JP2005088429A - Manufacturing method of three-dimensional shaped article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a three-dimensional shaped article having colored appearance and mechanical strength with good measurement precision at a low cost for a short time. <P>SOLUTION: In the manufacturing method of a three-dimensional shaped article successively repeating a process for forming a powder material on a support as a layer having a predetermined thickness and a process for bonding the powder material layer by a binder so as to have a cross-sectional shape formed by cutting a shaping object by a parallel cross section, the binder and/or the powder material contains an acylphosphine oxide compound and is cured by applying energy. <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.

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 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.
1) A step of forming a powder material on a support in a layer having a predetermined thickness (layer formation step), and a powder material layer with a binder so as to have a cross-sectional shape obtained by cutting a modeling object in a parallel cross section In the method for producing a three-dimensional structure including sequentially repeating the bonding step (cross-sectional shape forming step), the binder and / or the powder material contains an acyl phosphine oxide compound, and the powder material layer is cured by applying energy. A method for producing a three-dimensional structure characterized by
2) The method for producing a three-dimensional structure according to 1), wherein the binder is cured by applying light energy,
3) Two or more binders selected from the group consisting of at least one colored binder, a white colored binder, and a colorless, preferably colorless, transparent binder are used as the binder. 1) or 2) manufacturing method of the three-dimensional structure according to
4) The method for producing a three-dimensional structure according to any one of 1) to 3), wherein the colored binder comprises at least three binders of a yellow binder, a magenta binder, and a cyan binder,
5) Production of the three-dimensional structure according to any one of 1) to 4), wherein the colored binder comprises at least four binders of a yellow binder, a magenta binder, a cyan binder and a black binder. Method.

  The manufacturing method of the present invention makes it possible to manufacture a three-dimensional structure with high measurement accuracy, a smooth surface and excellent texture, and a high-quality three-dimensional structure that has been impossible until now is easily and inexpensively manufactured. It became possible to create.

  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. In a method for producing a three-dimensional structure including sequentially repeating a step of bonding with an agent (cross-sectional shape forming step), the binder includes a polymerization initiator and is cured by applying energy. Related to manufacturing method.

  In the present invention, the binder supplied to the powder material contains a polymerization initiator. If necessary, the polymerization initiator can absorb active energy rays to generate an active species that initiates polymerization, and initiates polymerization of the polymerizable compound to bind the powder material.

  The powder material used in the present invention preferably has an average particle size of 0.1 to 1,000 μm, more preferably 1 to 50 μm, and most preferably 3 to 30 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. The binder application region 2 is cured by the ultraviolet rays irradiated from the ultraviolet irradiation unit 9, thereby bonding the powder material over the entire thickness of the thin layer in the binder application region 2 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. The powder material is bonded by irradiating the region with ultraviolet rays and curing.
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 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 a powder joined body (three-dimensional structure) joined by the binder is taken out. The powder material that has not been joined can be recovered 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 joined bodies of powder materials corresponding to cut surfaces obtained by cutting a modeling object by 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 infiltration 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.
(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 binder polymerizable compound and pulverization can be used. The binder polymerizable compound 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 preferably in the range of 0.8 to 50 μm, more preferably 3 to 30 μm. Here, the average particle diameter means a volume average particle diameter, and can be measured by, for example, Coulter Multisizer of Coulter.
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 ethylenically unsaturated monomers as binding agent, the refractive index of the bonding agent the monomer 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, “substantially transparent” or “nearly transparent” in the present invention means that the transmittance is 50% or more per 1 cm of the optical path.

(Binder)
As the binder, any binder that cures by applying energy can be used, but a UV curable binder can be preferably used. The UV curable binder contains at least one polymerizable compound as an essential component, and has a function of binding almost all constituent materials by UV light and binding a powder material. The polymerization initiator is included in the binder and / or powder material. As a ratio of each constituent material, the ratio of the photopolymerization initiator to the total amount of the polymerizable compound and the photopolymerization initiator is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight. Used in. The content of the polymerizable compound is preferably 90 to 99.5% by weight, more preferably 95 to 99.9% by weight.
The liquid viscosity (25 ° C.) of the binder is preferably 5 to 100 mPa · s, and more preferably 10 to 50 mPa · s. It is preferable that a polyfunctional monomer having a high viscosity and a monofunctional monomer having a low viscosity are appropriately mixed and used so as to be in this viscosity range.

(Polymerizable compound)
As the polymerizable compound that can be used in the UV curable binder, a compound in which addition polymerization or ring-opening polymerization is initiated by radical species generated from the photopolymerization initiator by UV light irradiation and a polymer is preferably used. As a polymerization mode of addition polymerization, radical polymerization may be mentioned. Moreover, radical polymerization is mentioned as a polymerization mode of ring-opening 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 (that is, a bifunctional, trifunctional and 4-6 functional polymerizable compound), 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.

