WO2017199323A1 - Composition d'agent de traitement pour précurseur d'objet tridimensionnel - Google Patents

Composition d'agent de traitement pour précurseur d'objet tridimensionnel Download PDF

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WO2017199323A1
WO2017199323A1 PCT/JP2016/064560 JP2016064560W WO2017199323A1 WO 2017199323 A1 WO2017199323 A1 WO 2017199323A1 JP 2016064560 W JP2016064560 W JP 2016064560W WO 2017199323 A1 WO2017199323 A1 WO 2017199323A1
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Prior art keywords
dimensional object
object precursor
acrylate
agent composition
support material
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Japanese (ja)
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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 PCT/JP2016/064560 priority Critical patent/WO2017199323A1/fr
Priority to TW106115578A priority patent/TW201809205A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00

Definitions

  • the present invention relates to a three-dimensional object precursor treating agent composition.
  • 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, 3D CG, and the like.
  • a 3D printer system a hot melt lamination system (hereinafter also referred to as an FDM system), an inkjet ultraviolet curing system, an optical modeling system, a laser sintering system, and the like are known.
  • the FDM method is a modeling method for obtaining a three-dimensional object by heating / melting and extruding and laminating polymer filaments, and unlike other methods, does not use a material reaction.
  • FDM 3D printers are small and inexpensive, and have become popular in recent years as devices with little post-processing.
  • a three-dimensional object is formed by stacking a modeling material constituting the three-dimensional object and a support material for supporting the three-dimensional structure of the modeling material.
  • the carboxylic acid in the (meth) acrylic acid copolymer is neutralized by an alkali. It is used to dissolve and dissolve in an alkaline aqueous solution.
  • the (meth) acrylic acid-based copolymer contained in the support material used in this method is dissolved in the hydrophobic group and the three-dimensional object precursor treating agent from the viewpoint of heating / melt extrusion by a 3D printer and lamination.
  • each has a hydrophilic group, so that treatment alone is not sufficient, and a method of removing the support material by further immersing in an organic solvent or heated water is mentioned (for example, No. 2014-83744 and JP-A-2016-2683).
  • the three-dimensional object precursor treating agent composition of the present invention comprises a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.
  • the method for producing a three-dimensional object of the present invention includes a modeling step of obtaining 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 treatment composition. And a method of manufacturing a three-dimensional object by a hot melt lamination method having a support material removal step of removing the support material.
  • a conventional three-dimensional object precursor treatment agent takes time to remove a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic group and a hydrophobic group.
  • the reactivity can be increased by increasing the concentration of alkali in the three-dimensional object precursor treatment agent or increasing the temperature when the three-dimensional object precursor is immersed in the three-dimensional object precursor treatment agent. It is possible to raise.
  • the removal capability of the support material is significantly reduced.
  • a three-dimensional object precursor treatment agent is used repeatedly, but this not only consumes the active ingredient of the three-dimensional object precursor treatment agent for these dissolution and dispersion, but also dissolves and disperses the support material in three dimensions. If it is not uniformly dispersed in the object precursor treating agent, there is a high possibility that problems such as redeposition will occur.
  • the present invention provides a three-dimensional object precursor treating agent composition capable of quickly removing a support material containing a (meth) acrylic acid copolymer in a gap between three-dimensional objects, and the three-dimensional object.
  • a method for producing a three-dimensional object by a hot melt lamination method using an object precursor treating agent composition is provided.
  • the three-dimensional object precursor treating agent composition of the present invention comprises a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.
  • the method for producing a three-dimensional object of the present invention includes a step of obtaining 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 treating agent composition. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has the support material removal process which removes the said support material.
  • a three-dimensional object precursor treating agent composition capable of quickly removing a support material containing a (meth) acrylic acid copolymer in a gap between three-dimensional objects in a small amount, and the tertiary It is possible to provide a method for producing a three-dimensional object by a hot melt lamination method using the original object precursor treating agent composition.
  • the three-dimensional object precursor treating agent composition of the present embodiment includes a three-dimensional object and a three-dimensional object including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.
  • a three-dimensional object precursor treating agent composition for removing the support material from an object precursor, the three-dimensional object precursor treating agent composition comprising: (a) an alkaline agent; and (b) a nonionic system Contains penetrant.
  • the reactivity can be increased by increasing the concentration of alkali in the three-dimensional object precursor treating agent or by increasing the temperature when the three-dimensional object precursor is immersed in the three-dimensional object precursor treating agent.
  • the support material swells, and the support material cannot be removed promptly.
  • the alkali metal salt contained in the conventional three-dimensional object precursor treating agent composition is the most. It was considered as an excellent active ingredient. However, it has been found that the alkali metal salt impedes water and swells instead, thereby inhibiting removal.
  • the swelling of the (meth) acrylic acid copolymer is suppressed by including (a) an alkaline agent and (b) a nonionic penetrant, Also, the support material containing the (meth) acrylic acid copolymer can be quickly removed.
  • the alkali agent (a) may be either an inorganic alkali agent or an organic alkali agent.
  • the inorganic alkali agent include alkali metal hydroxides and alkali metal carbonates.
