JP2005254534A - Method for manufacturing three-dimensional shaped article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for faithfully manufacturing a target three-dimensional shaped article inclusive of its shape and a hue. <P>SOLUTION: In the method for manufacturing the three-dimensional shaped article including a process for forming a layer containing a powder material on a support and a process for bonding the obtained powder material layer imagewise by a binder, the binder contains a polymerizable compound and a refractive index adjusting agent. This manufacturing method has an effect for manufacturing the three-dimensional shaped article having colored appearance and excellent in precision in a short time at low cost. <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 including a step of imagewise bonding a powder material layer with a binder.

  Conventionally, on the basis of cross-sectional data obtained by slicing a three-dimensional object, a thin layer of powder is image-wise combined with a binder in correspondence with each cross-sectional shape, and a cross-sectional shape composed of the combined thin layers is obtained. A technique for creating a modeled object that becomes a three-dimensional model of a modeled object by sequentially laminating 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 the inkjet nozzle head is scanned over the thin layer surface of this powder, based on sliced cross-sectional data of the modeling object, The binder is discharged in accordance with the cross-sectional 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 three-dimensional modeling technique that can faithfully manufacture a target three-dimensional model including not only its shape but also its color. The object of the present invention is to produce a three-dimensional structure excellent in transparency having a colored appearance in a short time and at a low cost.

The above object of the present invention has been achieved by the following means.
A method for producing a three-dimensional structure including a step of forming a layer containing a powder material on a support and a step of imagewise bonding the obtained powder material layer with a binder, wherein the binder has a refractive index The manufacturing method of the three-dimensional structure characterized by including a regulator.

  According to the present invention, by incorporating a refractive index adjusting agent in the binder, it becomes possible to precisely match the refractive index of the powder material and the binder, and it is possible to produce a highly transparent three-dimensional structure. It becomes. As a result, a high-quality three-dimensional structure that has been impossible until now can be manufactured simply, inexpensively and stably.

  The present invention is a method for producing a three-dimensional structure including a step of forming a layer containing a powder material on a support, and a step of imagewise bonding the obtained powder material layer with a binder. The agent includes a polymerizable compound and a refractive index adjusting agent, and relates to a method for producing a three-dimensional structure. More specifically, the present invention is based on a step of forming a powder material on a support in a layer having a predetermined thickness (layer formation step), and a cross-sectional data obtained by slicing a modeling target, so that the cross-sectional shape thereof is obtained. And a method of manufacturing a three-dimensional structure including sequentially repeating a step (cross-sectional shape forming step) of bonding the powder material layer imagewise with a binder.

  The powder material used in the present invention preferably has an average particle size of 0.05 to 1,000 μm, more preferably 0.07 to 100 μm, and most preferably 0.08 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 25 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 slicing a modeling target object on a large number of surfaces, and with coloring corresponding to the shape, if necessary. 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. The binder application region 2 is bonded by the entire thickness of the thin layer in the binder application region 2 by being cured by the ultraviolet rays irradiated from the ultraviolet irradiation unit 9 to form a cross-sectional shape, and It is combined with the cross-sectional shape immediately below.
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 light and curing, the powder material is bonded.
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. Specifically, data produced using three-dimensional CAD (such as an STL format) can be converted into sliced cross-sectional data having a thickness of 10 to 500 μm. 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. In the present invention, the colored binder does not include a white colored binder.
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. If necessary, a binder (black binder) colored with a black (black) dye may be used in combination as a colored binder. 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. Moreover, a desired effect can be expressed by using a binder (white binder) containing a white pigment such as titanium white.
The total discharge amount of the colored binder, the colorless binder and the white binder is preferably constant per unit area.
As another example of forming the colored cross-sectional shape, after discharging only a colorless ultraviolet 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 ultraviolet exposure on the surface of the binder discharged by the ultraviolet exposure apparatus at the same time as or after the discharge of the ultraviolet curable binder, a bonded body of powder material is generated.
When the atmosphere of ultraviolet 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) that is image-wise 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.
The absolute value of (n ₁ −n ₂ ) is preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.01 or less. It is preferable to reduce the difference in refractive index because the total light transmittance is improved and the fogging is reduced.
The cloudiness (cloudiness value) can be measured with a haze meter, and the smaller the haze, the more the three-dimensional structure without fogging. In the present invention, haze was measured using HGM-2DP manufactured by Suga Test Co., Ltd. The haze value is preferably 50% or less, more preferably 40% or less, for a molded product having a thickness of 3 mm.

