JP5443826B2 - Manufacturing method of three-dimensional structure, three-dimensional structure material, and three-dimensional structure - Google Patents

Description

  The present invention relates to a method for manufacturing a three-dimensional structure, a material for three-dimensional structure used in the manufacturing method, and a three-dimensional structure obtained by the manufacturing method.

  In recent years, various additive manufacturing methods have been developed as a technique for modeling a three-dimensional three-dimensional object by computer control. These additive manufacturing methods have the following advantages compared to conventional modeling by removal processing such as cutting (including casting, plastic processing, and molding of a mold for injection molding). That is, (1) Even a three-dimensional object with a complicated internal structure that cannot contain a cutting tool can be automatically produced by a single modeling process. (2) Tool exchange and tool wear due to non-contact processing Tool management such as countermeasures is unnecessary, and unattended operation is possible at night. (3) Since no chips are generated and there is no noise / vibration, it can be operated in the office work environment. (4) Machine The advantage is that anyone can operate it without requiring specialized knowledge about processing.

As a representative method of the layered manufacturing method having such a feature, an optical modeling method, a powder sintering method, an extrusion method, a sheet cutting method, an ink jet method, and the like are known.
Among them, the optical modeling method is known to be able to produce a high-definition three-dimensional modeled object because the liquid is cured. The stereolithography method irradiates a liquid photocurable resin with light such as ultraviolet laser light, and cures the irradiated portion by a polymerization reaction to form a solidified layer. This is a method of generating a three-dimensional object having a desired shape by sequentially stacking the solidified layers by repeating a process of sinking a minute amount from the liquid surface and forming the next solidified layer by light irradiation. This stereolithography method is disclosed in Patent Document 1, for example.

JP-A-5-237944

  However, in the optical modeling method, the photocurable resin liquid that was not used for modeling in the tank is affected by the light irradiation during modeling, and its performance deteriorates. Was invited. In addition, since the laser head necessary for curing the resin material is very expensive, it is difficult to make a multi-head. Furthermore, it is necessary to limit the scanning speed of the laser beam in order to irradiate the light amount necessary for curing the resin material, and there is a problem that the modeling speed cannot be improved to a certain extent. In addition, the stereolithography method has a drawback that a full-color model cannot be formed in principle.

  The present invention aims to solve the above problems. That is, an object of the present invention is to provide a method for producing a three-dimensional structure that can produce a full-color and high-definition object at high speed. Furthermore, this invention aims at providing the three-dimensional modeling material obtained by the three-dimensional modeling material used for the said manufacturing method, and the said manufacturing method.

The above-described problems of the present invention have been solved by means described in the following <1>, <6>, and <7>. It is described below together with <2> to <5> which are preferred embodiments.
<1> A step of forming the liquid B in a layer having a predetermined thickness and a solid by mixing the liquid to be mixed with the liquid B in a layer of the liquid B so as to have a cross-sectional shape obtained by cutting the modeling target object in a parallel cross section. A step of applying a liquid A capable of forming a liquid, and a method for producing a three-dimensional structure characterized by sequentially repeating
<2> The method for producing a three-dimensional structure according to <1>, wherein the liquid A and / or the liquid B contains a dye and / or a pigment,
<3> One of the liquid A or the liquid B has two or more cationic residues and / or groups that can be induced to a cationic residue, and the other one is an organic acid residue and / or an organic acid salt. The method for producing a three-dimensional structure according to <1> or <2> above, having two or more residues,
<4> The step of applying the A liquid is a process of dripping the A liquid, and the dripping of the A liquid is performed by a nozzle capable of discharging minute liquid droplets, any one of the above <1> to <3> The manufacturing method of the three-dimensional structure as described in one,
<5> The method for producing a three-dimensional structure according to <4>, wherein the nozzle is an inkjet recording head or a dispenser,
<6> Three-dimensional modeling material including A liquid and B liquid used in the method for producing a three-dimensional structure according to any one of <1> to <5> above,
<7> A three-dimensional structure manufactured by the manufacturing method according to any one of <1> to <5> above.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the three-dimensional molded item which can produce a full-color high-definition molded item at high speed was able to be provided. Furthermore, according to this invention, the three-dimensional modeling material used by the said manufacturing method and the three-dimensional modeling thing obtained by the said manufacturing method were able to be provided.

It is schematic structure sectional drawing which shows an example 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 formed in each adjacent layer in manufacture of a three-dimensional structure. It is a top view which shows an example of the cross-sectional data subdivided into the grid | lattice form. It is a perspective view which shows one embodiment of the three-dimensional modeling apparatus which can be used in this invention.

The method for producing a three-dimensional structure of the present invention includes a step of forming the liquid B in a layer having a predetermined thickness, and a layer of the liquid B so as to have a cross-sectional shape obtained by cutting the modeling object in a parallel cross section. And the step of applying the liquid A capable of forming a solid by mixing with the liquid B, in order.
In the following description, the description of “A to B” indicating a numerical range means “A or more and B or less” unless otherwise specified. That is, a numerical range including A and B which are end points is represented.

(A liquid and B liquid)
As described above, the present invention is characterized by using the liquid A (solid formable liquid A) and the liquid B (solid formable liquid B) that can form a solid by mixing with each other.
The A liquid and the B liquid are not particularly limited as long as they form a solid when mixed with each other.
Here, “form a solid” means a state having a certain shape and volume. That is, liquid A and liquid B are liquids and have fluidity, whereas solids formed by mixing do not have fluidity. Here, the gel corresponds to a solid from the viewpoint of not having fluidity.

  Examples of combinations of compounds that form a solid when mixed include, for example, “Quarterly Chemical Review No. 8 Organic Polymer Gel” (edited by the Chemical Society of Japan, 1990), “Functional Polymer Gels and Latest Application Trends” (( Toray Research Center, Inc., 1996), Yoshihito Nagata, Wang Lin “Development Technology of Functional Polymer Gel” (CMC, 1999), etc. Can be mentioned.

  A specific combination of compounds that form a solid upon mixing includes, for example, a combination of compounds that gel by physical cohesion between molecules. Examples of the physical cohesion between molecules include ionic bonds and coordinate bonds, and combinations using them include two or more cationic residues and / or groups that can be induced to cationic residues. A combination of a compound (polyvalent cationic compound) and a compound having two or more organic acid residues and / or organic acid salt residues (multivalent anionic compound) can be mentioned. Each will be described below.