  • the organic alkali agent include organic amine compounds.
  • alkali metal hydroxide and alkali metal carbonate examples include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • alkali metal carbonate examples include lithium carbonate, sodium carbonate, and potassium carbonate.
  • the total content of the alkali metal hydroxide and alkali metal carbonate in the three-dimensional object precursor treating agent composition is 2.5% by mass from the viewpoint of quickly removing the support material from the three-dimensional object precursor. Is less than 2.0% by mass, more preferably 1.0% by mass or less, still more preferably less than 0.5% by mass, preferably 0% by mass or more, and more preferably. Is 0.01% by mass or more, more preferably 0.25% by mass or more.
  • organic amine compounds examples include primary monoamine compounds, secondary monoamine compounds, tertiary monoamine compounds, primary diamine compounds, secondary diamine compounds, tertiary diamine compounds, primary triamine compounds, secondary triamine compounds, and tertiary. Examples thereof include at least one selected from the group consisting of triamine compounds.
  • Examples of the primary monoamine compound include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, Examples thereof include n-decylamine and n-octadecylamine.
  • Examples of the secondary monoamine compound include methylethanolamine, ethylethanolamine, diisopropanolamine, diisopropylamine, diethanolamine, butylethanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, and methylbutylamine. , Methylhexylamine, dipentylamine, piperidine, morpholine, 2,6-dimethylmorpholine, and the like.
  • methylethanolamine, ethylethanolamine, diisopropanolamine, butylethanolamine, and diisopropylamine from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material
  • tertiary monoamine compound examples include trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamine, triethanolamine, hydroxyethylpiperazine, dimethylaminoethanol, diethylaminoethanol, N-tert-butyl.
  • Diethanolamine dimethylaminoethoxyethanol (trade name KL-26; manufactured by Kao Corporation), ethyldiethanolamine, butyldiethanolamine, 6-dimethylamino-1-hexanol (trade name KL-25; manufactured by Kao Corporation), 5- (dimethyl Amino) -2-pentanol, 5- (dimethylamino) -1-pentanol, 3- (diethylamino) -1-propanol, n-methylmorpholine, n-e Rumoruhorin, and 4- (2-hydroxyethyl) morpholine and the like.
  • dimethylaminoethanol, diethylaminoethanol, N-tert-butyldiethanolamine, dimethylaminoethoxyethanol are used from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and exhibiting good removal of the support material.
  • At least one selected from the group consisting of ethyldiethanolamine and 6-dimethylamino-1-hexanol is preferred, and 6-dimethylamino-1-hexanol is more preferred.
  • Examples of the primary diamine compound include ethylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, and the like.
  • Examples of the secondary diamine compound include piperazine and hydroxyethyl piperazine.
  • hydroxyethylpiperazine is preferable from the viewpoint of suppressing swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material.
  • Examples of the tertiary diamine compound include tetraethylhexanediamine, tetramethylhexanediamine (trade name KL-1; manufactured by Kao Corporation), tetramethylpropanediamine (trade name KL-2; manufactured by Kao Corporation), and (2-dimethyl).
  • Examples include aminoethyl) methylethanolamine (trade name KL-28; manufactured by Kao Corporation), tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, spartein, and trimethylaminopropylethanolamine.
  • tetramethylhexanediamine tetramethylpropanediamine
  • (2-dimethylaminoethyl) are used from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material.
  • At least one selected from the group consisting of methylethanolamine is preferred.
  • Examples of the primary triamine compound include 1,2,3-triaminopropane, triaminohexane, triaminononane, triaminododecane, and 1,3,6-triaminohexane.
  • Examples of the secondary triamine compound include N, N ′′ -dimethyldiethylenetriamine, N, N ′′ -diethyldiethylenetriamine, N, N ′′ -dipropyldiethylenetriamine, and N, N ′′ -dibutyldiethylenetriamine.
  • Examples of the tertiary triamine compound include N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N, N, N ′, N ′′, N ′′ -pentaethyldiethylenetriamine, N, N, N ′, N “, N” -pentapropyldiethylenetriamine, N, N, N ′, N ′′, N ′′ -pentabutyldiethylenetriamine and the like can be exemplified.
  • a secondary diamine compound, a tertiary diamine compound, a secondary triamine compound from the viewpoint of expressing good removal of the support material by suppressing swelling of the (meth) acrylic acid copolymer, and at least one selected from the group consisting of tertiary diamine compounds and at least one selected from the group consisting of secondary diamine compounds and tertiary diamine compounds are more preferable.
  • organic amine compounds from the viewpoint of suppressing swelling of the (meth) acrylic acid-based copolymer and imparting quick dispersion into the cleaning liquid to express good removal of the support material, an alcoholic hydroxyl group
  • the content of the organic amine compound in the three-dimensional object precursor treating agent composition is 0 from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material. 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1.0 mass% or more is still more preferable.
  • the content of the organic amine compound in the three-dimensional object precursor treating agent composition is 20 from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and expressing good removal of the support material. % By mass or less is preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is even more preferable.