  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)
In the present invention, the binder is a binder composition containing at least a polymerizable compound and a refractive index adjusting agent. The binder composition is also simply referred to as a binder.
The binder can contain other components in addition to the polymerizable compound and the refractive index adjuster. For example, a polymerization initiator and a polymerizable compound for adjusting viscosity can be contained.
The binder used in the present invention is preferably one that is cured by energy application. Binders that cure by “energy application” include resins that cure by a thermally activated chemical reaction. The binder has the property of initiating polymerization or cross-linking upon application of energy, polymerizing and curing.
The binder used in the present invention is preferably one that is cured by applying actinic radiation. The actinic radiation used in the present invention includes various types of radiation such as electron beams (β rays), ultraviolet rays, X rays, γ rays, and α rays. Among these, it is particularly preferable to use a binder that cures with ultraviolet rays (ultraviolet (UV) curable binder). In the case of curing by applying actinic radiation, a binder is preferable because the reaction does not proceed unless actinic radiation is applied from the outside, and the viscosity is stable. Hereinafter, an ultraviolet curable resin will be described as a representative example.
The ultraviolet curable binder has a refractive index adjuster, a photopolymerization initiator, and at least one polymerizable compound as essential components, and has a function of binding almost all constituent materials by ultraviolet irradiation 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.
Moreover, it is preferable that it is 0.1-10 weight% with respect to a polymeric compound, and, as for content of a refractive index modifier, it is more preferable that it is 1-5 weight%.

  The viscosity of the binder at 25 ° C. is preferably 5 to 100 mPa · s, and more preferably 10 to 50 mPa · s. 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.

[Refractive index modifier]
A refractive index adjusting agent (hereinafter referred to as a dopant) is a compound different from the refractive index of the polymerizable compound (polymer) after curing. These have a difference in solubility parameter of 7 (cal / cm) in comparison with a polymer produced by synthesis of a polymerizable compound as described in Japanese Patent No. 3332922 and JP-A-5-173026. ³⁾ is preferably within ^1/2, and more preferably 5 (cal ^/ cm ^{3) 1/2} within. The absolute value of the difference in refractive index between the polymer and the dopant is preferably 0.001 or more, and more preferably 0.005 or more. The dopant has a property that the refractive index of the polymer containing the dopant is changed as compared with the additive-free polymer. Those that can stably coexist with the polymer and are stable under the polymerization conditions of the polymerizable compound (polymerization conditions such as heating and pressurization) are preferred.
In the present invention, the refractive index is a value measured at 25 ° C. using sodium D-line.

  In addition, the dopant may be a polymerizable compound, and when a dopant of the polymerizable compound is used, the refractive index of the copolymer containing this as a copolymerization component is changed compared to a polymer not containing this. It is preferable to use those having the property of A material that has the above properties, can stably coexist with the polymer, and is stable under the polymerization conditions of the polymerizable compound can be used as the dopant.

  Examples of the dopant include benzyl benzoate (BEN), diphenyl sulfide (DPS), triphenyl phosphate (TPP), benzyl-n-butyl phthalate (BBP), diphenyl phthalate (DPP), and biphenyl (DP). , Diphenylmethane (DPM), tricresyl phosphate (TCP), diphenyl sulfoxide (DPSO), methyl butyrate (methyl-isobutyrate, MIB) and the like. Among these, BEN, DPS, TPP, DPSO, MIB preferable.

[Polymerizable compound]
As the polymerizable compound that can be used in the present invention, a compound in which addition polymerization or ring-opening polymerization is initiated by a radical species or a cationic species generated from a photopolymerization initiator by ultraviolet irradiation to produce a polymer is preferably 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.
As the polymerization mode of the present invention, radical polymerization is preferably used, but it can also be used in combination with a polymerizable compound that is cured by another polymerization mode. As the polymerizable compound, a compound that undergoes addition polymerization in particular by radical polymerization can be preferably used.