<Multivalent cationic compound / Multivalent anionic compound>
[Multivalent anionic compound]
The polyvalent anionic compound is a compound having two or more organic acid residues and / or organic acid salt residues in total.
As the polyvalent anionic compound, for example, two or more organic acid residues and / or organic acid salt residues (hereinafter, “organic acid residues” and “organic acid salt residues” are collectively referred to as “organic acid ( And a polymer compound having a salt) residue ”.
Examples of the organic acid residue used include organic acid residues listed in the following (1) to (6).
(1) Phenolic hydroxyl group (-Ar-OH)
(2) Sulfonamide group (—SO ₂ NH—R, —SO ₂ NH ₂ )
(3) substituted sulfonamide-based acid group (hereinafter, referred to as "active imide _{group".) (- SO 2 NHOR,} -SO 2 NHSO 2 R, -CONHSO 2 R)
(4) Carboxylic acid group (—CO ₂ H)
(5) Sulfonic acid group (—SO ₃ H)
(6) Phosphate ester group, phosphate group, phosphonate ester group (—OPO ₃ H ₂ , —PO ₃ H ₂ , —OP (O) H (OH))
In the above (1) to (6), Ar represents a divalent aryl linking group, and R represents a monovalent hydrocarbon group.
Among the organic acid residues selected from (1) to (6) above, (3) a substituted sulfonamide acid group, (4) a carboxylic acid group, (5) a sulfonic acid group, or (6) a phosphate ester group Those having a phosphoric acid group or a phosphonic acid ester group are preferred. (4) Carboxylic acid groups are more preferred from the viewpoint of ease of material synthesis and mechanical strength obtained.

  The organic acid salt may be either an inorganic salt or an organic salt. Alkali metal salts such as lithium salts, sodium salts and potassium salts, onium salts such as sulfonium salts and iodonium salts, tetraalkylammonium salts, tetra Quaternary ammonium salts such as aryl ammonium salts can be exemplified.

The polymer compound only needs to have two or more organic acid (salt) residues as a whole compound, and may have a plurality of monomer units each having one organic acid (salt) residue in the side chain, The monomer unit may have a side chain having two or more organic acid (salt) residues. The polyvalent anionic polymer compound can be obtained by addition polymerization of an ethylenically unsaturated compound having an organic acid (salt) residue.
In addition, as long as the polyvalent anionic compound has two or more organic acid (salt) residues as a whole compound, in addition to the monomer unit having an organic acid (salt) residue in the side chain, an organic acid ( Salt) A copolymer having a monomer unit having no residue may be used.

  The polyvalent anionic compound is not limited to a polymer compound as long as it has a plurality of the above-mentioned organic acid (salt) residues in one molecule, and can be used without any particular limitation. A low molecular compound having a plurality of organic acid (salt) residues may be used. Examples of low molecular weight compounds having a plurality of organic acid (salt) residues in one molecule include adipic acid, succinic acid, maleic acid, 1,2,3,4-butanetetracarboxylic acid, phthalic acid, sulfophthalic acid, etc. Is mentioned.

When the polyvalent anionic compound is used as the liquid A, the preferred molecular weight of the polyvalent anionic compound is 200 or more and 300,000 or less, more preferably 300 or more and 200,000 or less, and even more preferably 500. More than 100,000. When the molecular weight of the polyvalent anionic compound is within the above range, the strength is improved, which is preferable.
In particular, as the liquid A, it is preferable to use a polymer compound having an organic acid (salt) residue in the side chain as a polyvalent anionic compound, and the molecular weight of the polymer compound is 1,000 or more and 300,000 or less. It is preferably 3,000 or more and 200,000 or less, and more preferably 5,000 or more and 100,000 or less.

Moreover, when using the said polyvalent anionic compound as B liquid, the preferable molecular weight of the said polyvalent anionic compound is 30 or more and 100,000 or less, More preferably, it is 50 or more and 50,000 or less, More preferably Is 50 or more and 20,000 or less.
When the molecular weight of the polyvalent anionic compound is within the above range, the viscosity can be kept low, so that the leveling property of the liquid B is improved and the productivity is improved.

[Multivalent cationic compound]
The polyvalent cationic compound is a generic term for a cationic residue and / or a group that can be derived from a cationic residue (hereinafter referred to as “cationic residue” and “group that can be derived from a cationic residue”). (Also referred to as “cationic residue (inducible group)”) having two or more cationic residues, having two or more cationic residues, and having a group that can be induced to two or more cationic residues. It may be one having a group capable of being derived from a cationic residue and a cationic residue, and is not particularly limited.
Examples of the polyvalent cationic compound include a polymer compound having an onium salt. Examples of the onium salt include a sulfonium salt, an iodonium salt, a phosphonium salt, and an ammonium salt, and an ammonium salt is particularly preferable.
Moreover, as a group which can be induced | guided | derived to a cationic residue, a tertiary amino group can be illustrated and can be induced | guided | derived to a cationic residue by quaternizing a tertiary amino group.

  The polyvalent cationic compound can be used without particular limitation as long as it has a plurality of the above-mentioned cationic residues (inducible groups) in one molecule. For example, a low-valent polyvalent compound having a plurality of onium groups in one molecule can be used. Molecular compounds and the like can be used. Examples of the low molecular weight compound having a plurality of onium groups in one molecule include ammonium salts such as hexamethonium, decamethonium and pentamesonium, and two or more onium groups in one molecule shown in the following specific examples. Examples include sulfonium salts and iodonium salts. Examples of the inorganic polyvalent cationic compound include polyvalent inorganic ions such as magnesium ion, calcium ion, and barium ion.

When the polyvalent cationic compound is used as the liquid A, the polyvalent cationic compound preferably has a molecular weight of 200 or more and 300,000 or less, more preferably 300 or more and 200,000 or less, and even more preferably 500 or more and 100. , 000 or less. It is preferable that the molecular weight of the polyvalent cationic compound is within the above range because the strength is improved.
In particular, when a polyvalent cationic compound is used as the liquid A, the polyvalent cationic compound may be a polymer compound having two or more monomer units having a cationic residue (inducible group) in the side chain. Preferably, the molecular weight of the polymer compound is preferably 1,000 or more and 300,000 or less, more preferably 3,000 or more and 200,000 or less, and further preferably 5,000 or more and 100,000 or less.