  • the content of the organic amine compound in the composition for treating a three-dimensional object precursor is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 5 to 10% by mass is more preferable, and 1.0 to 8% by mass is even more preferable.
  • the nonionic penetrant in the present embodiment is a nonionic compound having a hydrophilic part such as an oxyalkylene group and a hydrophobic part such as a hydrocarbon group. More specifically, an oxyalkylene adduct having at least one group selected from the group consisting of an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms. It is preferable that
  • the nonionic penetrant has a viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and suppresses the swelling of the (meth) acrylic acid copolymer, thereby improving the support material's good removability.
  • a polyoxyalkylene alkyl ether represented by the following general formula (1) is used.
  • R 1 —O— (AO) m—H (1)
  • R 1 is an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms
  • AO is an oxyalkylene having 1 to 50 carbon atoms.
  • m is the average number of moles of AO added, and m is a number from 1 to 20.
  • the number of carbon atoms of the alkyl group represented by R 1 is a support material that suppresses the swelling of the (meth) acrylic acid copolymer from the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more from the viewpoint of maintaining good removability for a long time. From the same viewpoint, the number of carbon atoms of the alkyl group represented by R 1 is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less. Taking these viewpoints together, the number of carbon atoms of the alkyl group represented by R 1 is preferably 4 to 14, more preferably 5 to 12, and still more preferably 6 to 10.
  • Examples of the alkyl group represented by R 1 include hexyl, 2-ethylhexyl, isononyl, 2-hexyldecyl, and the like. Among these, a hexyl group is preferred from the viewpoint of achieving both gap cleaning properties and durability. And 2-ethylhexyl group is preferable, and 2-ethylhexyl group is more preferable.
  • the carbon number of the alkenyl group represented by R 1 is a support material that suppresses the swelling of the (meth) acrylic acid-based copolymer from the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more from the viewpoint of maintaining good removability for a long time.
  • the carbon number of the alkenyl group represented by R 1 is preferably 30 or less, more preferably 20 or less, and still more preferably 18 or less from the same viewpoint. Taking these viewpoints together, the carbon number of the alkenyl group represented by R 1 is preferably 3 to 30, more preferably 4 to 20, and still more preferably 6 to 18.
  • the number of carbon atoms of the aryl group represented by R 1 is a support material that suppresses the swelling of the (meth) acrylic acid copolymer and the viewpoint of quickly removing the support material in the gaps of the three-dimensional object. Is preferably 6 or more, more preferably 12 or more from the viewpoint of maintaining good removability for a long time.
  • the number of carbon atoms of the aryl group represented by R 1 is preferably 30 or less and more preferably 24 or less from the same viewpoint. Taking these viewpoints together, the aryl group represented by R 1 preferably has 6 to 30 carbon atoms, and more preferably 12 to 24 carbon atoms.
  • Examples of the aryl group represented by R 1 include a phenyl group, a styrenated phenyl group, a phenylethyl group, a distyrenated phenyl group, a tristyrenated phenyl group, a benzyl group, a benzylated phenyl group, a dibenzylated phenyl group, and a tribenzylated group.
  • Phenyl groups and the like can be exemplified, but among these, the viewpoint of quickly removing the support material in the gap of the three-dimensional object, and the good support material by suppressing the swelling of the (meth) acrylic acid copolymer A benzylated phenyl group is preferable from the viewpoint of maintaining removability for a long time.
  • the benzylated phenyl group is a phenyl group substituted with one or more benzyl groups.
  • the hydrogen atom of the benzene ring or the hydrogen atom of the methylene group may be substituted with a short chain hydrocarbon group such as a methyl group, for example, an alkyl group having 1 to 4 carbon atoms.
  • a styrene group is included in a benzyl group.
  • benzylated phenyl group examples include a monostyrenated phenyl group, a distyrenated phenyl group, a monobenzylated phenyl group, and a dibenzylated phenyl group, and among these, a support material in a gap between three-dimensional objects.
  • Monostyrenated phenyl group and distyrenated phenyl group from the viewpoint of promptly removing water and from the viewpoint of suppressing the swelling of the (meth) acrylic acid copolymer and maintaining good removability of the support material for a long time 1 or more types selected from are preferable, and a distyrenated phenyl group is more preferable.
  • the number of carbon atoms of the oxyalkylene group represented by AO is the viewpoint of quickly removing the support material in the gaps of the three-dimensional object, and the swelling of the (meth) acrylic acid copolymer Is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more, from the viewpoint of suppressing the above-mentioned and maintaining good removability of the support material for a long time.
  • the number of carbon atoms of the oxyalkylene group represented by AO is preferably 50 or less, more preferably 20 or less, and still more preferably 18 or less from the same viewpoint. Taking these viewpoints together, the number of carbon atoms of the oxyalkylene group represented by AO in the general formula (1) is preferably 1 to 50, more preferably 2 to 20, further preferably 3 to 20, and 4 to 18 Is even more preferable.
  • the m is a viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and suppresses the swelling of the (meth) acrylic acid-based copolymer and maintains good removability of the support material for a long time. From the viewpoint, 1 or more is preferable, and 2 or more is more preferable. From the viewpoint of suppressing foaming, m is preferably 20 or less, more preferably 18 or less, and still more preferably 12 or less. Taking these viewpoints together, the m is preferably 1 to 20, more preferably 2 to 18, and still more preferably 2 to 12.
