JP6346746B2 - Manufacturing method of three-dimensional structure, kit for manufacturing three-dimensional structure, and three-dimensional structure - Google Patents

Description

  The present invention relates to a method for manufacturing a three-dimensional structure, a kit for manufacturing a three-dimensional structure, and a three-dimensional structure.

  Conventionally, when a 3D printed material is obtained by stacking ink by a lamination method, a support material is required to form the overhang portion.

  Patent Document 1 describes an inkjet three-dimensional modeling apparatus in which a silicone material or a fluorine material is included as a support material.

  Patent Document 2 describes a three-dimensional molding method in which a support material is a mixture of propylene glycol, polyethylene glycol, glycerol and a photoinitiator and is removed with an aqueous alkaline solution.

  Patent Document 3 describes a method of recovering surplus of flowable resin with a roller. In this method, for the purpose of easily removing the support material finally, it is desirable to add a removable material to a material similar to the model material, specifically, a water-swelling gel, Wax, thermoplastic resin, water-soluble material, soluble material, etc. are used.

  Patent Document 4 discloses a model material for forming an optically shaped article in an ink jet molding method containing a curable resin component having a weighted average of SP values of 9.0 to 10.3; and a water-soluble monofunctional ethylenically unsaturated material. A support material for shape support at the time of optical modeling in an inkjet optical modeling method comprising a monomer, polypropylene glycol and / or water having a number average molecular weight of 100 to 5,000, and a photopolymerization initiator is described. Yes.

JP 2004-255839 A (published September 16, 2004) JP 2011-5658 A (published on January 13, 2011) JP 2013-67121 A (published April 18, 2013) JP 2012-111226 A (released on June 14, 2012)

  However, it is difficult to easily remove the support material described in Patent Document 1.

  Since the support material of Patent Document 2 has a slow curing speed, it takes a long time to produce a three-dimensional structure, and there is no suggestion for producing it in a shorter time.

  With the method described in Patent Document 3, it is difficult to obtain a printed matter in a short time and to remove the support material.

  Patent Document 4 has a large difference in shrinkage and moisture absorption between the model material and the support material, and is easily deformed. Therefore, there is a high possibility that further processing or the like will be required to obtain a desired shape, and as a result, it takes a long time to obtain a shaped object.

  The present invention has been made in view of such problems, and an object thereof is to manufacture a three-dimensional structure in a simple and short time.

  In order to solve the above-described problems, a method for producing a three-dimensional structure according to the present invention includes a model material printing step in which an acid value is 20 or less and printing is performed using a model material that is an active energy ray-curable ink. A support material printing step for printing a support material having an acid value of 80 or more and an active energy ray curable ink, and a support material removal step for removing the support material printed by the support material printing step. It is characterized by.

  By utilizing a large difference in acid value between the model material and the support material, the support material can be easily removed in a short time, and as a result, a three-dimensional structure can be manufactured easily and in a short time. For example, if a basic removal solution is used, the support material can be easily removed. In general, those having a low acid value are often difficult to dissolve in water, and those having a high acid value are often soluble in water. Therefore, the support material can be easily and easily removed even when water is used as a removing solution. be able to.

  In the method for manufacturing a three-dimensional structure according to the present invention, the model material may be a coloring ink containing a colorant or an ink not containing a colorant.

  When the model material includes a colorant, a three-dimensional structure colored in a desired color can be obtained. If the model material is an ink that does not contain a colorant, a three-dimensional structure without color can be obtained.

  In the three-dimensional structure manufacturing method according to the present invention, it is more preferable that the support material does not include a colorant or is an ink including an extender pigment. Even if the support material remains, the color tone of the model material can be prevented from being impaired.

  In the method for producing a three-dimensional structure according to the present invention, the model material does not substantially contain a (meth) acrylic acid group, and the support material is at least one of a (meth) acrylic acid group and a sulfonic acid group. It is more preferable to contain. The difference in acid value between the model material and the support material can be increased, and the support material can be removed more easily and quickly. Moreover, the three-dimensional structure excellent in dimensional stability can be provided. This is because if the difference in acid value is small, there may be an effect such as swelling on the model material depending on the dissolving agent, and the occurrence of this effect can be suppressed due to the large difference in acid value.