  When the polyvalent cationic compound is used as the liquid B, the polyvalent cationic compound preferably has a molecular weight of 30 or more and 100,000 or less, more preferably 50 or more and 50,000 or less, and still more preferably. Is 50 or more and 20,000 or less. When the molecular weight of the polyvalent cationic compound is within the above range, the viscosity can be kept low, so that the leveling property of the liquid B is improved and the productivity is improved, which is preferable.

  Specific examples of the polyvalent anionic compounds ((A-1) to (A-23)) and the polyvalent cationic compounds ((K-1) to (K-23)) are shown below. It is not limited to. In the following exemplary compounds, the polymerization ratio of the copolymer is shown in molar ratio.

Among the above exemplary compounds, from the viewpoint of strength and curing rate, the polyvalent anionic compound for liquid A includes (A-2), (A-4), (A-5), (A-6), (A-8) is preferable, and (A-5) and (A-6) are more preferable.
Moreover, as a polyvalent anionic compound for B liquid, (A-15), (A-16), (A-21), (A-23) are preferable, More preferably, (A-15), ( A-21).
In addition, from the viewpoints of strength and curing speed, the polyvalent cationic compound for liquid A is preferably (K-1), (K-2), (K-3), or (K-5), more preferably. (K-1) and (K-2).
Moreover, as a polyvalent cationic compound for B liquid, (K-14), (K-16), (K-18), (K-19), (K-20) are preferable, More preferably, ( K-18), (K-19), and (K-20).

Other than the combination of a polyvalent cationic compound and a polyvalent anionic compound, the combination of compounds that produce a solid when mixed is a combination of compounds in which a chemical reaction proceeds when two liquids are mixed and a covalent bond is generated. Examples of combinations thereof include (1) ring-opening compounds such as epoxy compounds and oxetane compounds (compounds capable of ring-opening reaction), and ring-opening compounds such as amine compounds, alcohol compounds, and carboxylic acid compounds. A combination with a compound that causes a ring-opening reaction by reacting (a compound that causes a ring-opening reaction), and (2) a combination of compounds capable of polycondensation such as an isocyanate compound and an amine compound and / or an alcohol compound. It is done.
Specific examples of these compounds are described below.

(1) Ring-opening compound and compound causing ring-opening reaction [ring-opening compound]
The ring-opening compound is a compound capable of ring-opening reaction, and examples of the ring-opening compound include epoxy compounds and oxetane compounds.
Examples of the epoxy compound may be any of glycidyl ether type, glycidyl ester type, glycidyl amine type, and alicyclic type.
Examples of the glycidyl ether type epoxy compound include diglycidyl ethers (for example, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether), tri- or more functional 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, polyglycidyl ether of phenol novolac resin, etc.) However, the present invention is not limited to these.

  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 compounds such as trisphenol methane type epoxy resin, aliphatic glycidyl ether compounds such as 1,4-butanediol glycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane tritriglycidyl ether .

Examples of the glycidyl ester compound include glycidyl ester of linolenic acid dimer.
Glycidyl ethers can be obtained commercially from Yuka Shell Epoxy Co., Ltd.

  Examples of glycidylamine type compounds include tetraglycidyldiamine diphenylmethane (TGDDM), triglycidyl isocyanurate (TGIC), hydantoin type, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-D) type, amino Examples include phenol type, aniline type, and toluidine type.

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 polyfunctional alicyclic epoxy compound include 4-vinylcyclohexylene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, and di (3,4-epoxycyclohexyl) adipate. , Di (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, di (2,3-epoxy-6-methylcyclohexylmethyl) adipate, and dicyclopentadiene dioxide. Various alicyclic epoxy compounds are commercially available and can be obtained from Union Carbide Japan Co., Ltd., Daicel Chemical Industries, Ltd., and the like.
Examples of the alicyclic epoxy compound include Celoxide 2021P, Celoxide 2081, Epolide GT-301, Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), EHPE (manufactured by Daicel Chemical Industries, Ltd.), and phenol novolac. Examples thereof include polycyclohexyl epoxy methyl ether of resin.
A glycidyl compound having a normal epoxy group having no alicyclic structure in the molecule can also be used without problems in the present invention.

As oxetane compounds that can be used in the present invention, known oxetane compounds such as those described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217 can be used, and polyvalent oxetane compounds can be used. Is preferred.
Oxetane compounds are commercially available, and examples thereof include OX-SQ and PNOX-1009 (manufactured by Toagosei Co., Ltd.).

[Compound causing ring-opening reaction]
Examples of the compound that causes a ring-opening reaction by reacting with a ring-opening compound such as the above epoxy compound or oxetane compound (a compound that causes a ring-opening reaction) include an amine compound and an alcohol compound.
As the amine compound, a polyamine compound having two or more amino groups is preferable, and as the polyamine compound, diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA), isophoronediamine (IPDA), 1, 3 -Bisaminomethylcyclohexane (1,3BAC), diaminodiphenylmethane (MDZ), m-phenylenediamine (MPDA), diaminodiphenylsulfone (DDS), dicyandiamide (DlCY) and the like.

As the alcohol compound, a polyalcohol (polyol) having two or more hydroxyl groups is preferable. As the polyol, those having a weight average molecular weight of 200 to 100,000 are widely used and classified into polyether polyols, polyester polyols, and other polyols. The
Examples of polyether polyols include polypropylene glycol (PPG), polytetramethylene glycol (PTMG), polymer polyol (polymerized with acrylonitrile / styrene in PPG), and modified products such as polyether polyamine.
Examples of the polyester polyol include condensed polyester polyol, lactone polyester polyol, and polycarbonate polyol. Examples of the condensed polyester polyol include a condensation dehydration reaction product of dibasic acid (mainly adipic acid) and glycol (ethylene glycol, 1,4-butanediol) or triol (trimethylolpropane).
Other polyols include polybutadiene polyol (butadiene having a hydroxyl group at the terminal and a copolymer), acrylic polyol (polyol having a hydroxyl group introduced into an acrylic copolymer), and partially saponified EVA (ethylene-vinyl acetate copolymer). . Other examples include phenolic polyols, phosphorus-containing polyols and halogen-containing polyols as flame retardant polyols, fluorine polyols, PET resin wastes and low-cost polyester polyols produced from DMT residues.