  • the content of the (b) nonionic penetrant is the viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and the swelling of the (meth) acrylic acid copolymer is suppressed. From the viewpoint of maintaining good removability for a long time, the content is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more in the three-dimensional object precursor treating agent composition.
  • the content of the (b) nonionic penetrant is the viewpoint of quickly removing the support material in the gap between the three-dimensional objects, and the swelling of the (meth) acrylic acid copolymer is suppressed.
  • the content of the nonionic penetrant (b) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in the three-dimensional object precursor treating agent composition. preferable.
  • the three-dimensional object precursor treating agent composition may contain a surfactant.
  • the support material in the gaps of the three-dimensional object can be quickly removed, and further, the (meth) acrylic acid copolymer is swollen. It is possible to maintain good removability of the support material for a long time.
  • the (b) nonionic penetrant is not included in the (c) surfactant.
  • surfactant examples include nonionic surfactants, amphoteric surfactants, and anionic surfactants.
  • anionic surfactant examples include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate , ⁇ -sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid mono- or diesters, sulfosuccinic acid esters, and the like.
  • alkyl ether sulfate examples include polyoxyethylene alkyl ether sulfate.
  • At least one selected from the group consisting of alkyl sulfates, alkyl ether sulfates, saturated fatty acid salts, and alkyl ether carboxylates is preferred.
  • Counter ions of the anionic group of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms And alkanolamine salts having 1 to 3 (for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.).
  • amphoteric surfactant examples include imidazoline, carbobetaine, amide betaine, sulfobetaine, hydroxysulfobetaine, amide sulfobetaine and the like, and betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are more preferable. Fatty acid amidopropyl betaine is more preferable.
  • nonionic surfactant examples include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene distyrenated phenyl ethers, higher fatty acid sucrose esters, polyglycerin fatty acid esters, higher grades other than the nonionic penetrant (b).
  • examples include fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, alkyl saccharide, alkyl amine oxide, alkyl amido amine oxide and the like. Of these, at least one selected from the group consisting of polyoxyalkylene alkyl ethers and polyoxyethylene distyrenated phenyl ethers is preferred.
  • the polyoxyalkylene alkyl ethers other than the (b) nonionic penetrant suppress the swelling of the (meth) acrylic acid-based copolymer from the viewpoint of quickly removing the support material in the gap between the three-dimensional objects. From the viewpoint of maintaining good removability of the support material for a long time, it is a polyoxyalkylene alkyl ether represented by the following general formula (2).
  • R 2 O— (EO) p (PO) q—H (2)
  • R 2 represents an alkyl group having 15 or more carbon atoms
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group
  • p and q are average added moles of EO and PO, respectively.
  • P is a number from 1 to 20
  • q is a number from 0 to 20.
  • the content of the surfactant is 0.05% by mass or less from the viewpoint of promptly removing the support material in the gap between the three-dimensional objects and maintaining good removability of the support material for a long time.
  • substantially 0% by mass is more preferable.
  • the three-dimensional object precursor treatment agent composition is water, a water-soluble organic solvent, ethylenediaminetetraacetate, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylate, as necessary, as long as the effects of the present invention are not impaired.
  • Builder components such as alginates, thickeners, pH adjusters, preservatives, rust inhibitors, pigments, colorants and the like may be included.
  • the developer composition containing the colorant changes color when the support material dissolves. Therefore, the colorant is also expected to function as an indicator that indicates the degree of progress and completion of development. it can.
  • the water content may be the balance of the three-dimensional object precursor treating agent composition (a total amount of 100% by mass).
  • the content of the water in the three-dimensional object precursor treating agent composition improves the stability and handling of the developer composition, and also improves the waste liquid treatability, etc.
  • the content of the water in the three-dimensional object precursor treating agent composition improves the stability and handling of the developer composition, and also improves the waste liquid treatability, etc.
  • To 99 mass% or less is preferable, 98 mass% or less is more preferable, and 97 mass% or less is still more preferable.
  • the water-soluble organic solvent exhibits the performance of disintegrating the support material and dissolving it in the developer composition.
  • the water-soluble organic solvent is preferably one that dissolves 1.5% by mass or more in 20 ° C. water.
  • Examples of the water-soluble organic solvent include water-soluble organic solvents selected from monohydric alcohols, polyhydric alcohols, and glycol ethers.
  • Examples of the monohydric alcohol include monohydric alcohols having 1 to 5 carbon atoms. Specifically, a monohydric alcohol selected from methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, and amyl alcohol is used. Can be mentioned.
  • Examples of the polyhydric alcohol include alkylene glycols having a repeating unit having 2 to 3 carbon atoms (hereinafter referred to as C2-C3 alkylene glycol).
  • C2-C3 alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, propylene glycol, dipropylene Examples include glycol and tripropylene glycol.
  • the C2-C3 alkylene glycol preferably has 1 to 10 oxyethylene groups or oxypropylene groups which are repeating units.
