WO2019039491A1 - 三次元物体前駆体処理剤組成物 - Google Patents

三次元物体前駆体処理剤組成物 Download PDF

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Publication number
WO2019039491A1
WO2019039491A1 PCT/JP2018/030910 JP2018030910W WO2019039491A1 WO 2019039491 A1 WO2019039491 A1 WO 2019039491A1 JP 2018030910 W JP2018030910 W JP 2018030910W WO 2019039491 A1 WO2019039491 A1 WO 2019039491A1
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Prior art keywords
dimensional object
agent composition
support material
object precursor
mass
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English (en)
French (fr)
Japanese (ja)
Inventor
橋本　良一
栄二 樫原
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Kao Corp
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Kao Corp
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Priority to CN201880052168.3A priority Critical patent/CN111032320A/zh
Priority to EP18847714.5A priority patent/EP3674064A4/en
Priority to US16/641,919 priority patent/US20200180226A1/en
Publication of WO2019039491A1 publication Critical patent/WO2019039491A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/35—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment

Definitions

  • the present invention relates to three-dimensional object precursor processing compositions.
  • the 3D printer is a type of rapid prototyping and is a three-dimensional printer that forms a three-dimensional object based on 3D data such as 3D CAD and 3D CG.
  • 3D data such as 3D CAD and 3D CG.
  • an ink jet ultraviolet curing method hereinafter, also referred to as an ink jet method
  • a hot melt lamination method an optical forming method, a laser sintering method and the like are known.
  • the inkjet method is a modeling method for obtaining a three-dimensional object by curing and laminating ultraviolet curing resin jetted from an inkjet head with ultraviolet light, and in order to model a three-dimensional object having a more complicated shape, , Forming a three-dimensional object, and laminating a support material for supporting a three-dimensional structure of the formation material to obtain a three-dimensional object precursor, and then removing the support material from the three-dimensional object precursor
  • An ultraviolet curing resin is also used as the support material (for example, JP-A-2015-221566).
  • the three-dimensional object precursor processing agent composition of the present invention is a three-dimensional object precursor processing agent composition for removing the support material from a three-dimensional object precursor having a support material and a forming material, which comprises an alkali metal It contains a hydroxide, an anionic emulsifier and water.
  • a method for producing a three-dimensional object according to the present invention comprises: forming a three-dimensional object precursor including a three-dimensional object and a support material, and bringing the three-dimensional object precursor into contact with the three-dimensional object precursor processing agent composition
  • the method is a method of manufacturing a three-dimensional object by an inkjet ultraviolet curing method having a support material removing process of removing the support material.
  • a method of removing the support material As a method of removing the support material, a method such as finishing with a brush after removing the support material manually using a metal spatula etc. may be mentioned. However, in this method, it is difficult to completely remove the support material attached to the surface or the gap of the three-dimensional object. There is also a method of removing the support material by using a three-dimensional object precursor processing agent composition or the like, but in the case of the conventional three-dimensional object precursor processing agent composition, it took time to dissolve the support material. When the dissolution of the support material takes time, the three-dimensional object in the three-dimensional object precursor may be eroded depending on the content of the three-dimensional object precursor processing agent composition.
  • the present invention relates to a three-dimensional object precursor treating agent composition capable of removing the support material more rapidly and sufficiently than in the prior art, and an inkjet ultraviolet curing method using the three-dimensional object precursor treating agent composition Provided is a method of manufacturing a three-dimensional object.
  • the three-dimensional object precursor processing agent composition of the present invention is a three-dimensional object precursor processing agent composition for removing the support material from a three-dimensional object precursor having a support material and a forming material, which comprises an alkali metal It contains a hydroxide, an anionic emulsifier and water.
  • a method for producing a three-dimensional object according to the present invention comprises: forming a three-dimensional object precursor including a three-dimensional object and a support material, and bringing the three-dimensional object precursor into contact with the three-dimensional object precursor processing agent composition
