JP2018083869A - Support material removal liquid for 3d printer, removal method of support material for 3d printer, and production method of solid molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support material removal liquid for a 3D printer which hardly causes yellowing of a solid molding, a support material removal method for a 3D printer which hardly causes yellowing of a solid molding, and a production method of a solid molding.SOLUTION: Provided are: a support material removal liquid for a 3D printer which contains water (A) and at least one oxidant (B) selected from an oxygen-based oxidant and a halogen-based oxidant; a support material removal method for a 3D printer, wherein, from a solid molding comprising a model material produced by using a 3D printer and supported on a support material, the support material is removed by using the support material removal liquid for a 3D printer of this invention; and, a production method of a solid molding, wherein, after producing a solid molding comprising a model material produced by using a 3D printer and supported on a support material, the support material is removed by using the support material removal liquid for a 3D printer of this invention.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a support material removing liquid for 3D printers, a support material removing method for 3D printers, and a method for manufacturing a three-dimensional model.

  3D printers are used in a wide range of fields such as various manufacturing industries, architecture, medical care, education, and aerospace. For example, 3D objects manufactured with 3D printers can be used as mockups for design studies and functional verification in various manufacturing and aerospace fields, as architectural models for presentations in the architectural field, and as surgical models in the medical field. As a model for pre-examination, it is used as a tool for manufacturing education in the education field. The 3D objects produced by 3D printers are images that can only be seen on the screen of a personal computer until now, but they can be picked up by hand. There is an advantage that it becomes easy.

  The 3D printer is a kind of rapid prototyping (three-dimensional modeling machine), and is an apparatus that manufactures a three-dimensional model by stacking materials one by one based on data such as 3D-CAD and 3D-CG. There are several types of modeling methods for manufacturing a three-dimensional model, and the characteristics of the materials that can be used for each method and the three-dimensional model to be manufactured are different. Therefore, it is necessary to select a modeling method suitable for the application. A typical modeling method is a heat-melting lamination method in which resin melted by heat is extruded from a nozzle and stacked to manufacture a three-dimensional model, and a material jet that manufactures a three-dimensional model by solidifying the resin sprayed from an inkjet head with ultraviolet rays. Binder jetting method, in which liquid binder is sprayed from an inkjet head to solidify the powder one by one to produce a three-dimensional model, and a three-dimensional model is manufactured by irradiating and sintering a powdered material. Examples of the powder sintering method are as follows.

  As a modeling method, a hot melt lamination method that can manufacture a three-dimensional modeled object with almost the same strength as a plastic product and a colorful three-dimensional modeled object with many color variations; a solid with various hardness by mixing multiple materials A material jetting method that can manufacture a three-dimensional object and a three-dimensional object with high accuracy is often used. However, in the hot melt lamination method and material jetting method, a support material may be required to support the three-dimensional structure (model material) until it solidifies. In that case, after the three-dimensional structure has solidified A process for removing the support material is required.

As the support material removing liquid for removing the support material, for example, the following are proposed.
(A) 1% by mass or more and 20% by mass or less of a water-soluble organic solvent, (b) 0.5% by mass or more and 20% by mass or less of an alkali metal hydroxide, (c) 0.2% by mass or more of an organic alkali agent, 20% by mass or less, (d) a surfactant containing 0.1% by mass or more, 20% by mass or less, and water, and the mass ratio of the content of (b) to the content of (c) (b) / ( c) is a developer composition for a 3D printer modeled article, which is 1/4 or more and 1 / 0.4 or less (Patent Document 1).

JP 2014-83744 A

  However, when the support material is removed with the developer composition for a 3D printer shaped article described in Patent Document 1, there is a problem that the obtained three-dimensional shaped article turns yellow for some reason. Therefore, a support material removing liquid having an effect of preventing yellowing is desired.

  It is an object of the present invention to provide a support material removing liquid for 3D printer that hardly causes yellowing of a three-dimensional model, a method for removing a support material for 3D printer that can suppress yellowing of a three-dimensional model, and a method of manufacturing a three-dimensional model. To do.

