WO2016059987A1 - Matériau soluble destiné à un moulage tridimensionnel - Google Patents

Matériau soluble destiné à un moulage tridimensionnel Download PDF

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Publication number
WO2016059987A1
WO2016059987A1 PCT/JP2015/078113 JP2015078113W WO2016059987A1 WO 2016059987 A1 WO2016059987 A1 WO 2016059987A1 JP 2015078113 W JP2015078113 W JP 2015078113W WO 2016059987 A1 WO2016059987 A1 WO 2016059987A1
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Prior art keywords
copolymer
mass
monomer unit
dimensional object
group
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PCT/JP2015/078113
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English (en)
Japanese (ja)
Inventor
吉村　忠徳
拓馬 木村
丈士 平井
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花王株式会社
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Priority claimed from JP2014250054A external-priority patent/JP6491467B2/ja
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to EP15850615.4A priority Critical patent/EP3208073B1/fr
Priority to US15/518,812 priority patent/US10738142B2/en
Priority to CN201580044372.7A priority patent/CN106660266B/zh
Publication of WO2016059987A1 publication Critical patent/WO2016059987A1/fr

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    • 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
    • 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
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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

Definitions

  • the present invention relates to a soluble material for three-dimensional modeling.
  • the present invention relates to a soluble material for three-dimensional modeling used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a 3D printer, particularly a hot melt lamination type 3D printer.
  • 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.
  • a method for removing the support material from the three-dimensional object precursor a method using a methacrylic acid copolymer as the support material and removing the support material by immersing the three-dimensional object precursor in an alkaline aqueous solution (for example, JP-T 2008-507619 and JP-T 2012-509777).
  • This method utilizes the fact that the carboxylic acid in the methacrylic acid copolymer is neutralized with an alkali and dissolved in an aqueous alkali solution.
  • the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer. And at least one copolymer selected from the group consisting of the following (I) to (III).
  • R 1 represents a straight-chain alkyl group or branched alkyl group having 1 to 8 carbon atoms.
  • n 1 to 3
  • R 2 represents hydrogen or a methyl group.
  • R 3 represents an alkyl group having 1 or 2 carbon atoms.
  • the method for producing a three-dimensional object according to the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removal for removing the support material by bringing the three-dimensional object precursor into contact with an alkaline aqueous solution. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has a process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.
  • the support material of the present invention is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and is selected from the group consisting of the following (I) to (III): And at least one copolymer.
  • R 1 represents a straight-chain alkyl group or branched alkyl group having 1 to 8 carbon atoms.
  • n 1 to 3
  • R 2 represents hydrogen or a methyl group.
  • R 3 represents an alkyl group having 1 or 2 carbon atoms.
  • the methacrylic acid copolymers disclosed in JP-T-2008-507619 and JP-T-2012-509777 have a low dissolution rate in an alkaline aqueous solution
  • the methacrylic acid copolymer was used as a support material.
  • the three-dimensional object precursor is immersed in an alkaline aqueous solution for a long time, the three-dimensional object in the three-dimensional object precursor tends to be eroded by alkali. Therefore, application of polyester resins such as polylactic acid (PLA) having low resistance to alkali has been limited as a material for three-dimensional objects.
  • PLA polylactic acid
  • the present invention is suitable for manufacturing a three-dimensional object by the FDM method, has a high dissolution rate in an alkaline aqueous solution, can be quickly removed from the three-dimensional object precursor, and suppresses or reduces damage to the three-dimensional object.
  • a three-dimensional modeling soluble material for a support material a three-dimensional object modeling method using the three-dimensional modeling soluble material, and a support material.
  • the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer. And at least one copolymer selected from the group consisting of the following (I) to (III).
  • R 1 represents a straight-chain alkyl group or branched alkyl group having 1 to 8 carbon atoms.
  • n 1 to 3
  • R 2 represents hydrogen or a methyl group.
  • R 3 represents an alkyl group having 1 or 2 carbon atoms.