(2) Combinations of polycondensable compounds such as isocyanate compounds and amine compounds and / or alcohol compounds Ring-opening compounds such as epoxy compounds and oxetane compounds and reaction with the above ring-opening compounds such as amine compounds and alcohol compounds As a combination of compounds other than the combination of compounds that cause a ring-opening reaction, a chemical reaction proceeds and a covalent bond is generated when the two liquids are mixed, an isocyanate compound and an amine compound and / or an alcohol compound The combination of the compound which can be polycondensed like these is mentioned.

The isocyanate compound is a compound having one or more isocyanato groups in the molecule, and is preferably a compound having two or more isocyanato groups.
Specific examples of the isocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI (MDI), tolidine diisocyanate (TODI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), paraphenylene diisocyanate, Aromatic or aromatic polyisocyanates such as hydrogenated XDI and hydrogenated MDI; aliphatic isocyanates such as isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI); other lysine diisocyanates (LDI) and tetramethylxyresodiisocyanates (TMXDI) and the like.

  Moreover, as a combination of said isocyanate compound and a compound which can be polycondensed, an amine compound, an alcohol compound, etc. are mentioned, for example, As said specific example, said polyamine compound, a polyol compound, etc. are mentioned.

  The A liquid and the B liquid can be appropriately selected from the combinations described above. Among these, one of the A liquid and the B liquid is a polyvalent cationic compound, and the other is a polyvalent anionic compound. The combination of is preferable. More preferably, the liquid A is a polymer compound having two or more organic acid (salt) residues or a polymer compound having two or more cationic residues (inducible groups). More preferably, the liquid B is a low molecular weight compound having two or more cationic residues (inducible groups) or a low molecular weight compound having two or more organic acid (salt) residues.

  The preferable content of the polyvalent anion compound and the polyvalent cationic compound is preferably selected as long as the curability of the obtained three-dimensional structure can be imparted, and is not particularly limited. The amount is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, and still more preferably 1 to 20% by weight with respect to the total amount of the liquid. It is preferable for the content of the polyvalent anionic compound and the polyvalent cationic compound to be in the above-mentioned range since the ink jet marking has high stability and a solid product having good curability can be obtained.

(Additive)
In the present invention, a coloring agent, a solvent, a wetting agent, a fluidity enhancing agent, and the like can be added to the liquid A and / or liquid B in addition to the above components.
<Colorant>
When coloring a three-dimensional structure, colored A liquid and / or B liquid can be used.
When manufacturing a full-color three-dimensional structure, it is preferable to color A liquid. The colored liquid A is preferably a combination of the three primary colors of yellow (Y), magenta (M), and cyan (C), which are the three primary colors of the subtractive color method. In the present invention, the liquid A colored yellow is referred to as “yellow liquid A”, the liquid A colored magenta is referred to as “magenta liquid A”, and the liquid A colored cyan is referred to as “cyan liquid A”. The M dye and the C dye may be liquid A colored in two shades. The colorless A liquid can be used to adjust the color density of CMY. Moreover, A liquid (white A liquid) containing white pigments, such as titanium white, and A liquid (black A liquid) colored with black (black) dye can be used together, and a desired effect can be expressed.
The total discharge amount of the colored A liquid, colorless A liquid, and white A liquid is preferably constant per unit area, for example, per grid point or per adjacent 4 grid points. However, the total amount of these A liquids can also be increased more than an internal lattice point in the contour lattice point which forms the external shape of a three-dimensional structure.
A colored three-dimensional structure can be produced by adding a colorant to the A liquid and / or the B liquid, and in particular, a full-color tertiary having a desired coloring pattern by adding the colorant to the A liquid. An original model can be manufactured.
Colorants that can be used in the present invention are broadly classified into dyes and pigments, and dyes can be preferably used. In addition, as a coloring agent, it is not limited to the compound as described in this specification, What kind of coloring agent can be used if it is a dye and a pigment which show solubility to A liquid.

〔dye〕
By using dyes of yellow (Y), magenta (M) and cyan (C), 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, couplers represented by formulas (1) and (2) of No. 513,496A (particularly Y-28 on page 18). A coupler represented by the formula (I) of claim 1 of US Pat. No. 568,037A, a coupler represented by the general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576, General of paragraph 0008 of 4-274425 A coupler represented by (I), a coupler described in claim 1 on page 40 of European Patent 498,381A1 (particularly D-35 on page 18), and represented by formula (Y) on page 4 of 447,969A1. Couplers (especially Y-1 (page 17), Y-54 (page 41)), represented by the formulas (II) to (IV) in columns 7 to 58 of column 7 of US Pat. No. 4,476,219. And ketoimine type dyes obtained from the couplers (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, pyrazole compounds represented by the general formula (Y-II) described in JP-A-2003-73598 are more preferably used, and Y-1 shown below can be exemplified.

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.
Among them, a pyrazolotriazole azomethine compound represented by the general formula (III) described in JP-A No. 2002-121414 is preferably used, and examples thereof include M-1 and M-6 shown below.

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) C-1, C-101 and C-105 which are preferably used and can be exemplified below.

  If necessary, a black (black) dye may be used in combination with the CMY3 primary colors. The black dye can also 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. ) Kodansha (published in 1986), chemicals for inkjet printers-Development trends and prospects of materials-"CMC Corporation (published in 1997), Takeshi Amari" Inkjet printers-Technology and materials ", etc. .

[Pigment]
The pigment is not particularly limited, and all commercially available organic pigments and inorganic pigments, or pigments dispersed in an insoluble resin or the like as a dispersion medium, or a resin grafted on 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 by the YMCA liquid on the contour of the cross-sectional shape and to provide a white reflective layer directly under 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 liquid A containing white pigment (white liquid A) 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 according to the types of the B liquid and the A liquid.

In the present invention, a CMY pigment can be used as a colorant in place of the above-described CMY dye.
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 (Victoria 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).

  The average particle diameter of the pigment is preferably 0.001 to 100 μm, more preferably 0.01 to 50 μm, and further preferably 0.1 to 10 μm. It is preferable that the average particle diameter of the pigment is within the above numerical range because the dispersion stability of the pigment is good and a colorful three-dimensional product is obtained.