  • examples of polyhydric alcohols other than C2 to C3 alkylene glycol include polyhydric alcohols having 2 to 8 carbon atoms. Specifically, trimethylene glycol, 1,3-octylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-pentanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, glycerin, Examples include trimethylolethane and trimethylolpropane.
  • the water-soluble organic solvents may be used alone or in combination of two or more.
  • a water-soluble organic solvent selected from propylene glycol, dipropylene glycol, and tripropylene glycol is preferable, and a water-soluble organic solvent selected from ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol is more preferable.
  • the three-dimensional object manufacturing method of the present embodiment includes a three-dimensional object and a three-dimensional object precursor including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units. And a method for producing a three-dimensional object by a hot melt lamination method, which has a support material removing step of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition and removing the support material. It is. According to the method for producing a three-dimensional object of this embodiment, the support material containing the methacrylic acid copolymer can be removed more quickly than in the past. The reason why such an effect is exhibited may be the same as the reason why the three-dimensional object precursor treating agent composition exhibits the effect.
  • a modeling process for obtaining a three-dimensional object precursor including a three-dimensional object and a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units is a known hot-melt lamination method.
  • the step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the method for producing a three-dimensional object by the 3D printer can be used.
  • the modeling material that is the material of the three-dimensional object can be used without particular limitation as long as it is a resin that is used as a modeling material in a conventional FDM three-dimensional object manufacturing method.
  • the modeling material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin.
  • ABS resin and / or polylactic acid resin are preferable from the viewpoint of modeling by a 3D printer. Is more preferable, and ABS resin is more preferable.
  • the three-dimensional modeling soluble material that is a material of the support material includes a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.
  • hydrophilic monomer examples include acrylic acid, methacrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl methacrylate, and methacrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid, ⁇ -hydroxyacrylic acid and the like.
  • at least one selected from the group consisting of acrylic acid and methacrylic acid is preferable from the viewpoint of the removability of the support material.
  • hydrophobic monomer examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, acrylic Lauryl acid, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, methacrylic acid 2-ethylhexyl acid, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridec
  • the (meth) acrylic acid copolymer may contain monomer units other than the hydrophilic monomer and the hydrophobic monomer.
  • the support material removing step is a step of removing the support material by bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition.
  • the method of bringing the three-dimensional object precursor into contact with the three-dimensional object precursor treating agent composition may be agitated after being immersed in the treatment liquid, exposed to a strong water stream, or moved. It is done.
  • a method of immersing the three-dimensional object precursor in the three-dimensional object precursor treating agent composition is preferable. From the viewpoint of improving the removability of the support material, it is possible to promote the dissolution of the support material by irradiating ultrasonic waves during the immersion.
  • the pH of the three-dimensional object precursor treating agent composition is preferably 10 or more, more preferably 11 or more, from the viewpoint of solubility of the support material.
  • the pH of the three-dimensional object precursor treating agent composition is preferably 14 or less, more preferably 13 or less, from the viewpoint of suppressing or reducing damage to the modeling material. Taking these viewpoints together, the pH of the three-dimensional object precursor treating agent composition is preferably 10 to 14, more preferably 10 to 13, and still more preferably 11 to 13.
  • the amount of the three-dimensional object precursor treating 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 solubility of the support material.
  • the amount of the three-dimensional object precursor treating agent composition used is preferably 10,000 times by mass or less, more preferably 5000 times by mass or less, still more preferably 1000 times by mass or less, with respect to the support material from the viewpoint of workability. More preferably, it is less than mass times.
  • the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of solubility of the support material. From the same viewpoint, the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 80 ° C. or less, and more preferably 70 ° C. or less. Taking these viewpoints together, the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 to 80 ° C, more preferably 40 to 70 ° C.
  • the time for bringing the soluble material for 3D modeling into contact with the 3D object precursor treating agent composition is preferably 5 minutes or more from the viewpoint of the removability of the support material.
  • the time for contacting the three-dimensional modeling soluble material with the three-dimensional object precursor treatment agent composition is preferably 180 minutes or less, more preferably 120 minutes or less from the viewpoint of reducing damage to the three-dimensional object, 90 minutes or less is more preferable, and 60 minutes or less is even more preferable.
  • the time for contacting the three-dimensional modeling soluble material with the three-dimensional object precursor treating agent composition is preferably 5 to 180 minutes, more preferably 5 to 120 minutes, and more preferably 5 to 90 minutes. Is more preferable, and 5 to 60 minutes is even more preferable.
  • ⁇ 1> To remove the support material from a three-dimensional object precursor including a three-dimensional object and a support material containing a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units.
  • the three-dimensional object precursor treatment agent composition wherein the three-dimensional object precursor treatment agent composition contains (a) an alkali agent and (b) a nonionic penetrant.
  • Agent composition ⁇ 2> The three-dimensional object precursor treatment agent composition according to ⁇ 1>, wherein (a) the alkali agent is preferably at least one selected from the group consisting of an inorganic alkali agent and an organic alkali agent.
  • the alkali metal hydroxide is preferably at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • Treatment agent composition is preferably at least one selected from the group consisting of lithium carbonate, sodium carbonate, and potassium carbonate.