  • the method is a method of manufacturing a three-dimensional object by an inkjet ultraviolet curing method having a support material removing process of removing the support material.
  • a three-dimensional object precursor processing agent composition capable of removing the support material more rapidly and sufficiently than before and an inkjet ultraviolet curing using the three-dimensional object precursor processing agent composition It is possible to provide a method of manufacturing a three-dimensional object by the method.
  • the three-dimensional object precursor processing agent composition of the present embodiment (hereinafter sometimes referred to simply as a processing agent composition) is for removing the support material from a support material and a three-dimensional object precursor having a forming material.
  • a three-dimensional object precursor treating agent composition comprising an alkali metal hydroxide, an anionic emulsifier, and water. According to the three-dimensional object precursor processing agent composition of the present embodiment, the support material can be removed more quickly than in the prior art.
  • alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide and potassium hydroxide. One or more of these may be used in combination. Among these, sodium hydroxide is preferable from the viewpoint of rapidly removing the support material.
  • the content of the alkali metal hydroxide in the treatment agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, from the viewpoint of rapidly removing the support material.
  • the content of the alkali metal hydroxide in the treatment agent composition is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less from the viewpoint of rapidly removing the support material. From these viewpoints, the content of the alkali metal hydroxide in the treatment agent composition is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 3 to 10% by mass. .
  • anionic emulsifier examples include fatty acid, alkyl sulfuric acid ester, alkyl ether sulfuric acid ester, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, and alkyl phosphoric acid, and salts thereof. One or more of these may be used in combination. Among these, from the viewpoint of rapidly removing the support material, alkyl diphenyl ether disulfonate is preferable, and sodium salt of alkyl diphenyl ether disulfonic acid is more preferable. Examples of commercially available products of such anionic emulsifiers include Perex SS-H (alkyl diphenyl ether sulfonic acid sodium salt; manufactured by Kao Corporation).
  • the content of the anionic emulsifier in the treatment agent composition is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of rapidly removing the support material and improving the clearance washing property. And 1% by mass or more is more preferable.
  • the content of the anionic emulsifier in the processing agent composition is preferably 10% by mass or less, more preferably 8% by mass or less, and 5% by mass or less from the viewpoint of rapidly removing the support material and suppressing foaming. More preferable. If these viewpoints are put together, 0.2-10 mass% is preferable, as for content of the said anionic emulsifier in the said processing agent composition, 0.5-8 mass% is more preferable, and 1-5 mass% is further more preferable. preferable.
  • water examples include ultrapure water, pure water, ion exchange water, distilled water, and normal tap water.
  • the water content may be the balance of the treatment composition (the total amount being 100% by mass).
  • the content of water in the treatment agent composition is preferably 70% by mass or more, more preferably 75% by mass or more, and still more preferably 80% by mass or more.
  • the content of water in the treatment agent composition is preferably 98% by mass or less, more preferably 95% by mass or less, and still more preferably 93% by mass or less, from the viewpoint of rapidly removing the support material. From these viewpoints as a whole, the content of water in the treatment agent composition is preferably 70 to 98% by mass, more preferably 75 to 95% by mass, and still more preferably 80 to 93% by mass.
  • the treating agent composition is a water-soluble organic solvent, an organic alkali agent, a dispersing agent, ethylenediaminetetraacetic acid salt, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylate, if necessary, as long as the effects of the present invention are not impaired.
  • Alginates and other builder components such as thickeners, pH adjusters, preservatives, rust inhibitors, pigments, coloring agents and the like may be included.
  • the color of the treatment agent composition containing a colorant changes as the support material dissolves, so the colorant is also expected to function as an indicator that indicates the progress degree and the end time of treatment. it can.