  The content of the colorant is preferably selected as long as a desired coloring can be imparted to the three-dimensional structure to be obtained, and is not particularly limited. However, the liquid A or liquid B (preferably liquid A) is used. The total solid content excluding the solvent is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, and still more preferably 1 to 20% by weight. It is preferable for the content of the colorant to be within the above numerical value range because the stability of inkjet marking is high and a colorful three-dimensional object is obtained.

<Solvent>
In the present invention, it is preferable to add a solvent to the liquid A and / or liquid B.
The solvent is preferably a solvent that is contained in each of the liquid A and the liquid B and dissolves a component that can form a solid by mixing, but is a solvent that can disperse the component that can form the solid. There is no particular limitation. Moreover, a solvent can also be used individually by 1 type and may use 2 or more types of solvents together.

The said solvent can be suitably selected according to the component which can form solid, the coloring agent to add, etc.
Preferably, it is water or a hydrophilic organic compound, and examples of the hydrophilic organic compound include monohydric alcohols such as methanol, ethanol and propanol, polyhydric alcohols such as ethylene glycol, diethylene glycol and propylene glycol.
Most preferably, the solvent is water.
In particular, when a combination of a polyvalent cationic compound and a polyvalent anionic compound is used as a component capable of forming a solid, it is preferable to use water or a hydrophilic organic compound, and it is more preferable to use water. . In addition, when a combination of a polyvalent cationic compound and a polyvalent anionic compound is used as a component capable of forming a solid, a polyvalent cationic compound and / or a polyvalent anionic compound, and a colorant, etc. The content of all components constituting the three-dimensional structure including other additives is preferably 0.01 to 50% by weight, more preferably 0.1 to 40% by weight with respect to the liquid A or liquid B. %, More preferably 1 to 30% by weight, and it is preferable to add a solvent.

  The solvent contained in the liquid A and the solvent contained in the liquid B are preferably compatible with each other. That is, when the solvent contained in the liquid A and the solvent contained in the liquid B are mixed, it is preferable to use a combination of solvents that form a single phase without separation. Thereby, mixing of A liquid and B liquid is performed more rapidly, and since solid formation is quick, it is preferable.

<Wetting agent>
In the present invention, it is also preferable to add a wetting agent to the liquid A and / or liquid B. When a wetting agent is added to the B liquid, it is preferable because evaporation of the solvent from the surface of the B liquid layer can be delayed and a finer three-dimensional structure can be manufactured. Further, it is preferable to add a wetting agent to the liquid A because drying / clogging of the nozzle for dropping the liquid A can be prevented.
Specifically, glycerol can be exemplified as a particularly preferable wetting agent when the solvent is aqueous. In addition, other polyhydric alcohols can be exemplified as the wetting agent, and other polyhydric alcohols include ethylene glycol, diethylene glycol and propylene glycol, which are also known in the art to retard evaporation, It is not limited to these. Other wetting agents include thiodiethanol, n-methylpyrrolidinone and dimethylhydantoin.

<Fluidity enhancer>
In the present invention, the liquid A and / or the liquid B may contain a fluidity enhancer.
Fluidity enhancers have some humectant properties, but mainly change the hydrodynamic or wetting properties of the liquid to maximize the volume of liquid ejected by nozzles such as inkjet printheads. It works like this. The enhancement of fluidity is considered to be a viscoelastic phenomenon that increases the flow rate of liquid. Thereby, a thick layer can be formed and a three-dimensional structure can be manufactured more quickly. Specific compounds that increase the fluidity of the liquid either by reducing the friction between the jet liquid and the nozzle inner wall or by reducing the viscosity of the liquid include ethylene glycol diacetate and sulfuric acid. An example is potassium aluminum.
Other suitable compounds used as flow enhancers can be selected from the following list, but are not limited thereto. Tetraethylene glycol dimethyl ether, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dodecyldimethylammoniopropane sulfonate, glycerol triacetate, ethyl acetoacetate, and polyvinylpyrrolidone having a molecular weight of about 30,000, polyethylene glycol, poly It can be selected from water-soluble polymers including acrylic acid and sodium polyacrylate. For ionic polymers such as sodium polyacrylate, the increase in fluidity varies with pH. Salts that can be used to increase fluidity include potassium sulfate, potassium aluminum sulfate, sodium hydrogen phosphate and sodium polyphosphate.

(Properties of liquid A and liquid B)
In the present invention, it is preferable to add the A liquid to the B liquid by dropping, and it is more preferable that the dropping of the A liquid is performed by a nozzle capable of discharging a fine droplet. Here, the micro droplet refers to a droplet of 1 ml or less. The fine droplets of the liquid A are preferably 0.01 pl to 1 ml, more preferably 0.1 pl to 100 μl, still more preferably 1 pl to 10 μl.
The nozzle is preferably an ink jet recording head or a dispenser, and particularly preferably an ink jet recording head. Here, the dispenser is a liquid dispensing device, and is marketed by Iwashita Engineering Co., Ltd., Tsunami, Ishikawajima General-Purpose Machine Service Co., Ltd., etc. Examples of the dispenser method include a flow rate control method, a pressurization control method, a flow path control method, and a volume measurement method, and are not particularly limited.
The ink jet recording head is preferably an on-demand type ink jet recording head, and examples thereof include a thermal method, a piezo method, and an electrostatic method. However, in the present invention, a piezo ink jet recording head can be particularly preferably used. . Use of the piezo method is preferable because the ink discharge amount is excellent in controllability and the liquid A can be discharged without heating.

That is, the step of applying the A liquid to the B liquid layer is preferably a process of discharging the A liquid onto the B liquid layer by inkjet. The preferable physical property in such a use aspect is demonstrated.
In the present invention, when the liquid A is ejected by inkjet, the viscosity is preferably 7 to 30 mPa at a temperature at the time of ejection (for example, 20 to 80 ° C., preferably 25 to 50 ° C.) in consideration of ejectability. · S, more preferably 7 to 25 mPa · s. For example, the viscosity of the liquid A at room temperature (25 to 30 ° C.) is preferably 35 to 500 mPa · s, more preferably 35 to 200 mPa · s.
Moreover, in this invention, the surface tension in 30 degreeC of A liquid becomes like this. Preferably it is 20-30 mN / m, More preferably, it is 23-28 mN / m.