  In the three-dimensional structure manufacturing method according to the present invention, it is more preferable that the support material includes a water-soluble vinyl monomer that becomes water-soluble in the homopolymer. Since it becomes easy to remove the support material with water, the support material can be removed more easily and quickly.

  In the method for manufacturing a three-dimensional structure according to the present invention, it is more preferable that the model material printing step and the support material printing step are performed by an inkjet method. Flexible shapes can be modeled with high accuracy.

  In the three-dimensional structure manufacturing method according to the present invention, it is more preferable that the support material removing step is performed using at least one of an alkaline aqueous solution and alcohol. Since the support material used in the present invention quickly dissolves in the alkaline aqueous solution and alcohol, the support material can be removed more easily and quickly.

  In the three-dimensional structure manufacturing method according to the present invention, it is more preferable that the support material is water-soluble and the support material removing step is performed using water. Support material can be quickly removed by easy-to-handle water. In addition, those that are water-soluble and have an acid value of 80 or more dissolve very rapidly in water. Therefore, a three-dimensional structure can be obtained in a shorter time.

  The kit for producing the three-dimensional structure according to the present invention has an acid value of 20 or less, a model material that is an active energy ray-curable ink, an acid value of 80 or more, and an active energy ray curing. And a support material that is a mold ink.

  Since it can utilize for the manufacturing method of the three-dimensional structure which concerns on this invention mentioned above, a three-dimensional structure can be manufactured easily and in a short time.

  A three-dimensional structure formed by a model material having an acid value of 20 or less and an active energy ray curable ink and a support material having an acid value of 80 or more and an active energy ray curable ink. Is also within the scope of the present invention.

  According to the present invention, there is an effect that a three-dimensional structure can be manufactured easily and in a short time.

<Method for producing three-dimensional structure according to the present invention>
In the method for producing a three-dimensional structure according to the present invention, the acid value is 20 or less, the model material printing step of printing using a model material that is an active energy ray-curable ink, and the acid value is 80 or more, It includes a support material printing step for printing a support material that is an active energy ray curable ink, and a support material removing step for removing the support material printed by the support material printing step. By utilizing a large difference in acid value between the model material and the support material, the support material can be easily removed in a short time, and as a result, a three-dimensional structure can be manufactured easily and in a short time. For example, if a basic removal solution is used, the support material can be easily removed. In general, those having a low acid value are often difficult to dissolve in water, and those having a high acid value are often soluble in water. Therefore, the support material can be easily and easily removed even when water is used as a removing solution. be able to.

[Model material]
The model material used in the method for producing a three-dimensional structure according to the present invention has an acid value of 20 or less and is an active energy ray curable ink.

  In this specification, the “acid value” is the number of mg of potassium hydroxide necessary to neutralize free acid groups present in 1 g of ink (model material or support material). In addition, when the polymerization component contained in the ink is acrylic and the ink does not contain other free acid groups, potassium hydroxide necessary for neutralizing the free acid groups present in 1 g of the acrylic component. It is possible to approximate the mg number as an acid value.

  An active energy ray-curable ink is an ink that cures when irradiated with active energy rays. Since it can be cured quickly, mixing of the model material and the support material can be suppressed. Therefore, an ink jet method that discharges both the model material and the support material can be suitably used.

  The type of active energy rays required for curing by the model material used in the method for producing a three-dimensional structure according to the present invention is not particularly limited, and examples thereof include X-rays, electron beams, and ultraviolet rays. Of these, ultraviolet rays are preferred. That is, UV curable ink is preferable as the model material.

  As a light source such as an ultraviolet ray, a light source used in a conventionally known UV curable inkjet ink may be employed. For example, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp and the like can be mentioned. Examples of commercially available products include H lamp, D lamp, and V lamp manufactured by Fusion System.

When the model material is an ultraviolet curable ink, it is preferable that the model material is cured by irradiation with 50 to 1000 mJ / cm ² of accumulated light with ultraviolet rays emitted from an ultraviolet light source, and cured at 50 to 200 mJ / cm ² . More preferably.