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, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Mention may be made of pentaerythritol di (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 an ultraviolet curable binder together with an ultraviolet 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 ultraviolet 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.

The volatile component after curing of the ultraviolet curable binder is preferably 5% by weight or less. For this reason, it is 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 remaining uncured polymerizable compound can be post-polymerized by ultraviolet irradiation or heating after the three-dimensional structure is manufactured.

[Polymerization initiator]
The binder used in the present invention can be cured with a thermal polymerization initiator, but is preferably cured with a photopolymerization initiator.
The photopolymerization initiator used in the present invention refers to a compound that generates active radical species or cation species by applying active light, and initiates and accelerates the polymerization reaction of the binder. Ultraviolet rays are preferred as the active light. In addition, gamma rays, alpha rays, electron beams, etc., known as active energy rays, can be used in place of active rays.

Examples of the polymerization initiator that generates radicals by the action of light are preferably acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, benzyl compounds, acylphosphine oxide compounds, and the like. 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-methylpropiophenone, 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. Examples of the acyl phosphine oxide compound include bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, and the like.
Since the sulfonium salt and iodonium salt, which are usually used as photocation generators described below, 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. Among these, aromatic sulfonium salts and the like are preferable because they are thermally relatively stable. 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.

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.

  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.

[Polymerization compound for viscosity adjustment]
As the polymerizable compound for adjusting viscosity, a compound having a low viscosity and copolymerizable with the polymerizable compound is used. For example, acrylate, methacrylate, acrylamides can be mentioned. Specifically, tolyloxyethyl (meth) acrylate, phenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethylene glycol di (meth) acrylate, divinylbenzene, Methylene bisacrylamide, 1,6-di (meth) acryloyloxyhexane, etc., preferably, tolyloxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-di (meth) acryloyloxyhexane, etc. It is done.
In ring-opening polymerizable cyclic ethers, bifunctional or higher cyclic ethers generally have high reactivity but high viscosity. Monofunctional cyclic ethers can be used in combination to adjust the viscosity to low.

(Powder material)
The powder material used in the present invention is preferably a fine powder having an average particle size of 100 μm or less, and more preferably a fine powder having an average particle size of 0.8 to 50 μm. It is preferable for the average particle diameter to be in the above range since the surface glossiness of the resulting three-dimensional structure is improved. The particle size distribution may be wide, but is preferably narrow. The particle size distribution is preferably close to monodisperse, and the variation coefficient of the particle size distribution is preferably 20% or less, and particularly preferably 15% or less.
As the shape of the powder, any shape such as an amorphous shape, a spherical shape, a flat plate shape, a needle shape, or a porous shape can be used.
As the powder material, any of organic powder, inorganic powder, and inorganic / organic composite powder can be used, but organic powder is preferably used.

The range of the refractive index n ₁ of the organic powder is preferably 1.4 to 1.7.
Let n _{2 be} the refractive index of the binder in a state where organic powders 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.

  As the organic powder, 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 index provided by both the powder material and the binder can be made close.

  Examples of the organic powder include synthetic resin particles and natural polymer particles. It is preferable to use synthetic resin particles. Specifically, acrylic resin, olefin resin, phenol resin, styrene resin, divinylbenzene resin, urethane resin, polyester, polyamide, polyimide, acrylonitrile-butadiene-styrene copolymer, polyacrylonitrile, epoxy resin, fluororesin, melamine formaldehyde, Examples include polycarbonate, sulfone polymer, vinyl polymer, carboxymethyl cellulose, gelatin, starch, chitin, chitosan and the like. Among these, acrylic resins, olefin resins, phenol resins, styrene resins, divinylbenzene resins, and fluorine resins can be preferably used. Moreover, the said resin may be used individually or may be used in combination of 2 or more types.

The acrylic resin refers to a resin obtained by homopolymerization or copolymerization of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile. Here, the notation of (meth) acrylic acid is an abbreviated notation indicating that both structures of methacrylic acid or acrylic acid can be taken.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, stellaryl (meth) acrylate, (meth) acrylic acid 2 Examples include -hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and the like.
Moreover, polymethyl methacrylate can be preferably used as the acrylic resin.
Examples of the other acrylic resins include resins described in pages 6 to 12 of Mita Tatsumi's translation "Polymer Great Dictionary" Maruzen Co., Ltd. (1994).