The present invention has the following aspects.
<1> A 3D printer support material removing liquid comprising water (A) and at least one oxidizing agent (B) selected from the group consisting of an oxygen-based oxidizing agent and a halogen-based oxidizing agent.
<2> The support material removing liquid for 3D printer according to <1>, further including an alkali component (C).
<3> The support material removing solution for a 3D printer according to <1> or <2>, further including a surfactant (D).
<4> From a three-dimensional structure made of a model material supported by a support material manufactured using a 3D printer, using the support material removing liquid for 3D printer according to any one of <1> to <3> above A support material removing method for removing a support material for a 3D printer.
<5> After manufacturing a three-dimensional structure made of a model material supported by a support material using a 3D printer, the support using the support material removing liquid for 3D printer according to any one of <1> to <3> The manufacturing method of the three-dimensional molded item which removes material.

The support material removing liquid for 3D printer of the present invention hardly causes yellowing of the three-dimensional model.
According to the method for removing a support material for a 3D printer and the method for producing a three-dimensional structure of the present invention, yellowing of the three-dimensional structure can be suppressed.

It is a photograph of the three-dimensional molded item (object to be washed) supported by the support material. It is a photograph of the three-dimensional molded item after removing a support material and rinsing. It is the schematic for demonstrating the method of removing a support material from the three-dimensional molded item (object to be washed) supported by the support material.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In this specification, “(meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”.

<Support material remover for 3D printer>
The support material removing liquid for 3D printer of the present invention is at least one oxidation selected from the group consisting of water (A) (hereinafter also referred to as “component (A)”), oxygen-based oxidant and halogen-based oxidant. Agent (B) (hereinafter also referred to as “component (B)”).
The support material removing liquid for 3D printer of the present invention preferably further contains an alkali component (C) (hereinafter also referred to as “component (C)”) from the viewpoint of the removability of the support material.
The support material removing liquid for 3D printer of the present invention preferably further contains a surfactant (D) (hereinafter also referred to as “component (D)”) from the viewpoint of improving the removal rate of the support material.
It is particularly preferable that the support material removing liquid for 3D printer of the present invention contains all of the components (A) to (D).
The support material removing liquid for 3D printer of the present invention may contain other components as necessary within the range not impairing the effects of the present invention.

(Water (A))
Examples of the component (A) include tap water, ion exchange water, distilled water, and the like, and any of them can be suitably used.

(Oxidizing agent (B))
The component (B) is at least one selected from the group consisting of oxygen-based oxidizing agents and halogen-based oxidizing agents.

An oxygen-based oxidant is a compound that generates active oxygen in water. Examples of the oxygen-based oxidizing agent include the following (B1) to (B8). One oxygen-based oxidizing agent may be used alone, or two or more oxygen-containing oxidizing agents may be used in combination.
(B1) Hydrogen peroxide.
(B2) Percarbonates such as ammonium percarbonate, sodium percarbonate, and potassium percarbonate.
(B3) Perborates such as sodium perborate monohydrate and sodium perborate tetrahydrate.
(B4) Percarboxylic acids such as peracetic acid, peroxybenzoic acid, peroxy-α-naphthoic acid, peroxylauric acid, and peroxystearic acid.
(B5) Dipercarboxylic acids such as 1,12-diperoxidedecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid and the like.
(B6) Organic peroxides other than (B4) and (B5), such as phthalimide peroxycaproic acid and benzoyl peroxide.
(B7) Superphosphate.
(B8) Persulfates such as persulfate or sodium persulfate, potassium persulfate, ammonium persulfate, sodium hydrogen persulfate, potassium hydrogen persulfate, potassium monohydrogen persulfate double salt.

Halogen-based oxidants are compounds that generate active halogens in water. Examples of the halogen-based oxidizing agent include the following (B9) to (B11). A halogen-type oxidizing agent may be used individually by 1 type, and may use 2 or more types together.
(B9) Hypochlorous acid, chlorous acid, perchloric acid, alkali metal salts such as lithium salts, sodium salts, and potassium salts thereof, or alkaline earth metal salts such as magnesium salts and calcium salts.
(B10) Halogenated isocyanuric acid compounds such as trichloroisocyanuric acid, dichloroisocyanuric acid, tribromocyanuric acid, dibromocyanuric acid, sodium dichloroisocyanurate, sodium dibromoisocyanurate, sodium dichloroisocyanurate, potassium dichloroisocyanurate .
(B11) 1,3-dibromo-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-dimethylhydantoin, 3-bromo-1-chloro-5,5-dimethylhydantoin, 1,3- Halogenated hydantoin compounds such as dichloro-5,5-dimethylhydantoin and 1,3-dichloro-5-ethyl-5-methylhydantoin.
The component (B) is preferably an oxygen-based oxidizing agent, more preferably (B2), (B3), or (B1) from the viewpoints of safety during handling and wastewater treatment.