  • the total content of the alkali metal hydroxide and alkali metal carbonate in the three-dimensional object precursor treatment agent composition is less than 2.5% by mass, preferably less than 2.0% by mass. More preferably, it is 1.0 mass% or less, More preferably, it is less than 0.5 mass%, Preferably it is 0 mass% or more, More preferably, it is 0.01 mass% or more, More preferably, it is 0.00.
  • ⁇ 7> The three-dimensional object precursor treatment composition according to any one of ⁇ 2> to ⁇ 6>, wherein the organic alkali agent is preferably an organic amine compound.
  • the organic amine compound is a primary monoamine compound, secondary monoamine compound, tertiary monoamine compound, primary diamine compound, secondary diamine compound, tertiary diamine compound, primary triamine compound, secondary triamine compound, and
  • the primary monoamine compound is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octyl.
  • the secondary monoamine compound is methylethanolamine, ethylethanolamine, diisopropanolamine, diisopropylamine, diethanolamine, butylethanolamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, Preferably, at least one selected from the group consisting of methylbutylamine, methylhexylamine, dipentylamine, piperidine, morpholine, and 2,6-dimethylmorpholine, methylethanolamine, ethylethanolamine, diisopropanolamine, butylethanolamine, And at least one selected from the group consisting of diisopropylamine is more preferable, and the three-dimensional object precursor according to ⁇ 8> or ⁇ 9> Treatment composition.
  • the tertiary monoamine compound is trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamine, triethanolamine, hydroxyethylpiperazine, dimethylaminoethanol, diethylaminoethanol, N-tert.
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 8> to ⁇ 10>, more preferably 6-dimethylamino-1-hexanol.
  • the primary diamine compound is preferably at least one selected from the group consisting of ethylenediamine, 1,4-diaminobutane, and 1,6-diaminohexane, ⁇ 8> to ⁇ 11>
  • a three-dimensional object precursor treatment composition ⁇ 13>
  • the three-dimensional object according to any one of ⁇ 8> to ⁇ 12>, wherein the secondary diamine compound is preferably at least one selected from the group consisting of piperazine and hydroxyethylpiperazine, more preferably hydroxyethylpiperazine.
  • Precursor treatment agent composition is preferably at least one selected from the group consisting of piperazine and hydroxyethylpiperazine, more preferably hydroxyethylpiperazine.
  • the tertiary diamine compound is tetraethylhexanediamine, tetramethylhexanediamine, tetramethylpropanediamine, (2-dimethylaminoethyl) methylethanolamine, tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, At least one selected from the group consisting of sparteine and trimethylaminopropylethanolamine is preferred, and at least selected from the group consisting of tetramethylhexanediamine, tetramethylpropanediamine, and (2-dimethylaminoethyl) methylethanolamine.
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 8> to ⁇ 13>, wherein one or more are more preferable.
  • the primary triamine compound is at least one selected from the group consisting of 1,2,3-triaminopropane, triaminohexane, triaminononane, triaminododecane, and 1,3,6-triaminohexane.
  • the secondary triamine compound is at least selected from the group consisting of N, N ′′ -dimethyldiethylenetriamine, N, N ′′ -diethyldiethylenetriamine, N, N ′′ -dipropyldiethylenetriamine, and N, N ′′ -dibutyldiethylenetriamine.
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 8> to ⁇ 15>, wherein one or more are preferable.
  • the tertiary triamine compound is N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N, N, N ′, N ′′, N ′′ -pentaethyldiethylenetriamine, N, N, N ′ , N ′′, N ′′ -pentapropyldiethylenetriamine, and at least one selected from the group consisting of N, N, N ′, N ′′, N ′′ -pentabutyldiethylenetriamine is preferable, any one of ⁇ 8> to ⁇ 16>
  • the organic amine compound is preferably at least one selected from the group consisting of secondary diamine compounds, tertiary diamine compounds, secondary triamine compounds, and tertiary triamine compounds, secondary diamine compounds, and tertiary.
  • the content of the organic amine compound in the three-dimensional object precursor treating agent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. More preferably, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, still more preferably 8% by mass or less, preferably 0.1 to 20% by mass, 0.5 to 15%.
  • the nonionic penetrant is a nonionic compound having a hydrophilic part such as an oxyalkylene group and a hydrophobic part such as a hydrocarbon group.
  • the nonionic penetrant includes an alkyl group having 4 to 14 carbon atoms and 3 to 3 carbon atoms.
  • it is an oxyalkylene adduct having at least one group selected from the group consisting of 30 alkenyl groups and aryl groups having 6 to 30 carbon atoms, ⁇ 1> to ⁇ 20> Three-dimensional object precursor treating agent composition.
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 1> to ⁇ 21>, wherein the nonionic penetrant is preferably a polyoxyalkylene alkyl ether represented by the following general formula (1).
  • R 1 —O— (AO) m—H (1) (In the general formula (1), R 1 is an alkyl group having 4 to 14 carbon atoms, an alkenyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and AO is an oxyalkylene having 1 to 50 carbon atoms.