Olefin resin refers to a polymer of olefin, and includes polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly (1-pentene), poly (3-methyl-1-butene), poly (1-hexene), Poly (3-methyl-1-pentene), poly (4-methyl-1-pentene), poly (1-heptene), poly (4-methyl-1-hexene), poly (5-methyl-1-hexene) Etc. can be illustrated. Polyethylene and polypropylene can be preferably used.
Examples of the other olefin resin include resins described in pages 102 to 109, translated by Tatsushi Mita, “Polymer Dictionary”, published by Maruzen Co., Ltd. (1994).

A phenol resin refers to a resin obtained by addition condensation of phenols and aldehydes. When an acid catalyst is used for the addition condensation reaction, a novolak type resin is obtained, and when a base catalyst is used, a resol type resin is obtained. Examples of phenols include phenol, p-cresol, m-cresol, resorcinol and the like. Examples of aldehydes include formaldehyde, salicylaldehyde, s-trioxane and the like.
Examples of the other phenols and aldehydes include compounds described in the Chemical Society of Japan, “4th edition, Experimental Science Course 28, Polymer Synthesis” (1992), pages 427-430.

Styrene resin refers to a homopolymer or copolymer of a styrene monomer. Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, α-methylstyrene, o-chlorostyrene, p-chlorostyrene, chloromethylstyrene, and the like. Polystyrene can be preferably used.
Examples of the styrene monomer copolymer include copolymers described in pages 506 to 507 of Mita Tatsumi's “Polymer Daiten Dictionary”, Maruzen Co., Ltd. (1994).

Divinylbenzene resin refers to a homopolymer or copolymer of divinylbenzene monomer. Examples of the divinylbenzene monomer include divinylbenzene and chlorodivinylbenzene. Moreover, said styrene monomer can be illustrated as a monomer copolymerized with a divinylbenzene monomer.
Polydivinylbenzene can be preferably used as the divinylbenzene resin.

  The fluororesin is a polymer containing fluorine. Examples of the fluororesin include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer, and the like. Of these, polytetrafluoroethylene can be preferably used.

The urethane resin indicates a polymer obtained by addition polymerization of a polyfunctional isocyanate and a polyol. Examples of the polyfunctional isocyanate include toluene diisocyanate, diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the polyol include polyether polyol, polyester polyol, and aliphatic polyol.
Examples of the other polyfunctional isocyanates and polyols include compounds described in Keiji Iwata, “Polyurethane Handbook”, Nikkan Kogyo Shimbun (1987), pages 77 to 81 and pages 99 to 117.

  Examples of natural polymer particles include carboxymethyl cellulose, gelatin, starch, chitin, chitosan and the like.

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 inorganic / organic composite powder include composites of the organic powder and the inorganic powder.

(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) in columns 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. Among these, a pyrazole compound represented by the general formula (Y-II) described in JP-A-2003-73598 is more preferably used.
Y-1 shown below can be preferably used as a yellow dye.

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.
M-1 shown below can be preferably used.

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 preferably used as a cyan dye.

  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, commonly 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. Ultraviolet rays can be guided from the ultraviolet light source to the powder material surface using an ultraviolet transmissive optical fiber.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

Hereinafter, the materials used in the examples of the present invention are as follows.
DPHA (dipentaerythritol hexaacrylate: in-house synthesized product)
TMPTMA (Trimethylolpropane trimethacrylate: manufactured by Daicel UCB)
2-hydroxy-2-methylpropiophenone (manufactured by Ciba Specialty Chemicals (Ciba S.C))
Titanium oxide (KRONOS KA-15; particle size 0.4 μm: manufactured by Titanium Industry Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl ketone (manufactured by Ciba S.C)

<Example 1>
(Preparation of UV-curable binder "colorless binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Dopant: Diphenyl sulfide 0.4g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
The above components were mixed with stirring to obtain a colorless binder.

(Preparation of UV curable binder "white binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
White pigment: Titanium oxide 3g
The above components were kneaded with a three-roll mill to obtain a white binder.