(Alkali component (C))
The component (C) is not particularly limited. Component (C) includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; silicates such as sodium orthosilicate, sodium metasilicate, potassium metasilicate and sodium sesquisilicate; phosphoric acid such as trisodium phosphate Salts; carbonates such as disodium carbonate, sodium hydrogencarbonate and dipotassium carbonate; borate salts such as sodium borate; amines and the like. As the component (C), one type may be used alone, or two or more types may be used in combination.
(C) As a component, from a viewpoint of the removability of a support material and cost, an alkali metal hydroxide and a silicate are preferable, and an alkali metal hydroxide is more preferable.

(Surfactant (D))
Examples of component (D) include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

Examples of the anionic surfactant include known ones. Specifically, soaps, alkylbenzene sulfonates, higher alcohol sulfates, sulfates of higher alcohol alkylene oxide adducts, α-sulfo fatty acid esters, α-olefin sulfonates, alkane sulfonates, monoalkyl phosphates Examples include ester salts.
Alkyl is usually straight-chain or branched alkyl having 10 to 14 carbon atoms. The higher alcohol is usually a linear or branched unsaturated or saturated higher alcohol having 8 to 24 carbon atoms. The fatty acid is usually an unsaturated or saturated fatty acid having 6 to 22 carbon atoms. The α-olefin is usually an α-olefin having 14 to 16 carbon atoms. The alkane is usually a linear or branched alkane having 14 to 18 carbon atoms. Examples of the alkyleneoxy group of the alkylene oxide adduct include an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and a styreneoxy group. The portion to which the alkylene oxide is added may be composed of one type of alkyleneoxy group or may be composed of two or more types of alkyleneoxy groups. When it consists of 2 or more types of alkyleneoxy groups, there is no restriction | limiting in the addition form of alkylene oxide. Examples of the addition form of alkylene oxide include random addition, block addition, a combination of random addition and block addition, and the like. The addition number of alkylene oxide is 1-20 mol.

  Examples of the cationic surfactant include known ones. Specifically, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, etc. are mentioned.

Nonionic surfactants include known ones. Specifically, higher alcohol alkylene oxide adduct, fatty acid esterified product of higher alcohol alkylene oxide adduct, alkyl or alkenylphenol alkylene oxide adduct, fatty acid alkylene oxide adduct, higher fatty acid ester of polyhydric alcohol alkylene oxide adduct , Aliphatic amine alkylene oxide adduct, fatty acid amide alkylene oxide adduct, polyalkylene glycol type of polyoxypropylene alkylene oxide adduct, glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sucrose fatty acid ester A monohydric alcohol type is mentioned.
The higher alcohol is usually a linear or branched unsaturated or saturated higher alcohol having 8 to 22 carbon atoms. The alkyl or alkenyl phenol is a straight or branched unsaturated or saturated alkyl or alkenyl phenol usually having 6 to 22 carbon atoms. The fatty acid is usually an unsaturated or saturated fatty acid having 10 to 22 carbon atoms. The polyhydric alcohol is usually a polyhydric alcohol having 3 to 12 carbon atoms. The aliphatic amine is usually a linear or branched unsaturated or saturated aliphatic amine having 8 to 22 carbon atoms. Examples of the alkyleneoxy group of the alkylene oxide adduct include an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and a styreneoxy group. The portion to which the alkylene oxide is added may be composed of one type of alkyleneoxy group or may be composed of two or more types of alkyleneoxy groups. When it consists of 2 or more types of alkyleneoxy groups, there is no limitation on the addition form of alkylene oxide. Examples of the addition form of alkylene oxide include random addition, block addition, a combination of random addition and block addition, and the like. The addition number of alkylene oxide is usually 1 to 20 mol.

  As the component (D), anionic surfactants and nonionic surfactants are preferable from the viewpoint of rinsing properties and economy, and alkylbenzene sulfonates, higher alcohol sulfates, sulfates of higher alcohol alkylene oxide adducts. , Α-olefin sulfonate anionic surfactants; higher alcohol alkylene oxide adducts and fatty acid alkylene oxide adduct nonionic surfactants are more preferred.

(Other ingredients)
Other components include solubilizers such as alcohols and glycols; builder components such as ethylenediaminetetraacetate, carboxymethylcellulose, polyvinylpyrrolidone and polyacrylate; thickeners; pH adjusters; preservatives; Pigments, colorants, fragrances, fluorescent colorants, enzymes, bactericides, and the like.