  The model material used in the method for manufacturing a three-dimensional structure according to the present invention can be polyfunctional. This improves sensitivity to light. If it is polyfunctional, it can be cured by an ultraviolet light emitting semiconductor element such as a UV-LED or an ultraviolet light emitting semiconductor laser. The reason why the model material has high sensitivity is as follows. That is, it is modeled (cured) at low illuminance by the crosslinking effect brought about by being multifunctional. In addition, since a photopolymerization initiator and a sensitizer suitable for the light source can be selected, the sensitivity to light can be increased.

(Polymerization component)
More preferably, the model material does not substantially contain a (meth) acrylic acid group. That is, the polymerization component contained in the model material is preferably a (meth) acrylic monomer having substantially no free acid group. The difference in acid value between the model material and the support material can be increased, and the support material can be removed more easily and quickly. Moreover, the three-dimensional structure excellent in dimensional stability can be provided.

  There is no limitation in particular as a (meth) acryl monomer, A well-known (meth) acryl monomer can be used.

  For example, methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl , Isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl and other monofunctional methacrylates having 1,3-butylene glycol, 1,4-butanediol, 1,5-pentane Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethyl Dimethacrylates such as glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dimethacrylate of tris (2-hydroxyethyl) isocyanurate, 4 mol or more per 1 mol of neopentyl glycol Dimethacrylate of diol obtained by adding ethylene oxide or propylene oxide, dimethacrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, 3 mol or more per mol of trimethylolpropane Diol or trimethacrylate of triol obtained by adding ethylene oxide or propylene oxide, 4 mol or more of ethylene oxide per 1 mol of bisphenol A Dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, polymethacrylate of dipentaerythritol, ethylene oxide modified phosphate methacrylate, ethylene oxide modified alkyl phosphorus Examples include polyfunctional methacrylates such as acid methacrylates.

  Moreover, it is possible to raise the intensity | strength and solvent resistance of a model material hardened | cured material by using a polyfunctional monomer together. Other polyfunctional monomers that can be included in the model material are not particularly limited, and known polyfunctional monomers can be used. For example, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octane Diacrylate such as diol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dis of tris (2-hydroxyethyl) isocyanurate Diacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of acrylate, neopentyl glycol, 2 mol of ethylene oxide or propylene to 1 mol of bisphenol A Diol of diol obtained by adding xoxide, 3 mol or more of ethylene oxide or propylene oxide added to 1 mol of trimethylolpropane, 4 mol or more of ethylene oxide per 1 mol of bisphenol A Or polyfunctionality such as diacrylate of triol obtained by adding propylene oxide, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyacrylate of dipentaerythritol, ethylene oxide modified phosphate acrylate, ethylene oxide modified alkyl phosphate acrylate Acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyl Having a vinyl ether group such as di- or trivinyl ether compounds such as diglycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether Examples thereof include a polymerizable compound. These may be used alone or in combination of two or more.

  The model material may contain a reactive oligomer such as an acrylate oligomer having a high molecular weight from the viewpoint of improving the cured coating film performance. The amount of the reactive oligomer is preferably a small amount in order to reduce the possibility that satellites are generated during ink jet ejection. For example, an amount that does not exceed 20% by mass with respect to the total amount of the active energy ray polymerizable compound is more preferable.

  Examples of reactive oligomers include urethane acrylate oligomers, epoxy acrylate oligomers, and polyester acrylate oligomers. Two or more types can be used in combination.

  The acrylate compound does not substantially contain an acid group, but the acid value may be 20 or less as an ink even when a free acid group is slightly generated by hydrolysis to show an acid value. That is, in the present invention, “substantially does not contain a (meth) acrylic acid group” includes a case where it contains a (meth) acrylic acid group which is generated by liberation.

(Photopolymerization initiator)
When the model material is an ultraviolet curable ink, the model material more preferably contains a photopolymerization initiator. As the photopolymerization initiator, a radical polymerization type photopolymerization initiator can be used.

  Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are preferably used. . Further, other molecular cleavage types include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like can be employed. In addition, a hydrogen abstraction type photopolymerization initiator such as benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenyl sulfide may be employed. These may be only one kind or a plurality of kinds may be mixed.

  Moreover, when using an LED lamp as an active energy ray source, it is preferable to select a photopolymerization initiator in consideration of the emission peak wavelength of the LED. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino)-is suitable as a photopolymerization initiator when using a UV-LED. 2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -butan-1-one), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6 -Trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone and the like.

  Examples of sensitizers for photopolymerization initiators include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N- An amine that does not cause an addition reaction with a polymerizable component such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone can also be used in combination.

  In order to increase the storage stability of the ink, a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt, etc. is added to the model material. You may add in 2 mass%.

(Coloring agent)
The model material may be a color ink containing a colorant or an ink not containing a colorant. When the model material includes a colorant, a three-dimensional structure colored in a desired color can be obtained. If the model material is an ink that does not contain a colorant, a three-dimensional structure without color can be obtained. The colorant may be a pigment or a dye.

  In the case of producing a three-dimensional object having a thickness, a three-dimensional object having a transparent and coloring effect can be obtained by using a dye as a colorant. Various dyes that have been used for conventional inkjet recording, such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and oil dyes. Dyes. Of these, oil-based dyes are particularly preferable from the viewpoints of solubility in ink polymerization components and color development of a cured product.

  In order to obtain an opaque three-dimensional object, it is preferable to employ a pigment as a coloring material, and for example, an inorganic pigment and an organic pigment can be employed.

  As the inorganic pigment, titanium oxide, iron oxide, and carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

  Specific examples of the pigment include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No. 2200B, etc. are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. made by Columbia, and Regal400R, 330R, 660R, MoguL made by Capote 700, Monarch 800, 880, 900, 1000, 1100, 1300, 1300, 1400, etc. are manufactured by Degussa Color Black FW1, FW2, FW2V, FW18, FW200, Color Black S150, S160, S170, Printex35, U, V, 140U, Special Black6, 5, 4A, 4 and the like.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 180, 185, 213 and the like.

  Examples of pigments used for magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 168, 184, 202, 209, C.I. I. Pigment violet 19 and the like.

  Examples of pigments used for cyan ink include C.I. I. And CI Pigment Blue 1, 2, 3, 15: 3, 15: 4, 60, 16, and 22.

  The average particle diameter of the pigment is preferably in the range of 10 to 300 nm, more preferably about 50 to 200 nm. Further, in order to obtain the addition amount of the colorant, sufficient image density and light fastness of the printed image, it is preferably contained in the range of 1 to 20% by mass of the total amount of the ink.

  For the pigment, it is preferable to use a pigment dispersant for the purpose of enhancing the dispersion stability with respect to the active energy dose compatible compound or the like. Specifically, Ajinomoto Fine Techno Co., Ltd. Ajisper (registered trademark) PB821, PB822, PB817, Abyssia Corporation Solsperse (registered trademark) 24000GR, 32000, 33000, 39000, Enomoto Kasei Co., Ltd. Disparon (registered trademark) DA -703-50, DA-705, DA-725, and the like, but are not limited thereto. Further, the amount of the polymer dispersant used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 60% by mass with respect to the pigment. When the amount used is 10% by mass or more, sufficient dispersion stability is obtained, and when it is 80% by mass or less, the increase in the viscosity of the ink is suppressed, and the ejection stability is improved.

  The model material is preferably designed so that the viscosity after blending each monomer is approximately 1 to 100 mPa · sec, although it depends on the ink jet device to be used. The viscosity of the model material and the support material when ejected by inkjet may be different, but is preferably a close value in consideration of the ejection characteristics and curing characteristics of inkjet, and more preferably the same.

(Other ingredients)
The model material may be blended with a non-reactive resin such as an acrylic resin, an epoxy resin, a terpene phenol resin, or a rosin ester for the purpose of imparting adhesion to the substrate to be printed. The addition amount is preferably small. This is because the possibility that satellites are generated can be reduced and a decrease in solvent resistance can be prevented.