  • the number of carbon atoms of the alkyl group represented by R 1 is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
  • the alkyl group represented by R 1 is preferably at least one selected from the group consisting of hexyl, 2-ethylhexyl, isononyl, and 2-hexyldecyl, and is preferably a group consisting of a hexyl group and a 2-ethylhexyl group.
  • the number of carbon atoms of the alkenyl group represented by R 1 is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 18 or less.
  • the number of carbon atoms of the aryl group represented by R 1 is preferably 6 or more, more preferably 12 or more, preferably 30 or less, more preferably 24 or less, preferably 6 to 30, and more preferably 12 to 24
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 22> to ⁇ 25>.
  • the aryl group includes a phenyl group, a styrenated phenyl group, a phenylethyl group, a distyrenated phenyl group, a tristyrenated phenyl group, a benzyl group, a benzylated phenyl group, a dibenzylated phenyl group, and a tribenzylated phenyl group.
  • the three-dimensional object precursor treatment composition according to any one of ⁇ 22> to ⁇ 26>, wherein at least one selected from the group is preferred, and a benzylated phenyl group is more preferred.
  • the benzylated phenyl group is preferably at least one selected from the group consisting of a monostyrenated phenyl group, a distyrenated phenyl group, a monobenzylated phenyl group, and a dibenzylated phenyl group, a monostyrenated phenyl group, And at least one selected from the group consisting of distyrenated phenyl groups, more preferably distyrenated phenyl groups, and the three-dimensional object precursor treating agent composition according to ⁇ 27>.
  • the number of carbon atoms of the oxyalkylene group represented by AO in the general formula (1) is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and 50 or less.
  • 20 or less is more preferable, 18 or less is more preferable, 1 to 50 is preferable, 2 to 20 is more preferable, 3 to 20 is still more preferable, and 4 to 18 is still more preferable, ⁇ 22> to ⁇ 28>
  • the m is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 18 or less, still more preferably 12 or less, preferably 1 to 20, more preferably 2 to 18, more preferably 2 to
  • the three-dimensional object precursor treating agent composition according to any one of ⁇ 22> to ⁇ 29>, wherein 12 is more preferred.
  • the content of the nonionic penetrant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 10% by mass or less in the three-dimensional object precursor treatment agent composition.
  • composition for treating a three-dimensional object precursor according to any one of ⁇ 22> to ⁇ 30> preferably 5% by mass or less, more preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass.
  • ⁇ 32> The three-dimensional object precursor treatment composition according to any one of ⁇ 1> to ⁇ 31>, further comprising (c) a surfactant.
  • ⁇ 33> The three-dimensional object precursor treatment composition according to ⁇ 32>, wherein the (b) nonionic penetrant is not included in the (c) surfactant.
  • the content of the surfactant in the three-dimensional object precursor treating agent composition is preferably 0.05% by mass or less, and more preferably substantially 0% by mass, ⁇ 32> or ⁇ 33>
  • ⁇ 35> A three-dimensional object, and a modeling process for obtaining a three-dimensional object precursor including a support material including a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, and the three-dimensional object A method for producing a three-dimensional object by a hot-melt laminating method, comprising a support material removing step of bringing an object precursor into contact with a three-dimensional object precursor treating agent composition and removing the support material, wherein the three-dimensional object precursor A method for producing a three-dimensional object, wherein the treatment composition is the three-dimensional object precursor treatment composition according to any one of ⁇ 1> to ⁇ 34>.
  • the molding material is preferably at least one thermoplastic resin selected from the group consisting of ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin, and ABS resin and / or polylactic acid resin is preferable.
  • the three-dimensional modeling soluble material that is a material of the support material preferably includes a (meth) acrylic acid-based copolymer having a hydrophilic monomer and a hydrophobic monomer as monomer units, ⁇ 35> or ⁇ 35>36>.
  • the method for producing a three-dimensional object according to 36> is preferably at least one thermoplastic resin selected from the group consisting of ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin, and ABS resin and / or polylactic acid resin is preferable.
  • the hydrophilic monomer is acrylic acid, methacrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl methacrylate, methacrylic acid.
  • At least one selected from the group consisting of 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, itaconic acid, maleic acid, fumaric acid, ⁇ -hydroxyacrylic acid is preferable.
  • the hydrophobic monomer is 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, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate , 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate,
  • the pH of the three-dimensional object precursor treating agent composition is preferably 10 or more, more preferably 11 or more, preferably 14 or less, more preferably 13 or less, more preferably 10 to 14, and more preferably 10 to 13
  • the temperature of the three-dimensional object precursor treating agent composition in the support material removing step is preferably 25 ° C or higher, more preferably 40 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower, 25
  • ⁇ 42> Use of the composition according to any one of ⁇ 1> to ⁇ 34> as a three-dimensional object precursor treatment agent.
  • Examples 1A to 8A, Comparative Example 1A and Comparative Example 2A> [Production of evaluation samples]
  • ABS Stratasys ABS resin
  • SR-30 a soluble material for three-dimensional modeling (methacrylic acid copolymer manufactured by Stratasys; monomer unit; methacrylic)
  • An evaluation sample three-dimensional object precursor
  • FIG. 1 is a schematic diagram showing the shape of the evaluation sample
  • FIG. 2 is a schematic diagram showing the cross-sectional shape of the evaluation sample.