(Ratio of each component)
The proportion of the oxygen-based oxidant as component (B) is preferably 0.01 to 35% by mass, and 0.05 to 10% by mass, out of 100% by mass of the support material removing liquid for 3D printers, from the viewpoint of handleability. Is more preferable, and 0.1-3.5 mass% is further more preferable.
The proportion of the halogen-based oxidant as component (B) is preferably 0.01 to 15% by mass, and 0.05 to 10% by mass, out of 100% by mass of the support material removing liquid for 3D printer, from the viewpoint of handleability. Is more preferable, and 0.1-6 mass% is further more preferable.

When the support material removing liquid for 3D printer contains the component (C), the amount of the component (C) is preferably such that the P alkalinity of the support material removing liquid for 3D printer falls within the following range.
The P alkalinity of the support material removing liquid for 3D printer is preferably more than 0 g / L and 65 g / L or less, and more preferably 4 g / L or more and 26 g / L or less from the viewpoint of the removability of the support material.
The P alkalinity is determined as follows.
Take the support material removal liquid for 3D printer in a beaker and put the electrode of pH meter. Tilt the 3D printer support material removal solution with 1 mol / L hydrochloric acid while gently stirring with a magnetic stirrer until pH 8.3. From the obtained titer, the P alkalinity converted into the amount of sodium hydroxide is calculated by the following formula (I).
P alkalinity (g / L: NaOH) = 1 × A × f / 1000 × 40 / B × 100 (I)
Where 1 is the valence of hydrochloric acid, A is the titration (mL) of 1 mol / L hydrochloric acid, f is the factor of 1 mol / L hydrochloric acid, and 40 is the molecular weight of NaOH. , B is the mass (g) of the support material removal liquid for 3D printers.

  When the support material removal liquid for 3D printer contains (D) component, the ratio of (D) component is the support material removal liquid for 3D printer from a viewpoint of the rinsing property, economical efficiency, and the influence on the environment at the time of disposal. Among 100 mass%, more than 0 mass% and 20 mass% or less are preferable, and 0.1 mass% or more and 5 mass% or less are more preferable.

(Preparation of support material removal liquid for 3D printer)
The order of adding each component when preparing the support material removing liquid for 3D printer is not particularly limited.
The support material removing liquid for 3D printer is prepared by preparing a concentrated liquid of 3D printer support material removing liquid containing component (A) and component (B), and diluting with component (A) immediately before use to support material for 3D printer. It is good also as a removal liquid. When the concentrated liquid of the support material removing liquid for 3D printer contains the component (C), the two-component type in which the component (B) and the component (C) are separated from the viewpoint of stability is preferable. In the two-pack type, the component (A) may be blended with either the component (B) or the component (C). When the component (D) is included, the component (D) You may mix | blend with any of a component and (C) component.

(Function and effect)
Since the support material removing liquid for 3D printer of the present invention described above contains the component (B) having an oxidizing action, the support material is removed from the three-dimensional object using the support material removing liquid for 3D printer. In addition, it is difficult to yellow the three-dimensional model.

<3D printer support material removal method>
The 3D printer support material removing method according to the present invention includes a 3D model made of a model material supported by a support material manufactured using a 3D printer in a method for manufacturing a 3D model to be described later. It is a method of removing the said support material using the support material removal liquid for water.
The support material removal liquid for 3D printer may be prepared by mixing each component in advance, or may be prepared by mixing each component immediately before use.

  The removal of the support material with the support material removal liquid for 3D printer is performed by bringing the support material removal liquid for 3D printer into contact with the three-dimensional object to which the support material is attached. Examples of the contact method include an immersion method, an immersion rocking method, an immersion stirring method, an immersion bubbling method, a submerged jet method, an immersion ultrasonic cleaning method and the like. The immersion stirring method and the immersion ultrasonic cleaning method are preferable.

  The temperature of the support material removal liquid for 3D printers is appropriately set according to the properties of the support material removal liquid for 3D printers, the effect on the three-dimensional structure, the evaporation of water, and the like. The temperature of the support material removing liquid for 3D printer is preferably 10 to 100 ° C, more preferably 20 to 100 ° C, from the viewpoint of the removability of the support material.