  In addition, the model material is a polyester-based resin for adjusting surfactants, leveling additives, matting agents, and film physical properties as necessary within a range that does not impair the effects of the present invention and does not impair ejection stability. Polyurethane resin, vinyl resin, acrylic resin, rubber resin, and waxes can be added.

  As a method for producing a model material, for example, when a pigment is included, a mixture including a pigment and an active energy dose-matching compound, a polymer dispersant as necessary, a resin, and a conventionally known disperser such as a bead mill is used. Then, after the pigment is dispersed, a photopolymerization initiator is added, and an additive such as a surface tension adjuster is added if necessary, followed by stirring and dissolution. After preparing a high-concentration pigment dispersion (mill base) using a conventionally known disperser such as a bead mill in advance, the active energy ray polymerizable compound in which the photopolymerization initiator is dissolved, the additive, etc. are stirred and mixed to create a model. A material may be manufactured.

  As a stirring device and a dispersing device for dispersing a pigment, for example, conventionally known beads mill, ultrasonic homogenizer, high-pressure homogenizer, paint shaker, ball mill, roll mill, sand mill, sand grinder, dyno mill, disper mat, SC mill, nanomizer, and the like. Can be mentioned.

[Model material printing process]
The model material printing step included in the method for manufacturing a three-dimensional structure according to the present invention is a step of printing using a model material.

  The method for printing using the model material is not particularly limited, but it is more preferably performed by the ink jet method. Flexible shapes can be modeled with high accuracy.

  In addition, the ink jet method is preferably digitally controllable, and can print in a non-contact manner on a recording medium and a model material and a support material formed by being discharged and cured last time. As the ink jet method, any conventionally known method can be used. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.

  The model material used in the method for manufacturing a three-dimensional structure according to the present invention is excellent in adhesiveness to a plastic material. This is because the surface of the plastic material is once wetted by the monomer by the process of curing after landing on the plastic material as a monomer. Therefore, it is possible to easily print on the surface of a plastic molded body or the like. Examples of plastic materials include ABS (acrylonitrile butadiene styrene) resin, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, and PC (polycarbonate), which are used as general-purpose injection molding plastics. / ABS resin, ABS polymer alloy such as PBT (polybutylene terephthalate) / ABS, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic acid ester / styrene) resin, PC (polycarbonate) resin, acrylic resin, methacrylic resin, PP (polypropylene) resin, and the like.

  In addition, as a recording medium, a film made of a plastic material such as a thermoplastic resin film for packaging material can be adopted. Examples of thermoplastic resin films used for food packaging include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film). And polyolefin films such as polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment such as uniaxial stretching or biaxial stretching. The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary.

  Since the discharged model material needs to be cured by energy rays, for example, a step of printing an image by discharging the model material onto a recording medium, and a wavelength peak of 365 to 420 nm using a light emitting diode (LED). It is possible to form an image by curing the image by irradiating an active energy ray in the range.

[Support material]
The support material used in the method for producing a three-dimensional structure according to the present invention has an acid value of 80 or more and is an active energy ray curable ink.

  The description of the active energy ray-curable ink is based on the description given in the above section [Model material] except for the matters described here.

The support material is more preferably an ultraviolet curable ink like the model material. When the support material is an ultraviolet curable ink, it is preferably one that is cured by irradiation with an integrated light amount of 50 to 1000 mJ / cm ² with ultraviolet rays emitted from an ultraviolet light source, and is cured at 50 to 200 mJ / cm ² . More preferably.

  Since the support material used in the method for producing a three-dimensional structure according to the present invention can appropriately select a photopolymerization material and a sensitizer that match the light source, the sensitivity to light is good. Therefore, it can be cured by an ultraviolet light emitting semiconductor element such as a UV-LED or an ultraviolet light emitting semiconductor laser.

  More preferably, the support material includes at least one of a (meth) acrylic acid group and a sulfonic acid group. At this time, it is more preferable that the model material does not substantially contain a (meth) acrylic acid group. The difference in acid value between the model material and the support material can be increased, and the support material can be removed more easily and quickly. Moreover, the three-dimensional structure excellent in dimensional stability can be provided. This is because if the difference in acid value is small, there may be an effect such as swelling on the model material depending on the dissolving agent, and the occurrence of this effect can be suppressed due to the large difference in acid value.