The B liquid needs to be a liquid that can form a liquid layer on the bottom plate or the manufactured three-dimensional structure. From the said viewpoint, it is preferable that the viscosity at the time of manufacture of the three-dimensional structure of B liquid is 2-100,000 mPa * s, It is more preferable that it is 3-1,000 mPa * s, 5-1,000 mPa -More preferably, it is s.
In addition, although the temperature at the time of manufacture is not specifically limited, From the ease of manufacture of a three-dimensional modeling apparatus and the point of the expense at the time of preparation, it is preferable that it is 15 to 50 degreeC, and it is especially preferable that it is room temperature.

(Three-dimensional modeling material)
The three-dimensional modeling material of the present invention includes the A liquid and the B liquid. The three-dimensional modeling material of the present invention is preferably a three-dimensional modeling material composed of the A liquid and the B liquid.
Moreover, A liquid and / or B liquid can also be made into a concentrated liquid.
Specifically, the three-dimensional modeling apparatus may be configured so as to be diluted immediately before use, or the A liquid and / or the B liquid diluted in advance may be used, and is not particularly limited. In addition, in this specification, when preferable content of each component in A liquid and B liquid is described, this content means content (concentration) at the time of use.

(Method for manufacturing a three-dimensional structure)
The manufacturing method of the three-dimensional structure of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic cross-sectional view illustrating an example of a method for producing a three-dimensional structure according to the present invention.
In FIG. 1, the three-dimensional modeling apparatus 1 includes a modeling container 10, and the modeling container 10 is provided with a B liquid supply port 30 that supplies a B liquid. In the modeling container 10, a bottom plate 12 that can be moved up and down is provided. B liquid is supplied into the modeling container 10, a B liquid layer is formed on the bottom plate 12, and A liquid is supplied onto the thin layer of B liquid from the nozzle 21 of the A liquid applying unit 20 according to the cross-sectional shape data. The The A liquid application region forms a solid by mixing the A liquid and the B liquid to form a cross-sectional shape, and is combined with the cross-sectional shape below the second layer after the second layer. By application of the A liquid, the B liquid area (A liquid application area) to which the A liquid is applied between the B liquid surface and the bottom plate or the three-dimensional structure becomes a solid. By applying the A liquid while scanning the A liquid applying unit 20 in the horizontal direction, a cross-sectional shape having a predetermined pattern is obtained.
Next, the bottom plate 12 is moved downward by one slice pitch, B liquid is newly supplied according to the amount of movement, and a B liquid layer is formed. On the newly formed B liquid layer, the A liquid is applied from the nozzle 21 of the A liquid applying unit 20 according to the next adjacent cross-sectional shape data, and a new A liquid applying area is formed. A solid is formed in this area | region by mixing A liquid and B liquid.

The slice pitch (lamination pitch) is preferably 1 to 500 μm, more preferably 5 to 300 μm, and still more preferably 10 to 200 μm.
Moreover, it is preferable that the amount of droplets of the liquid A to be applied is 0.01 pl to 100 μl, more preferably 0.1 pl to 10 μl, and still more preferably 1 pl to 1 μl.
It is preferable that the slice pitch and the amount of droplets are within the above ranges because the strength is high and a high-definition three-dimensional structure can be obtained.

After the formation of the thin layer of the B liquid and the application of the A liquid are sequentially repeated as many times as necessary, the three-dimensional structure 40 can be obtained by separating the B liquid in the region where the A liquid is not applied.
In the three-dimensional structure manufacturing method of the present invention, unlike the conventional optical modeling method, the three-dimensional structure can be manufactured by applying the liquid A without irradiating light. Therefore, the three-dimensional modeling apparatus can be manufactured at a low cost.
In addition, it is possible to manufacture a three-dimensional structure that is excellent in color reproducibility, which is impossible with conventional stereolithography. Specifically, the liquid B is colorless and transparent or white, preferably colorless and transparent, and the liquid A containing a colorant is applied to the liquid B. A three-dimensional structure having a desired color can be manufactured by using the A liquid applying unit 20 including a plurality of nozzles 21 and applying the A liquid having different colors from each nozzle.

In the conventional optical modeling method, since the resin liquid supplied to the modeling container has photocurability, there is a problem that the resin liquid is hardened and thickened while the three-dimensional structure is manufactured, and the resin liquid cannot be reused. . In this invention, it is not necessary to make B liquid photocurable, B liquid hardens | cures only by mixing with A liquid, and there is almost no deterioration of B liquid other than A liquid provision area | region. Therefore, after manufacturing the three-dimensional structure, the liquid B other than the liquid A application area can be collected and reused.
FIG. 2 is a perspective view schematically showing the cross-sectional shape formed in each adjacent layer 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 B liquid layer forming step and the 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 the liquid B to be laminated is cut out from the model data, and shape data and coloring data indicating a cross-sectional area 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 B liquid layer (slice pitch at the time of creating cross-sectional data) and the number of layers (the number of sets of colored shape data) when modeling the modeling object are controlled from the computer to drive the pattern creation device. Is input to the department.

In the third step, the liquid B serving as a material for manufacturing the three-dimensional structure is supplied in the modeling stage.
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. A typical example will be described below using an inkjet method 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 A liquid is appropriately discharged from each inkjet discharge nozzle based on the color data. As the liquid A, it is preferable to use two or more liquids A selected from the group consisting of at least one colored liquid A, a white liquid A, and a colorless and transparent liquid A.

In the present invention, it is also preferable that at least one lattice point located in the outermost layer of the modeled object is provided with A liquid 1.05 to 5 times the A liquid applied to the grid point positioned inside the modeled object. It is one of. It is preferable that A liquid to provide is 1.1 to 2.5 times. It is preferable that the amount of the liquid A to be applied is within the above range because the surface glossiness and strength of the molded article are improved.
The at least one grid point located in the outermost layer of the modeled object is the grid point of the entire bottom layer cross-sectional shape of the modeled object, the grid point of the entire cross-sectional shape of the top layer, and the middle located between the bottom layer and the top layer It means that a grid point (contour grid point) constituting the outer contour shape of the cross-sectional shape of the layer may be included, and one or a plurality of grid points (adjacent grid points) adjacent to these may be included as appropriate. In this case, it is not always necessary to discharge the liquid A increased to the same degree at the contour grid points and the adjacent grid points. The discharge magnification can be adjusted with an appropriate gradient. Even in the case of adjustment, it is not necessary to set the contour grid point to the maximum magnification, and it is also possible to maximize the discharge magnification of the adjacent grid point immediately adjacent to the contour grid point.
FIG. 3 is a plan view showing an example of cross-sectional data subdivided into a grid generated in the second step. In FIG. 3, the hatched grid is the area where the A liquid is discharged. At this time, you may make high the discharge magnification of the lattice point located in the outermost layer of a molded article. In the middle cross-sectional shape, it is preferable to discharge a larger amount of liquid A to the contour lattice points corresponding to the outer surface than the internal lattice points. The discharge magnification may be increased up to adjacent grid points for several grids adjacent to the contour grid point. The adjacent number lattice is preferably 1 to 10 lattice portions, more preferably 1 to 5 lattice portions. The discharge magnification can be adjusted by changing the discharge amount at one time and / or increasing the number of discharges to the same grid point.