  • FIG. 1 is a schematic diagram showing the shape of the evaluation sample.
  • the evaluation sample is a three-dimensional object having a trunk portion 1, a leg portion including a leg portion 21 and a leg portion 22, and a three-dimensional object precursor made of a support material.
  • the leg part 21 and the leg part 22 are connected in the trunk
  • FIG. 2 is a schematic view showing the cross-sectional shape of the evaluation sample.
  • the body portion 1 has a shaft passing portion 11.
  • the leg portion 21 and the leg portion 22 are connected by an axis (not shown) passing through the shaft-passing portion 11, and if there is no support material indicated by the support material outer edge portion 3, the leg portion 21 according to the evaluation sample and The leg portion composed of the leg portion 22 is movable with respect to the trunk portion 1.
  • the distance between the shaft connecting the leg portion 21 and the leg portion 22 in the shaft passing portion 11 and the surface of the shaft passing portion 11 is 0.6 mm.
  • Examples 1B to 5B, Comparative Example 1B and Comparative Example 2B> [Evaluation method: endurance operation time] An aqueous solution having the composition shown in Table 3 was prepared and used as a three-dimensional object precursor treating agent composition according to Examples 1B to 5B, Comparative Example 1B, and Comparative Example 2B. The evaluation sample is immersed in the three-dimensional object precursor treatment agent composition according to Examples 1B to 5B, Comparative Example 1B, and Comparative Example 2B at a liquid temperature of 60 ° C., and the leg 21 of FIG. The time (durability moving time) until the leg part which consists of the leg part 22 became movable was measured.
  • Example 1B-5B and Comparative Example 1B and the results of evaluation of the three-dimensional object precursor treating agent composition according to Examples 1A-5A and Comparative Example 1A having the same composition other than the three-dimensional modeling soluble material durability moving time
  • trunk part 11 shaft through part 21: leg part 22: leg part 3: support material outer edge part

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Abstract

La composition d'agent de traitement pour précurseur d'objet tridimensionnel de l'invention est destinée à retirer un matériau de support qui contient un copolymère à base d'acide (méth)acrylique possédant un monomère hydrophile et un monomère hydrophobe en tant qu'unité monomère, d'un précurseur d'objet tridimensionnel contenant un objet tridimensionnel et ledit matériau de support. Ladite composition d'agent de traitement pour précurseur d'objet tridimensionnel comprend (a) un agent alcalin et (b) un agent mouillant non ionique. Plus précisément, l'invention permet de fournir une composition d'agent de traitement pour précurseur d'objet tridimensionnel capable de retirer rapidement et par petites quantités un matériau de support comprenant un copolymère à base d'acide (méth)acrylique, qui se trouve dans les interstices d'un objet tridimensionnel. L'invention permet également de fournir un procédé de fabrication d'objet tridimensionnel selon un procédé de stratification par thermofusion mettant en œuvre cette composition d'agent de traitement pour précurseur d'objet tridimensionnel.
PCT/JP2016/064560 2016-05-17 2016-05-17 Composition d'agent de traitement pour précurseur d'objet tridimensionnel Ceased WO2017199323A1 (fr)

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Cited By (1)

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WO2020110935A1 (fr) 2018-11-26 2020-06-04 花王株式会社 Composition d'agent de traitement de précurseur d'objet tridimensionnel

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JP2001354996A (ja) * 2000-06-09 2001-12-25 Jsr Corp 光造形物の洗浄剤および洗浄方法
JP2012052024A (ja) * 2010-09-01 2012-03-15 Arakawa Chem Ind Co Ltd 光造形樹脂成形体用洗浄剤組成物
JP2014083744A (ja) * 2012-10-23 2014-05-12 Kao Corp ３ｄプリンタ造形物用現像液組成物
WO2016059987A1 (fr) * 2014-10-14 2016-04-21 花王株式会社 Matériau soluble destiné à un moulage tridimensionnel
JP2016078284A (ja) * 2014-10-14 2016-05-16 花王株式会社 三次元造形用可溶性材料

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JP2001354996A (ja) * 2000-06-09 2001-12-25 Jsr Corp 光造形物の洗浄剤および洗浄方法
JP2012052024A (ja) * 2010-09-01 2012-03-15 Arakawa Chem Ind Co Ltd 光造形樹脂成形体用洗浄剤組成物
JP2014083744A (ja) * 2012-10-23 2014-05-12 Kao Corp ３ｄプリンタ造形物用現像液組成物
WO2016059987A1 (fr) * 2014-10-14 2016-04-21 花王株式会社 Matériau soluble destiné à un moulage tridimensionnel
JP2016078284A (ja) * 2014-10-14 2016-05-16 花王株式会社 三次元造形用可溶性材料

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Publication number Priority date Publication date Assignee Title
WO2020110935A1 (fr) 2018-11-26 2020-06-04 花王株式会社 Composition d'agent de traitement de précurseur d'objet tridimensionnel

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