(Preparation of UV curable binder "Yellow Binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Dopant: Diphenyl sulfide 0.4g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
Colorant: Y-1 0.8g
Y-1, the following M-1, and the following C-1 are as described in the detailed description.
The above components were mixed by stirring to obtain a yellow binder.

(Preparation of UV curable binder "Magenta binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
Colorant: M-1 0.8g
The above components were mixed with stirring to obtain a magenta binder.

(Creation of UV curable binder "Cyan binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone 0.5 g
Dopant: Diphenyl sulfide 0.4g
Colorant: C-1 0.8g
The above components were mixed with stirring to obtain a cyan binder.

(Preparation of UV curable binder "Black Binder")
Polymerizable compound: DPHA 10 g
Polymerizable compound: TMPTMA 10 g
Dopant: Diphenyl sulfide 0.4g
Photopolymerization initiator: 0.6 g of 2-hydroxy-2-methylpropiophenone
Coloring agent: Y-1 0.3 g
M-1 0.2g
C-1 0.4g
The above components were mixed with stirring to obtain a black binder.

(Create 3D model)
As a powder material, a powder material layer of one layer is laid with a rod so that a copolymer A of methyl methacrylate and styrene (refractive index adjusted to 1.520, average particle diameter 12 μm) is about 100 μm thick. Thereafter, a yellow binder, a magenta binder, a cyan binder, a black binder, a white binder, and a colorless transparent binder are appropriately discharged from each inkjet discharge nozzle based on the color data.
The inkjet method using the ultraviolet 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. As a standard amount, 2 nl droplets were discharged. Next, a three-dimensional structure was created by repeatedly forming a powder forming layer having a thickness corresponding to one slice pitch and supplying a binder corresponding to the cross-sectional shape corresponding to the cross-section.

<Example 2>
Example 1 dopant: diphenyl sulfide 0.4 g
Instead of dopant: Methyl-iso-butyrate 0.5g
And a copolymer B of methyl methacrylate and styrene as a powder material instead of a copolymer A of methyl methacrylate and styrene as a powder material (refractive index adjusted to 1.520, average particle diameter 12 μm) The same evaluation as in Example 1 was performed by using (refractive index adjusted to 1.510, average particle diameter 12 μm).

<Comparative Example 1>
The dopant of Example 1 was prepared and evaluated according to the same production method as in Example 1 except that diphenyl sulfide was not used.
<Comparative example 2>
Dopant of Example 2: Methyl-iso-butyrate
According to the same production method as in Example 2, except that was not used.

(Evaluation methods)
The transparency of the transparent part of the obtained three-dimensional structure (thickness 3 mm) was evaluated by the haze of a haze meter (HGM-2DP type manufactured by Suga Test Instruments Co., Ltd.).

The above results are summarized in Table 1.
In Table 1, the difference in refractive index indicates the difference in refractive index between the polymerizable compound and the dopant.

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 (6)

Forming a layer comprising a powder material on a support; and
A method for producing a three-dimensional structure including a step of imagewise bonding the obtained powder material layer with a binder,
The method for producing a three-dimensional structure, wherein the binder contains a polymerizable compound and a refractive index adjusting agent. Forming a powder material on a support in a layer having a predetermined thickness; and
The method for producing a three-dimensional structure according to claim 1, comprising sequentially repeating the step of imagewise bonding the powder material layer with a binder so as to obtain a cross-sectional shape based on sliced cross-sectional data of the modeling object. .   The method for producing a three-dimensional structure according to claim 1 or 2, wherein the refractive index difference between the polymerizable compound after curing and the refractive index adjusting agent is 0.001 or more in absolute value.   The binder according to any one of claims 1 to 3, wherein two or more binders selected from the group consisting of at least one colored binder, a white binder, and a colorless binder are used as the binder. A manufacturing method of a three-dimensional structure.   The tertiary according to any one of claims 1 to 4, wherein the colored binder comprises at least two binders selected from the group consisting of a yellow binder, a magenta binder, a cyan binder, and a black binder. Manufacturing method of original model.   The method for producing a three-dimensional structure according to any one of claims 1 to 5, wherein the binder is an ultraviolet curable binder.

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