The colored liquid A is preferably a combination of the three primary colors of yellow (Y), magenta (M), and cyan (C), which are the three primary colors of the subtractive color method. The M dye and the C dye may be liquid A colored in two 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 A liquid, colorless A liquid, and white A liquid is preferably constant per unit area, for example, per grid point or per adjacent 4 grid points.
In addition, as another example of the formation process of the colored cross-sectional shape, after forming a solid in the A liquid application part by discharging only the colorless A liquid to the B liquid based on the shape data and mixing with the B liquid, the layer Based on the coloring data, a normal CMY ink that does not contain the liquid A can be a two-stage process that ejects the liquid B on the solid.

By sequentially repeating the third step to the fourth step, the colored solid formed by mixing the B liquid and the A liquid corresponding to the cut surface obtained by cutting the object to be modeled by a plurality of surfaces is sequentially stacked to form the tertiary. An original model can be manufactured.
In addition, solid is not formed in the area | region of B liquid to which A liquid is not provided.

  In the fifth step, the liquid B in the region where the liquid A is not applied is separated, and the three-dimensional structure is taken out. In addition, B liquid which A liquid A was not provided can be collect | recovered and it can utilize again as a material.

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. Cleaning is performed by washing the three-dimensional structure, and excess B liquid is removed. 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.
In addition, although the present Example demonstrated as an example the three-dimensional modeling target to which the coloring pattern etc. were given, in this invention, a three-dimensional modeling target is not limited to this. That is, it is needless to say that a monochromatic or colorless three-dimensional structure can be manufactured based on cross-sectional shape data that does not have color data.

(Three-dimensional structure manufacturing equipment)
Next, a manufacturing apparatus (three-dimensional modeling apparatus) for a three-dimensional structure that can be suitably used in the present invention will be described.
FIG. 4 is a perspective view showing an embodiment of a three-dimensional modeling apparatus that can be used in the present invention.
In FIG. 4, the three-dimensional modeling apparatus 1 includes a modeling container 10 to which a B liquid is roughly supplied, and an A liquid applying unit 20 that applies the A liquid to the B liquid from above.
The modeling container 10 includes a B liquid supply port 30 that supplies the B liquid to the modeling container 10. The B liquid supply port 30 is configured so that the B liquid can be supplied by a pump or the like (not shown), and the supply amount of the B liquid can be controlled. In addition, a bottom plate (not shown) is disposed inside the modeling container 10 so as to be movable up and down.

  Above the modeling container 10, the A liquid application unit 20 is disposed. The three-dimensional modeling apparatus 1 includes an X-axis guide rail 22b and a Y-axis guide rail 22a for moving the A liquid application unit 20 to two axes of the XY axes. Thereby, the A liquid provision part 20 moves along an XY axis, ie, parallel to a modeling surface.

A nozzle (not shown) is formed on the lower surface of the A liquid applying unit 20, and the A liquid is discharged from the nozzle. Moreover, it is comprised so that A liquid can be supplied to the said nozzle.
Said nozzle can be suitably selected from a well-known dispenser and an inkjet recording head. As the ink jet recording head, for example, a cleaning blade that cleans a face surface on which nozzles (ejection ports) are formed while moving in a predetermined cleaning direction, and a cleaning blade that is disposed downstream of the face surface, the cleaning surface is disposed. It can be set as the ink jet recording head provided with the absorber which absorbs A liquid adhering to a blade, for example, can refer to JP, 2007-38558, A JP, 2007-38604, A, etc.

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

<Liquid A (1)>
The following components were stirred with a stirrer to obtain liquid A (1).
Exemplified compound (A-1) (Aldrich): 10 parts by weight Colorant: Y-1: 2 parts by weight Water: 88 parts by weight

<A liquid (2)-A liquid (30)>
Liquid A (2) to liquid A (30) were obtained by changing the exemplified compound (A-1) of liquid A (1) to the compounds shown in Table 1.

<Liquid A (31)>
The following components were stirred with a stirrer to obtain liquid A (31).
-1,4-butanediol diglycidyl ether (Aldrich): 98 parts by weight-Colorant: Y-1: 2 parts by weight

<A liquid (32)-A liquid (45)>
By changing 1,4-butanediol diglycidyl ether of Liquid A (31) to the compounds shown in Table 1, Liquid A (32) to Liquid A (45) were obtained.
In Table 1, when the exemplified compound is a polymer, the molecular weight is described.

<Magenta A liquid (1)>
Magenta liquid A (1) was produced in the same manner as liquid A (1) except that M-1 was used instead of liquid A (1) Y-1.
<Cyan A liquid (1)>
Cyan A liquid (1) was produced by the same method as A liquid (1) except that C-1 was used instead of Y-1 of A liquid (1).
<Black A liquid (1)>
A black A liquid (1) was produced in the same manner as the A liquid (1) except that carbon black was used instead of Y-1 in the A liquid (1).
<White A liquid (1)>
The white A liquid (1) was manufactured by the method similar to A liquid (1) except having used the titanium oxide instead of Y-1 of A liquid (1).

<Liquid B (1)>
The following components were stirred with a stirrer to obtain liquid B (1).
Exemplified compound (A-1) (Aldrich): 2 parts by weight Water: 98 parts by weight

<B liquid (2) -B liquid (30)>
B liquid (2)-B liquid (30) were obtained by changing the exemplary compound (A-1) of B liquid (1) into the compound of Table 2.