  • Water-soluble organic solvent As the water-soluble organic solvent, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, Phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene diglycol and benzyl alcohol can be exemplified.
  • the water-soluble organic solvent means a solvent having an octanol / water distribution coefficient (LogPow) of 3.5 or less.
  • the content of the water-soluble organic solvent in the treatment agent composition is preferably less than 10% by mass, more preferably less than 1% by mass, and still more preferably substantially 0% by mass.
  • substantially 0% by mass means that the case of being mixed unavoidably at the time of production etc. is allowed.
  • Organic alkali agent An amine compound is mentioned as said organic alkali agent.
  • examples of the amine compound include the compounds described in JP-A-8-157887, paragraphs 0019 to 0028 (page 4, column 5, line 32 to page 5, column 7, line 48).
  • alkanolamine monoamine, diamine which may have a substituent, triamine which may have a substituent, morpholine which may have a substituent, having a substituent
  • amine compounds selected from pyridine which may be substituted, piperidine which may have a substituent, and tetraamine which may have a substituent.
  • Alkanolamines such as [2- (dimethylamino) ethyl] methylamino] ethanol, 2-[[3- (dimethylamino) propyl] methylamino] ethanol, N-aminoethylethanolamine, etc .; diaminopropane, diaminohexane, diaminooctane Diaminododecane, 4,4'-methylenebis (cyclohexylamine), 1,3-diaminoxylene, 1,3-bis (aminomethyl) cyclohexane, triethylenediamine, tetramethylethylenedia Minamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, methyldiaminopropane, dimethyldiaminopropane, dibutyldiaminopropane, diamines such as N-cyclohexyl-1,3-diamino
  • the content of the organic alkaline agent in the processing agent composition is increased, the removal performance of the support material may be reduced. Therefore, less than 1% by mass is preferable, and the content of the organic alkali agent in the processing agent composition is preferably substantially 0% by mass.
  • Dispersant examples include anionic dispersants, cationic dispersants, and nonionic dispersants. Among these, anionic dispersants are preferred, and anionic polycarboxylic acids are more preferred.
  • anionic polycarboxylic acid-based polymer dispersant examples include polyacrylic acid salts and copolymers of acrylic acid salts with acrylonitrile and methacrylic acid, copolymer salts of maleic acid and ⁇ -olefin, polystyrene sulfonate And copolymers of styrene sulfonate and acrylic acid, acrylonitrile, and methacrylic acid.
  • a salt that by which all or one part of an alkali metal, alkaline-earth metal, and a lower amine became an acid is mentioned.
  • Commercially available products of such anionic polycarboxylic acid type polymer dispersants include Demol EP (sodium salt of diisobutylene-maleic acid copolymer; manufactured by Kao Corporation).
  • 0.5 mass% or more is preferable, and, as for content of the said dispersing agent, 1 mass% or more is more preferable. 20 mass% or less is preferable from a viewpoint of removing a support material, and, as for content of the said dispersing agent, 15 mass% or less is more preferable.
  • the mass ratio of the anionic emulsifier to the polymer dispersant is the removal of the bulk support material 0.1 or more is preferable from a viewpoint which makes compatible the removability of the support material of property and a clearance gap, and 0.5 or more are more preferable.
  • the mass ratio of the anionic emulsifier to the dispersant is preferably 10 or less from the viewpoint of achieving both the removability of the bulk support material and the removability of the gap support material. And 5 or less are more preferable.
  • the mass ratio of the anionic emulsifier to the dispersant is preferably 0.1 to 10, and more preferably 0.5 to 5.
  • the treating agent composition can be used for producing a three-dimensional object by an inkjet method.
  • a forming process for obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and the three-dimensional object precursor processing agent composition The method of manufacturing a three-dimensional object by an ink jet method, comprising: According to the method for producing a three-dimensional object of the present embodiment, it is possible to remove the support material containing the methacrylic acid copolymer more quickly and sufficiently than in the prior art.
  • the shaping step can use a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in a method of manufacturing a three-dimensional object by a known inkjet method.
  • an ultraviolet curable acrylic resin is preferable.
  • the treating agent composition dissolves the support material but does not dissolve the forming material.
  • the soluble material for 3D modeling includes, for example, an ultraviolet-curable acrylic monomer, a water-soluble viscosity modifier, a wetting agent, and a photopolymerization initiator.
  • UV curable acrylic monomer examples include nonfunctional acrylic monomers, monofunctional acrylic monomers and polyfunctional acrylic monomers.