The contact time between the support material removing liquid for 3D printer and the three-dimensional object to which the support material is attached is appropriately set according to the remaining amount of the support material. In order to shorten the contact time, a part of the support material may be removed from the three-dimensional structure beforehand.
Examples of the method for removing the support material in advance include a mechanical method and a chemical method. Examples of the mechanical method include a method of removing a part of the support material by applying a mechanical load such as vibration; a method of removing a part of the support material by a water jet; a method of scraping off the support material by fingers. . Examples of the chemical method include a method of dissolving a support material using an organic solvent.

  The removal of the support material with the 3D printer support material removal liquid may be performed in several steps. When performing in several times, you may replace the 3D printer support material removal liquid with a new thing each time.

(Function and effect)
In the 3D printer support material removal method of the present invention described above, since the support material removal liquid for 3D printer containing the component (B) having an oxidizing action is used, the support material removal liquid for 3D printer is used. When the support material is removed from the three-dimensional structure, yellowing of the three-dimensional structure is suppressed.

<Method for manufacturing a three-dimensional model>
The manufacturing method of the three-dimensional molded item of this invention is a method which has the following process (a)-(c).
Process (a): The process of manufacturing the three-dimensional molded item which consists of a model material supported with the support material using 3D printer.
Step (b): A step of removing the support material after the step (a) using the support material removing liquid for 3D printer of the present invention.
Process (c): The process of processing a three-dimensional molded item with a rinse liquid after a process (b) as needed.

(Model material)
The model material is not particularly limited as long as it is a model material used in a 3D printer.

Examples of the model material include those containing a thermoplastic resin and a plasticizer in the case of the hot melt lamination method.
Thermoplastic resins include acrylonitrile-butadiene-styrene (ABS) resin, acrylate-styrene-acrylonitrile (ASA) resin, polycarbonate (PC) resin, PC / ABS alloy, polylactic acid resin, hydrophobic polysulfone resin, polyphenylsulfone resin , Polyetherimide resin, polyamide resin and the like.
Examples of the plasticizer include polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers, and phosphate ester plasticizers.

Examples of the model material include a material containing a photocurable resin and a photopolymerization initiator in the case of the material jetting method.
Examples of the photocurable resin include photocurable resins including acrylic monomers; epoxy acrylate oligomers, urethane acrylate oligomers, polyester acrylate oligomers, and the like.

Examples of the acrylic monomer include a photopolymerizable acrylic monomer. Examples of the photopolymerizable acrylic monomer include a non-functional acrylic monomer, a monofunctional acrylic monomer, and a polyfunctional acrylic monomer.
Non-functional acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate tartar. Libutyl, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, ( Examples include stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate.
Monofunctional acrylic monomers include (meth) acrylic acid, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (Meth) acrylic acid tetrahydrofurfuryl etc. are mentioned.
Polyfunctional acrylic monomers include ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, triethylene glycol di (meth) acrylate, (meth) Allyl acrylate, di (meth) acrylate tetraethylene glycol, tri (meth) acrylate trimethylolpropane, di (meth) acrylate decaethylene glycol, tetra (meth) acrylate pentaerythritol, di (meth) acrylate penta Examples include decaethylene glycol.

Examples of the epoxy acrylate oligomer include EBECRYL 3708 manufactured by Daicel Ornex, and CN2003 manufactured by Sartomer.
Examples of urethane acrylate oligomers include EBECRYL210, EBECRYL230, EBECRYL244, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL9270, Shin-Nakamura Chemical Co., Ltd. UV2000B, UV3000B, UV3200B, UV3310B, UV3700B, CN9006, C9007 manufactured by Sartomer, and the like.
Examples of the polyester acrylate oligomer include EBECRYL812, EBECRYL853, and EBECRYL884 manufactured by Daicel Ornex.

Examples of the photopolymerization initiator include known radical photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared region, and radical-based visible light polymerization initiators having photosensitivity in the wavelength range of 380 to 780 nm.
Examples of radical photopolymerization initiators include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenones such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone; 2-methylanthraquinone, 2 -Anthraquinones of derivatives such as chloroanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone; thioxanthones of derivatives such as oxanthone, 2,4-dimethylthioxanthone; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, Derivatives of benzophenones such as 4,4′-dichlorobenzophenone and N, N-dimethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like That.
Examples of radical-based visible light polymerization initiators include camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bis (cyclopentadienyl) titanium-dipentafluorophenyl, and the like.

(Support material)
The support material is not particularly limited as long as it is a support material used in a hot melt lamination method or a material jetting method.