  A specific example of a radical polymerizable compound that is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound is typically (meth) acrylic acid ester. Specific examples include isobornyl acrylate, ethylene glycol diester. (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, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) a Relate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate , Tri ((meth) acryloyloxyethyl) isocyanurate, polyester (meth) acrylate oligomer, bis [p- (3- ( Data) acryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p - ((meth) acryloxy ethoxy) phenyl] dimethyl methane, and the like.

  Here, the notation of the above (meth) acrylic acid ester is an abbreviated notation indicating that the structure of both a methacrylic acid ester and an acrylic acid ester can be taken.

In addition to (meth) acrylic acid esters, itaconic acid esters, crotonic acid esters, isocrotonic acid esters, maleic acid esters 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 radically polymerizable ethylenically unsaturated compound and a cationic polymerizable cyclic ether (epoxy derivative and / or oxetane derivative) can be used in combination as the UV curable binder. 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 UV 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 residual monomer can be post-polymerized by UV light irradiation or heating after the three-dimensional structure is manufactured.

(Polymer 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.

(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. A polymerization initiator (photo radical polymerization agent) that generates active radical species can be preferably used. 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. Salt compound.

  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 acetophenone compounds include 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-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, etc. It is done. Examples of the benzoin compound 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.

  In the present invention, an acyl phosphine oxide compound can be preferably used as the photoradical polymerization agent. Examples of the acylphosphine oxide compound include compounds represented by the following general formula (I) and compounds represented by the following general formula (II).

R ¹¹ and R ¹² in the general formula (I) each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group, and R ¹³ represents an alkyl group, an aryl group, or a heterocyclic group. Represents. R ¹¹ and R ¹² may combine to form a cyclic structure.

The alkyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group may have a substituent. Examples of the substituent include an alkyl group, aryl group, hydroxy group, nitro group, cyano group, halogen atom, alkylsulfonyl group, arylsulfonyl group, alkoxy group, alkoxycarbonyl group, aryloxy group, aryloxycarbonyl group, An acyl group, a (mono or dialkyl) amino group, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group and the like can be mentioned. The substituent includes a group obtained by removing one hydrogen atom from R ^{13 of the} compound represented by the general formula (I).

The alkyl group represented by R ¹¹ , R ¹² or R ¹³ may be either a saturated group or an unsaturated group, and may be linear, branched or cyclic. As this alkyl group, a C1-C30 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, an octadecyl group, a phenoxyethyl group, a cyclohexyl group, etc. Is mentioned. However, it is not limited to these.

Examples of the aryl group represented by R ¹¹ , R ¹² or R ¹³ include aryl groups having 6 to 30 carbon atoms. Of these, a phenyl group, a naphthyl group and the like are preferable. For example, a phenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyphenyl group, and a 2,6-dimethoxy group. Examples thereof include a phenyl group and a 2,6-dichlorophenyl group. However, it is not limited to these.

The heterocyclic group represented by R ¹¹ , R ¹² or R ¹³ is preferably a heterocyclic group containing an N, O or S atom, such as a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, or a pyrrolyl group. Is mentioned.

The alkoxy group represented by R ¹¹ or R ¹² is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, and a phenoxyethoxy group. However, it is not limited to these.

The aryloxy group represented by R ¹¹ or R ¹² is preferably an aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, methylphenyloxy group, chlorophenyloxy group, methoxyphenyloxy group, octyloxyphenyl. An oxy group etc. are mentioned. However, it is not limited to these.

R ¹⁴ and R ¹⁶ in the general formula (II) each independently represent an alkyl group, an aryl group, or a heterocyclic group, and R ¹⁵ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group. Represents. The alkyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group represented by R ¹⁴ , R ¹⁵ or R ¹⁶ may have a substituent. Examples of the substituent are the same as those in the formula (I).

  The alkyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group in the general formula (II) have the same meaning as in the general formula (I).

  Examples of the acylphosphine oxide compound represented by the general formula (I) or (II) include, for example, Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. Examples thereof include compounds described in JP-A No. 10-29997. Specific examples of the acylphosphine oxide compound include the following compounds (Exemplary Compounds (1) to (26)), but the present invention is not limited to these.

In the present invention, the acylphosphine oxide compound represented by at least one of the general formula (I) and the general formula (II) may be used alone or in combination of two or more.
In addition, the above acylphosphine oxide compound may be used in combination with other polymerization initiators, particularly the acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, benzyl compounds, and the like.

(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 Couplers represented by formulas (I) and (II) of No. 502,424A, and 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. Examples thereof include 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.