  • the said ultraviolet curable acrylic monomer is a monomer used as acrylic resin.
  • Nonfunctional acrylic monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, Lauryl acrylate, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl me
  • Monofunctional acrylic monomers such as acrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, methacrylic acid, diethylaminoethyl methacrylate, methacrylic acid
  • Monofunctional acrylic monomers such as acrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate.
  • the photopolymerization initiator may, for example, be a radical photopolymerization initiator or a cationic photopolymerization initiator.
  • radical type photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (4 2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methyl
  • water soluble viscosity modifier examples include polyethylene glycol and polyhydric alcohol.
  • wetting agent examples include glycerin and the like. Glycerin can also function as a water soluble viscosity modifier.
  • the soluble material for three-dimensional shaping includes, for example, 20% by mass to 50% by mass of an ultraviolet-curable acrylic monomer, 30% by mass to 74% by mass of a water-soluble viscosity modifier, and 5% by mass to 20% of a wetting agent % By mass or less and 1% by mass or more of a photopolymerization initiator.
  • the said modeling material contains an ultraviolet curable acrylic type monomer, an ultraviolet curable acrylic type oligomer, and a photoinitiator, for example.
  • the ultraviolet ray curable acrylic monomer according to the above-mentioned modeling material is the same as the ultraviolet ray curable acrylic monomer contained in the soluble material for three-dimensional formation.
  • the shaping material does not contain a water-soluble viscosity modifier and a wetting agent.
  • the modeling material has a higher degree of polymerization than the support material.
  • the amount of the treatment agent composition used is preferably 10 times by mass or more, and more preferably 20 times by mass or more with respect to the support material from the viewpoint of the solubility of the support material.
  • the use amount of the treatment agent composition is preferably 10000 mass times or less, more preferably 5000 mass times or less, still more preferably 1000 mass times or less, and further preferably 100 mass times or less from the viewpoint of workability. preferable.
  • the temperature of the treatment agent composition in the support material removing step is preferably 35 ° C. or less, more preferably 30 ° C. or less, from the viewpoint of suppressing deformation of the support material and the solubility.
  • the contact time of the support material with the treatment agent composition is preferably 5 minutes or more from the viewpoint of the removability of the support material. Further, the time for which the support material is in contact with the treatment agent composition is preferably 180 minutes or less, more preferably 120 minutes or less, still more preferably 90 minutes or less, from the viewpoint of reducing damage to the three-dimensional object. The following are more preferable. In these aspects, the contact time is preferably 5 to 180 minutes, more preferably 5 to 120 minutes, still more preferably 5 to 90 minutes, and still more preferably 5 to 60 minutes.
  • Examples 1 to 3 and Comparative Examples 1 to 3 [Preparation of evaluation sample]
  • a three-dimensional object of the shape shown in FIG. 1 was produced by Stratasys 3D printer (trade name: EDEN 350V).
  • a transparent ultraviolet-curable acrylic resin (trade name: RGD720) manufactured by Stratasys Inc. was used.
  • the five holes in the three-dimensional object shown in FIG. 1 extend to the opposite side.
  • each numerical value in FIG. 1 shows the dimension of a sample, and a unit is mm.
  • a Stratasys acrylic three-dimensional modeling soluble material (trade name: SUP 705) is packed, and in the filled support material portion, a 2.4 mm linear wire is inserted in the filled hole having a diameter of 3 mm.
  • Through holes were formed by using the removing agent so as to flow inside the support material, and six evaluation samples (three-dimensional object precursors) were produced.
  • FIG. 2 is a graph plotting the clearance removal rate of each evaluation sample measured every 30 minutes.
  • the three-dimensional object precursor processing agent composition according to the embodiment can remove the three-dimensional shaping soluble material by 120 minutes.

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PCT/JP2018/030910 2017-08-25 2018-08-22 三次元物体前駆体処理剤組成物 Ceased WO2019039491A1 (ja)

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CN201880052168.3A CN111032320A (zh) 2017-08-25 2018-08-22 三维物体前体处理剂组合物
EP18847714.5A EP3674064A4 (en) 2017-08-25 2018-08-22 TREATMENT COMPOSITION FOR PRECURSORS OF A THREE-DIMENSIONAL OBJECT
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US20200180226A1 (en) 2020-06-11

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