Examples of the support material include those containing a thermoplastic acrylic resin, polyvinyl alcohol, and a plasticizer in the case of the hot melt lamination method.
Thermoplastic acrylic resins include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, polyethylene glycol acrylate , Homopolymers of (meth) acrylic acid esters such as polyethylene glycol methacrylate; (meth) acrylic acid esters, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, styrene, α-methylene-γ-valerolactone , Α-hydroxyacrylic acid, vinyl alcohol methyl vinyl ether, styrene sulfonic acid, vinyl acetate, vinyl propionate, adamantyl methacrylate, copolymers with other monomers such as ethylene, propylene, and the like.
Examples of the plasticizer include the same plasticizers included in the model material.

In the case of the material jetting method, examples of the support material include those containing a photocurable resin, a photopolymerization initiator, a water-soluble viscosity modifier, and a wetting agent.
As a photocurable resin, the same thing as the photocurable resin contained in a model material is mentioned. The difference between the photocurable resin contained in the support material and the photocurable resin contained in the model material is that the degree of polymerization of the photocurable resin contained in the support material is lower than that of the model material.
As a photoinitiator, the thing similar to the photoinitiator contained in a model material is mentioned.
Examples of the water-soluble viscosity modifier include polyethylene glycol and polyhydric alcohol.
Examples of the wetting agent include glycerin (which may function as a water-soluble viscosity modifier).

  Support materials for hot melt lamination method and material jetting method are water-soluble polymers such as polyethylene glycol, poly (ethylene glycol / propylene glycol), carboxymethyl cellulose, starch, etc .; polyether ester; polyether ester amide; hydrophobic rubber A graft polymer in which a polymer such as polyacrylic acid having a hydrophilic group is grafted; a graft polymer in which polyoxazoline is grafted on silicone; a hydrophilic thermoplastic elastomer such as an ionic elastomer; a styrene-butadiene copolymer, a thermoplastic elastomer It may also contain a water-insoluble polymer such as

(Process (a))
As a modeling method for manufacturing a three-dimensional model using a 3D printer, a hot melt lamination method or a material jetting method is preferable.

(Process (b))
The support material is removed by the above-described support material removal method for a 3D printer of the present invention.

(Process (c))
A process (c) is performed by making a rinse liquid and a three-dimensional molded item contact. Examples of the contact method include an immersion method, an immersion rocking method, an immersion stirring method, an immersion bubbling method, a submerged jet method, an immersion ultrasonic cleaning method and the like. The immersion stirring method and the immersion ultrasonic cleaning method are preferable.
As the rinsing liquid, tap water, an acid aqueous solution, an alkali aqueous solution, an aqueous solution containing a surfactant, or the like is preferably used.

What is necessary is just to set suitably the contact time of a rinse liquid and a three-dimensional molded item according to the support material removal liquid for 3D printers, the residual amount of a support material, etc. FIG.
Step (c) may be performed in several steps. When performing by dividing into several times, you may replace the rinse liquid with a new thing every time.

(Function and effect)
In the manufacturing method of the three-dimensional modeled object of the present invention described above, since the support material removing liquid containing the oxidizing component (B) is used for removing the support material, the support for 3D printer is used. When the support material is removed from the three-dimensional structure using the material removing liquid, yellowing of the three-dimensional structure is suppressed.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Raw material for support material removal liquid for 3D printer>
The following components were prepared as raw materials for the support material removal liquid for 3D printers.
((A) component)
・ Ion exchange water.
((B) component)
·hydrogen peroxide,
Sodium percarbonate,
-Sodium hypochlorite.
((C) component)
·Sodium hydroxide,
Potassium hydroxide,
・ Sodium orthosilicate,
・ Diethanolamine,
-Triethanolamine.

((D) component)
-Sodium alkylbenzene sulfonate: sodium neutralized salt of Teikatox L-121 (manufactured by Teika Co., Ltd., alkyl carbon number: 10 to 14).
Higher alcohol alkylene oxide adduct 1: 8.5 mol ethylene oxide and 2.5 mol random propylene oxide adduct of a higher alcohol mixture having 12 to 13 carbon atoms.
Higher alcohol alkylene oxide adduct 2: 20 mol adduct of stearyl alcohol with ethylene oxide.
Higher alcohol alkylene oxide adduct 3: 6.8 mol ethylene oxide adduct of a higher alcohol mixture having 12 to 15 carbon atoms

<Preparation of support material removal liquid for 3D printer>
(Examples 1-25, Comparative Examples 1-13)
Immediately before the removal of the support material, the components shown in Tables 1, 2 and 3 were mixed in the compositions shown in Tables 1, 2 and 3 to prepare a support material removal liquid for 3D printers.