Hereinafter, the materials used in the examples of the present invention are as follows.
DPHA (dipentaerythritol hexaacrylate, in-house synthesized product)
Isobornyl acrylate (Daicel UCB)
Acylphosphine oxide compound (Exemplary Compound (2)) (Lucirin TPO; manufactured by BASF)
Acylphosphine oxide compound (Exemplary Compound (4)) (Lucirin TPO-L; manufactured by BASF)
Acylphosphine oxide compound (Exemplary compound (19)) (Irgacure 819; manufactured by Ciba Specialty Chemicals (Ciba S.C))
1: 1 mixture of acylphosphine oxide compound (Exemplary Compound (22)) and 1-hydroxycyclohexyl phenyl ketone (Irgacure 1850; manufactured by Ciba S.C.)
1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba S.C)
2-Hydroxy-2-methyl-1-phenylpropan-1-one (DAROCURE 1173; manufactured by Ciba S.C)
Titanium oxide (KRONOS KA-15 manufactured by Titanium Industry; particle size 0.4 μm)

<Example 1>
(Preparation of UV curable binder "colorless binder")
Polymerizable compound: DPHA 5 g
Polymerizable compound: isobornyl acrylate 15 g
Photopolymerization initiator: acylphosphine oxide compound (Exemplary Compound (2)) 0.6 g
The above components were mixed with stirring to obtain a colorless binder.

(Preparation of UV curable binder "white binder")
Polymerizable compound: DPHA 5 g
Polymerizable compound: isobornyl acrylate 15 g
Photopolymerization initiator: acylphosphine oxide compound (Exemplary Compound (2)) 0.6 g
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: isobornyl acrylate 10 g
Photopolymerization initiator: acylphosphine oxide compound (exemplary compound (2)) 0.5 g
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 components were mixed by stirring to obtain a yellow binder.

(Preparation of UV curable binder "Magenta binder")
Polymerizable compound: DPHA 5 g
Polymerizable compound: isobornyl acrylate 15 g
Photopolymerization initiator: acylphosphine oxide compound (exemplary compound (2)) 0.5 g
Colorant: M-1 0.8g
The above components were mixed with stirring to obtain a magenta binder.

(Preparation of UV curable binder "Cyan binder")
Polymerizable compound: DPHA 5 g
Polymerizable compound: isobornyl acrylate 15 g
Photopolymerization initiator: acylphosphine oxide compound (exemplary compound (2)) 0.5 g
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 5 g
Polymerizable compound: isobornyl acrylate 15 g
Photopolymerization initiator: acylphosphine oxide compound (exemplary compound (2)) 0.5 g
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)
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 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. A droplet was discharged so that
An exposure energy of 30 mJ / cm ² was applied to the powder material surface with a high-pressure mercury lamp.
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.

(Evaluation methods)
A cube shaped product having a length, width, and height of 3 cm created by the above method was used as an index.
In addition, the smoothness of the surface was sensory-evaluated by touching it with the hand and used as an index of texture.

<Example 2>
Acylphosphine oxide compound (Exemplary Compound (2)) as a polymerization initiator
Instead of acylphosphine oxide compound (Exemplary Compound (4))
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Example 3>
Acylphosphine oxide compound (Exemplary Compound (2)) as a polymerization initiator
Instead of acylphosphine oxide compound (Exemplary Compound (19))
A three-dimensional structure was created and evaluated in the same manner as in Example 1 except that was used.

<Example 4>
Acylphosphine oxide compound (Exemplary Compound (2)) as a polymerization initiator
A three-dimensional structure was prepared and evaluated in the same manner as in Example 1 except that a 1: 1 mixture of an acylphosphine oxide compound (Exemplary Compound (22)) and 1-hydroxycyclohexyl phenyl ketone was used instead of .

<Comparative Example 1>
Acylphosphine oxide compound (Exemplary Compound (2)) as a polymerization initiator
A three-dimensional structure was prepared and evaluated in the same manner as in Example 1 except that 1-hydroxycyclohexyl phenyl ketone was used instead of.

<Comparative example 2>
Acylphosphine oxide compound (Exemplary Compound (2)) as a polymerization initiator
A three-dimensional structure was prepared and evaluated in the same manner as in Example 1 except that 2-hydroxy-2-methyl-1-phenylpropan-1-one was used instead of.

  The above results are summarized in Table 1 below.

The curability was evaluated by sensory evaluation of the stickiness of the surface of the obtained molding.
(Curable)
○ ・ ・ ・ No stickiness × ・ ・ ・ With stickiness The texture was sensory evaluation and divided into the following ranks.
(Texture)
○ ・ ・ ・ Good × ・ ・ ・ Bad

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 (5)

  The step of forming the powder material on the support in a layer having a predetermined thickness and the step of bonding the powder material layer with a binder so as to obtain a cross-sectional shape obtained by cutting the object to be shaped in parallel cross sections are sequentially repeated. A method for producing a three-dimensional structure comprising: a binder and / or a powder material containing an acyl phosphine oxide compound, wherein the powder material layer is cured by applying energy.   The method for producing a three-dimensional structure according to claim 1, wherein the binder is cured by applying light energy.   3. The binder according to claim 1, wherein two or more kinds of binders selected from the group consisting of at least one colored binder, a white colored binder, and a colorless binder are used as the binder. A manufacturing method of a three-dimensional structure.   The method for producing a three-dimensional structure according to any one of claims 1 to 3, wherein the colored binder comprises at least three binders of 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 4, wherein the colored binder comprises at least four binders of a yellow binder, a magenta binder, a cyan binder, and a black binder.

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