  Polymerization components included in the support material include, for example, monomers having a free carboxylic acid group such as acrylic acid, methacrylic acid, crotonic acid, and maleic acid, vinyl sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, and acrylamide. A polymerizable monomer having a sulfonic acid group such as -t-butylsulfonic acid may be used alone or in combination of two or more. If necessary, the acid value may be adjusted to 80 or more in combination with the acrylates described in the section of [Model material]. By combining acrylates of the same system, the shrinkage rate between the model material and the support material can be made closer. At this time, the acrylate compound to be combined is preferably a monofunctional monomer that can be easily dissolved by water or an organic solvent after curing.

  The support material is preferably water-soluble. When a water having a high acid value is made water-soluble, it is easily dissolved by water. That is, the support material is water-soluble, and the support material removal step is more preferably performed using water. Since the acid value is 80 or more and the water-soluble support material is extremely soluble in water, a three-dimensional structure can be obtained in a shorter time. Further, the support material can be quickly removed by water that is easy to handle.

  The support material more preferably contains a water-soluble vinyl monomer that becomes water-soluble in the homopolymer. Since it becomes easy to remove the support material with water, the support material can be removed more easily and quickly. Further, it is more preferable to use a water-soluble vinyl compound such as N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropylacrylamide, and vinyl methyl ether, which can make the homopolymer water-soluble. This is because the detergency with water, alkaline aqueous solution and alcohol is further improved. However, the ratio of these water-soluble vinyl polymers in the ink is 50% by mass or less in consideration of the occurrence of flight bending due to the alteration of the ink due to moisture absorption on the end face of the inkjet head and the dimensional stability of the resulting three-dimensional printed matter. Is preferred.

  The support material preferably does not contain a colorant. In addition, considering the suppression of curing shrinkage, the purpose of weight increase, hardness adjustment, the removal effect by removing liquid, etc., the support material is a known extender pigment such as talc, colloidal silica, barium sulfate, aluminum hydroxide, calcium carbonate, etc. May be included. As described above, the support material does not include the colorant or includes the extender pigment, so that the color tone of the model material can be prevented from being impaired even if the support material remains.

  Note that the descriptions of the (photopolymerization initiator) and (other components) described in the [Model Material] section can also be applied to the support material.

  Although the support material depends on the ink jet device to be used, it is preferable to design the support material so that the viscosity after blending each monomer is approximately 1 to 100 mPa · sec, as in the model material.

[Support material printing process]
The support material printing step included in the method for manufacturing a three-dimensional structure according to the present invention is a step of printing using a support material.

  The method for printing using the support material is not particularly limited, but it is more preferably performed by the ink jet method. Flexible shapes can be modeled with high accuracy.

  Note that the description of the ink jet method and the plastic material as the recording medium described in the section [Model material printing step] can be applied to the support material printing step.

  The order of the model material printing process and the support material printing process is not particularly limited, and may be set as appropriate according to the specifications of the manufacturing apparatus to be used. For example, the support material printing process may be performed while performing the model material printing process by simultaneously ejecting the model material and the ink material using an inkjet recording apparatus. Further, for example, after the support material is discharged to configure only the support material, the model material printing process is performed after the support material printing process so that the model material is discharged to the region where the model material should be configured. Good. Further, for example, after forming the model material by discharging the model material, the support material printing process is performed after the model material printing process is performed so that the support material is discharged so that the structure of the model material is supported. You may do it.

[Support material removal process]
The support material removing step included in the method of manufacturing a three-dimensional structure according to the present invention is a step of removing the support material printed by the support material printing step.

  The support material removing step is more preferably performed using at least one of water, an alkaline aqueous solution, and alcohol. Since the support material used in the present invention quickly dissolves in the alkaline aqueous solution and alcohol, the support material can be removed more easily and quickly. Moreover, since a thing with a high acid value is generally easy to melt | dissolve in water, a support material can be easily and rapidly removed by removing a support material using the water which is easy to handle. That is, it is more preferable that the support material is water-soluble and the support material removal step is performed using water.

