1 or 2, wherein the binder is cured by applying light energy. 4. The binder according to claim 1, wherein at least one binder selected from the group consisting of at least one colored binder, a white colored binder, and a colorless binder is used. The manufacturing method of the three-dimensional structure according to one. The method for producing a three-dimensional structure according to any one of claims 1 to 4, wherein the colored binder comprises at least three binders: a yellow binder, a magenta binder, and a cyan binder. The method for producing a three-dimensional structure according to any one of claims 1 to 5, wherein the colored binder comprises at least four binders of a yellow binder, a magenta binder, a cyan binder, and a black binder. . The binder according to any one of claims 1 to 6, wherein the binder comprises (a) at least one trifunctional or higher (meth) acrylate, and (b) at least one monofunctional and / or bifunctional (meth) acrylate. The manufacturing method of the three-dimensional structure described. The method for producing a three-dimensional structure according to claim 7, wherein the tri- or higher functional (meth) acrylate is tetrafunctional, pentafunctional or hexafunctional (meth) acrylate. The method for producing a three-dimensional structure according to any one of claims 1 to 8, wherein an organic solvent having a boiling point of 150 ° C or lower is used as the viscosity modifier of the binder.

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