<Liquid B (31)>
The following components were stirred with a stirrer to obtain liquid B (31).
・ 100 parts by weight of 1,4-butanediol diglycidyl ether (Aldrich)

<B liquid (32) -B liquid (45)>
Liquid B (32) to liquid B (45) were obtained by changing 1,4-butanediol diglycidyl ether of liquid B (31) to the compounds shown in Table 2.
In Table 2 below, when the exemplified compound used was a polymer, the molecular weight was described.

<Comparison X solution (1)>
The following components were stirred with a stirrer to obtain a comparative X solution (1).
Colorant: Y-1: 2 parts by weight Water: 98 parts by weight

<Comparison X solution (2)>
The following components were stirred with a stirrer to obtain a comparative X solution (2).
-Ethylene glycol dimethyl ether (Aldrich): 98 parts by weight-Colorant: Y-1: 2 parts by weight

<Comparison Y liquid (1)>
The following components were stirred with a stirrer to obtain a comparative Y liquid (1).
・ Water: 100 parts by weight

<Comparison Y liquid (2)>
The following components were stirred with a stirrer to obtain a comparative Y liquid (2).
・ Ethylene glycol dimethyl ether (Aldrich): 100 parts by weight

Example 1
Using the three-dimensional modeling apparatus described in the specification, the liquid A (1) supplied from the liquid A supply hose to the liquid injection nozzle is applied to the liquid B (27) installed in a thin layer on the bottom plate. By spraying from the hole, a thin-layer cured product having a cross-sectional shape obtained by cutting the modeling target object along a parallel cross-section was obtained.
Here, a piezo-type ink jet recording head was used as the liquid A ejection nozzle, and the amount of liquid A discharged was 6 pl per dot. One slice pitch was set to 50 μm.

(Examples 2 to 15 and Comparative Examples 1 to 4)
A three-dimensional structure was manufactured in the same manner as in Example 1, except that the liquid A (1) and liquid B (27) were changed to those shown in Table 3 in Example 1.

<Strength evaluation>
A plate having a diameter of 5 cm and a thickness of 1 cm was prepared by the method of Example 1, placed on a donut-shaped table having a diameter of 4 cm (outer diameter of 4 cm, inner diameter of 3 cm) and a thickness of 1 cm, and a weight of 100 g was placed on the plate. The time until the plate broke was evaluated.
This evaluation shows that the longer the time, the higher the strength.

<Curing speed>
Liquid B was filled in the petri dish to a depth of 1 cm, and liquid A droplets were dropped from above with a dropper, and the time until curing was measured.
This evaluation shows that the shorter the time, the faster the curing rate.

(Example 16)
Evaluation was carried out in the same manner as in Example 1 except that Magenta A liquid (1) was used instead of A liquid (1) in Example 1.

(Example 17)
Evaluation was performed in the same manner as in Example 1 except that Cyan A liquid (1) was used instead of A liquid (1) in Example 1.

(Example 18)
Evaluation was carried out in the same manner as in Example 1, except that the black A liquid (1) was used instead of the A liquid (1) in Example 1.

(Example 19)
Evaluation was performed in the same manner as in Example 1, except that the white A liquid (1) was used instead of the A liquid (1) in Example 1.
The results are shown in Table 4 below.

<Example 20>
As a result of performing modeling by filling different nozzles with yellow A liquid (1), magenta A liquid (1), cyan A liquid (1), black A liquid (1), and white A liquid (1), A model was obtained.

DESCRIPTION OF SYMBOLS 1 3D modeling apparatus 10 Modeling container 12 Bottom plate 20 A liquid provision part 21 Nozzle 22a Y-axis guide rail 22b X-axis guide rail 30 B liquid supply port 40 Three-dimensional structure

Claims (10)

Forming the liquid B into a layer having a predetermined thickness;
Shaped object a to be cut sectional shape cross section parallel to the layer of liquid B, a step of applying a formable liquid A solid by mixing with solution B, to sequentially repeat a
One of the liquid A or the liquid B contains a cationic residue and / or a compound having two or more groups that can be induced to a cationic residue, and the other one is an organic acid residue and / or an organic acid salt. A method for producing a three-dimensional structure, comprising a compound having two or more residues (organic acid (salt) residues) .   The method for producing a three-dimensional structure according to claim 1, wherein the liquid A and / or the liquid B contains a dye and / or a pigment. The step of applying the solution A is a step of dropping the liquid A, dripping of the liquid A is carried out by ejectable nozzle fine droplets, production of three-dimensional molded article according to claim 1 or 2 Method. The manufacturing method of the three-dimensional structure according to claim 3 , wherein the nozzle is an ink jet recording head or a dispenser.   The organic acid (salt) residue includes (1) a phenolic hydroxyl group (—Ar—OH), (2) a sulfonamide group (—SO ₂ NH-R, -SO ₂ NH ₂ ), (3) substituted sulfonamide acid groups (—SO ₂ NHOR, -SO ₂ NHSO ₂ R, -CONHSO ₂ R), (4) carboxylic acid group (—CO ₂ H), (5) sulfonic acid group (-SO _Three H), (6) phosphate group, phosphate group, phosphonate group (-OPO _Three H ₂ , -PO _Three H ₂ , -OP (O) H (OH)) (wherein Ar represents a divalent aryl linking group and R represents a monovalent hydrocarbon group), and a group of these organic acid salts The manufacturing method of the three-dimensional structure according to any one of claims 1 to 4, which is selected from the following.   The compound having two or more organic acid residues and / or organic acid salt residues is selected from the group consisting of the following (A-1) to (A-23). The manufacturing method of the three-dimensional structure according to 2.

  The cationic residue and / or the compound having two or more groups that can be induced to a cationic residue is a polymer compound having an onium salt, a low molecular compound having a plurality of onium groups in one molecule, and an inorganic The method for producing a three-dimensional structure according to any one of claims 1 to 6, wherein the three-dimensional structure is selected from the group consisting of polyvalent cationic compounds.   The cationic residue and / or the compound having two or more groups that can be induced to a cationic residue is selected from the group consisting of the following (K-1) to (K-23). The manufacturing method of the three-dimensional structure as described in any one.

The three-dimensional modeling material containing A liquid and B liquid used for the manufacturing method of the three-dimensional structure as described in any one of Claims 1-8 . A three-dimensional structure manufactured by the manufacturing method according to any one of claims 1 to 8 .

Images