  Specific examples of the removing liquid for removing the support material are preferably water when the support material is dissolved in water as described above. Also, alkaline aqueous solution, alcohol, ether solvent, ester solvent, lactone solvent, ketone Any solvent that dissolves only the support material without dissolving the model material, such as a system solvent, an aromatic solvent, or an aliphatic solvent, can be used as appropriate. In particular, a removal solution composed of water, an alkaline aqueous solution, and alcohol is preferable from the viewpoint of safety and ease of handling.

  As the alkaline aqueous solution, for example, an aqueous solution of a water-soluble basic substance such as a basic salt such as sodium hydroxide, alcoholamine, or sodium bicarbonate is more preferable.

  As alcohol, low boiling point alcohols, such as methanol, ethanol, propyl alcohol, and its aqueous solution are more preferable.

<Kit for manufacturing a three-dimensional structure according to the present invention>
A kit for producing a three-dimensional structure according to the present invention has an acid value of 20 or less, a model material that is an active energy ray-curable ink, and an acid value of 80 or more, and an active energy ray-curable ink. And a support material. Since it can utilize for the manufacturing method of the three-dimensional structure which concerns on this invention mentioned above, a three-dimensional structure can be manufactured easily and in a short time.

  The model material and the support material conform to the above description.

  Moreover, the kit for manufacturing the three-dimensional structure according to the present invention may include other objects. For example, the kit for manufacturing the three-dimensional structure according to the present invention may include a removal liquid for removing the support material.

  Whatever the configuration, the kit for producing a three-dimensional structure according to the present invention includes the above-described model material and support material, and therefore can produce a three-dimensional structure easily and in a short time.

  Moreover, the kit for manufacturing the three-dimensional structure according to the present invention may include an instruction describing a procedure for removing the support material after printing the model material and the support material.

<Three-dimensional structure according to the present invention>
The three-dimensional structure according to the present invention has an acid value of 20 or less, a model material that is an active energy ray curable ink, an acid value of 80 or more, and a support material that is an active energy ray curable ink, Is formed by. In other words, the three-dimensional structure according to the present invention includes the cured model material and the cured support material.

  Since the three-dimensional structure according to the present invention is resistant to moisture absorption and has good dimensional stability, it can be used for a desired application while being integrated with the model material without removing the support material. .

  By removing the support material from the three-dimensional structure according to the present invention, it is possible to obtain a three-dimensional structure in which the model material has a desired structure. The model material, the support material, and the removal of the support material are the same as described above.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in the embodiments are also included. It is included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to the following Example at all. In the following examples, “parts” refers to parts by mass.

[Model material ink example]
Mimaki Engineering Co., Ltd. UV ink LH-100 ink (acid value 2)
[Support Material Ink Example 1]
Acrylic acid 30 parts Tetrahydrofurfuryl alcohol 25 parts 2-phenoxyethyl acrylate 39 parts Irgacure 369 4 parts DTEX-S 2 parts The above composition was dissolved and filtered through a 1 micron filter to obtain a clear support material ink. The acid value of this ink was 234.

[Support Material Ink Example 2]
Methacrylic acid 13 parts Tetrahydrofurfuryl alcohol 25 parts 2-phenoxyethyl acrylate 56 parts Irgacure 369 4 parts DTEX-S 2 parts The above composition was dissolved and filtered with a 1 micron filter to obtain a clear support material ink. The acid value of this ink was 85.

[Support Material Ink Example 3]
Acrylic acid 13 parts N-Vinylcaprolactam 20 parts Tetrahydrofurfuryl alcohol 25 parts 2-phenoxyethyl acrylate 56 parts Irgacure 369 4 parts DTEX-S 2 parts The above composition is dissolved and filtered with a 1 micron filter to provide a clear support material ink Got. The acid value of this ink was 85.

[Support Material Ink Example 4]
Acrylic acid 5 parts Tetrahydrofurfuryl alcohol 25 parts 2-phenoxyethyl acrylate 64 parts Irgacure 369 4 parts DTEX-S 2 parts The above composition was dissolved and filtered through a 1 micron filter to obtain a clear support ink. The acid value of this ink was 39.