<Evaluation method>
In order to confirm the effect of the support material removing liquid for 3D printer of the present invention, the support material was removed, and then the three-dimensional model was yellowed and the support material was evaluated for removability. The results are shown in Table 1, Table 2 and Table 3.

(Manufacture of 3D objects)
As a model material, UV curable acrylic resin (Stratasys Japan Co., Ltd., Object VeroClear RGD810) was prepared.
As a support material, water-soluble UV curable acrylic resin: (Stratasis Japan, Object Support SUP707) was prepared.
Using a material jetting type 3D printer (Stratasis Japan Co., Ltd., Object Eden260S), a three-dimensional structure made of a model material supported by a support material at a lamination pitch of 16 μm (hereinafter also referred to as an object to be washed). Manufactured. A photograph of the three-dimensional structure (object to be washed) supported by the support material is shown in FIG. 1, and a photograph of the three-dimensional structure after removing the support material and rinsing is shown in FIG.

(Removal of support material)
As shown in FIG. 3, 1000 mL of the support material removing liquid 12 for 3D printer was placed in a 2 L beaker 10 and the stirring bar 14 at the bottom of the beaker 10 was rotated at 300 rpm. The object to be cleaned 18 placed in the polypropylene resin net 16 is immersed in the support material removing liquid 12 for the 3D printer in the beaker 10 so as not to come into contact with the stirring bar 14, and the temperature is 20 ° C. and the time is 4 hours. Was processed.

(rinse)
Except that the support material removing liquid for 3D printer was changed to the rinsing liquid, the same apparatus as that for removing the support material was used, and the treatment was performed under the following conditions.
Rinse solution: ion exchange water,
Temperature: 20 ° C
Time: 1 minute
Number of times: 3 times (the rinse solution was replaced every time).

(Yellowing of 3D objects)
After rinsing, the three-dimensional model was visually confirmed and evaluated according to the following criteria. The yellowing of the three-dimensional structure was determined to be acceptable if it was 3 or more.
3: Yellowing was not confirmed in the three-dimensional modeled object.
2: Slight yellowing was confirmed in the three-dimensional structure.
1: Yellowing was confirmed in the three-dimensional structure.

(Removability of support material)
After rinsing, the three-dimensional model was visually confirmed and evaluated according to the following criteria. If the support material removability was 3 or more, it was judged to be acceptable.
4: All support materials were removed.
3: Most of the support material was removed, but the support material remained slightly on the surface of the three-dimensional structure.
2: The support material could not be removed, and the support material could be confirmed on the surface of the three-dimensional structure and the gap between the three-dimensional structure.
1: Most of the support material could not be removed, and the support material remained in the entire three-dimensional structure.

  By removing the support material using the support material removing liquid for 3D printer of the present invention, yellowing of the three-dimensional model can be suppressed. Therefore, according to the support material removing liquid for 3D printer of the present invention, the support material removing method for 3D printer, and the manufacturing method of the three-dimensional structure, the texture of the material of the model material is maintained and the 3D-CAD and 3D-CG are maintained. It is possible to obtain a three-dimensional shaped object with high accuracy according to the data.

10 Beakers,
12 Support material removing liquid for 3D printer,
14 Stir bar,
16 Resin net,
18 The item to be washed.

Claims (5)

Water (A),
A support material removing solution for a 3D printer, comprising: at least one oxidizing agent (B) selected from the group consisting of an oxygen-based oxidizing agent and a halogen-based oxidizing agent.   The support material removing liquid for 3D printer according to claim 1, further comprising an alkaline component (C).   The support material removing liquid for 3D printer according to claim 1 or 2, further comprising a surfactant (D).   The said support material using the support material removal liquid for 3D printers as described in any one of Claims 1-3 from the three-dimensional molded item which consists of a model material supported with the support material manufactured using the 3D printer. Removing support material for 3D printer.   After manufacturing the three-dimensional molded item which consists of a model material supported with the support material using 3D printer, the said support material is used using the support material removal liquid for 3D printers as described in any one of Claims 1-3. The manufacturing method of the three-dimensional molded item to remove.