[Support Material Ink Example 5]
Tetrahydrofurfuryl alcohol 25 parts 2-phenoxyethyl acrylate 68 parts Irgacure 369 4 parts DTEX-S 2 parts The above composition was dissolved and filtered through a 1 micron filter to obtain a clear support material ink. The acid value of this ink was zero.

[Example 1]
Using the YMCK color ink of the model material ink example and the ink of the support material ink example 1, the model material ink and the support material ink are printed at different positions by the UV printer UJF-6042 manufactured by MIMAKI ENGINEERING CO., LTD. Obtained.

  The solid support part of the three-dimensional object was washed away in a 2% sodium hydroxide solution, and finally rinsed with water and dried to obtain a three-dimensional model material with little distortion.

[Example 2]
Using the YMC color ink of the model material ink example and the support material ink example 2 as in Example 1, the model material ink and the support material ink are placed at different positions in the UV printer UJF-6042 manufactured by Mimaki Engineering Co., Ltd. Printing was performed to obtain a 3D printed material.

  The solid support material cured product portion of the three-dimensional object was washed away in an ethanol solution and dried to obtain a model material color three-dimensional object with less distortion.

Example 3
Using the YMCK color ink of the model material ink example and the support material ink example 3 in the same manner as in Example 1, the model material ink and the support material ink are placed at different positions in the UV printer UJF-6042 manufactured by Mimaki Engineering Co., Ltd. Printing was performed to obtain a 3D printed material with less distortion.

  The solid support material cured product portion of the three-dimensional object was washed away in water and dried to obtain a model material color three-dimensional object.

[Comparative Example 1]
Using the YMCK color ink of the model material ink example and the ink of the support material ink example 4, the model material ink and the support material ink are printed at different positions with the UV printer UJF-6042 manufactured by MIMAKI ENGINEERING CO., LTD. Obtained.

  Although the three-dimensional object was washed away in a 2% sodium hydroxide solution, the model material color three-dimensional object could not be obtained because the cured portion of the support material slightly swelled.

[Comparative Example 2]
Using the YMCK color ink of the model material ink example and the ink of the support material ink example 5, the model material ink and the support material ink are printed at different positions with the UV printer UJF-6042 manufactured by MIMAKI ENGINEERING CO., LTD. Obtained.

  Although the solid object was washed away in the ethanol solution, the model material color three-dimensional object could not be obtained because the cured portion of the support material slightly swelled.

  According to the present invention, it is possible to provide a full-color 3D printed material with high accuracy and in a short time using an active energy ray-curable ink and having a three-dimensional shape with a free shape and particularly excellent dimensional stability. Therefore, it can be used for manufacturing a three-dimensional structure.

Claims (5)

The acid value is 20 or less der Ru model material, and printed using a model material for the ink is an active energy ray-curable ink, the model material printing to shape by lamination method by curing by irradiation with an active energy ray Process,
And an acid value of 80 or more, a support member for supporting the upper SL model material, by printing a support material for the ink is an active energy ray-curable ink, by lamination method by curing with an active energy ray and support material printing step of molding,
Including a support material removal process for removing the support material shaped by the support material printing process,
The model material printing step and the support material printing step are performed simultaneously by simultaneously ejecting the model material ink and the support material ink to different positions by an inkjet method ,
The said support material removal process is performed using neutral or basic removal liquid, The manufacturing method of the three-dimensional structure characterized by the above-mentioned. The method for producing a three-dimensional structure according to claim 1, wherein the ink for a model material is a coloring ink containing a colorant or an ink not containing a colorant. The method for producing a three-dimensional structure according to claim 1 or 2, wherein the support material ink does not contain a colorant or is an ink containing an extender pigment. The said model material ink does not contain a (meth) acrylic acid group substantially, and the said support material ink contains at least one among a (meth) acrylic acid group and a sulfonic acid group. The manufacturing method of the three-dimensional structure according to claim 1. The method for producing a three-dimensional structure according to any one of claims 1 to 4, wherein the ink for a support material contains a water-soluble vinyl monomer that becomes water-soluble in a homopolymer.