  • the method for producing a three-dimensional object according to the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removal for removing the support material by bringing the three-dimensional object precursor into contact with an alkaline aqueous solution. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has a process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.
  • the support material of the present invention is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and is selected from the group consisting of the following (I) to (III): And at least one copolymer.
  • R 1 represents a straight-chain alkyl group or branched alkyl group having 1 to 8 carbon atoms.
  • n 1 to 3
  • R 2 represents hydrogen or a methyl group.
  • R 3 represents an alkyl group having 1 or 2 carbon atoms.
  • a three-dimensional modeling soluble material for a support material that has a high dissolution rate in an alkaline aqueous solution can be quickly removed from a three-dimensional object precursor, and can suppress or reduce damage to the three-dimensional object. Can be provided.
  • the present invention it is possible to provide a method for producing a three-dimensional object that can be quickly removed from the three-dimensional object precursor and that can suppress or reduce damage to the three-dimensional object.
  • a support material that has a high dissolution rate in an alkaline aqueous solution, can be quickly removed from the three-dimensional object precursor, and can suppress or reduce damage to the three-dimensional object.
  • the three-dimensional modeling soluble material of the present embodiment is a three-dimensional modeling soluble material that is used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer. And at least one copolymer selected from the group consisting of the following (I) to (III). (I) having a hydrophilic monomer unit represented by the general formula (1) and at least one selected from the group consisting of hydrophobic monomer units represented by the general formulas (4) to (6). And a copolymer having a content of the hydrophilic monomer unit in the copolymer of 20 to 80% by mass (hereinafter also referred to as copolymer (I)).
  • copolymer (II) having at least one selected from the group consisting of the hydrophilic monomer unit represented by the general formula (2) and the hydrophobic monomer unit represented by the general formula (7), Copolymer having a content of the hydrophilic monomer unit in the polymer of 20 to 80% by mass (hereinafter also referred to as copolymer (II)) (III)
  • the hydrophilic monomer unit represented by the general formula (3) and the hydrophobic monomer unit represented by the general formula (8), and the hydrophilic monomer unit in the copolymer Copolymer having a content of 20 to 80% by mass hereinafter also referred to as copolymer (III)
  • the support material made of the soluble material for 3D modeling has a high dissolution rate in an alkaline aqueous solution, can be quickly removed from the 3D object precursor, and can suppress or reduce damage to the 3D object.
  • the reason why the three-dimensional modeling soluble material has such an effect is not clear, but is considered as follows.
  • the copolymer contained in the composition described in JP-T-2008-507619 contains monomer units derived from methacrylic acid.
  • the copolymer is presumed to have reduced or reduced access / diffusion of water and water-soluble alkali due to the hydrophobicity of the ⁇ -position methyl group adjacent to the carboxyl group of the monomer unit derived from methacrylic acid.
  • the copolymers (I) to (III) contained in the three-dimensional modeling availability material according to the present embodiment are composed of monomer units derived from acrylic acid, itaconic acid, and maleic acid (fumaric acid). At least one selected from the above has a hydrophilic monomer unit.
  • the hydrophilic monomer unit does not have a hydrophobic methyl group derived from methacrylic acid, it has higher hydrophilicity than the monomer unit derived from methacrylic acid.
  • these are incorporated in the polymer, it is considered that the affinity for water is increased, the diffusion of alkali into the surface / inside of the polymer is increased, and the solubility of the copolymer in the aqueous alkali solution can be enhanced. Further, since the surface of the support material forms an interface with air, the hydrophobic monomer unit tends to segregate on the surface.
  • a copolymer including a hydrophilic monomer unit and a hydrophobic monomer unit it is considered that more hydrophobic monomer units are segregated on the surface of the copolymer in which the hydrophobic monomer units are chained. For this reason, the hydrophilic monomer unit and the hydrophobic monomer unit are uniformly dispersed like an alternating copolymer to prevent segregation of the hydrophobic monomer unit on the surface of the support material and to increase the hydrophilicity of the surface of the support material. It is thought that you can.
  • the homogeneity of the monomer unit in the copolymer produced by radical polymerization can be estimated from the radical reactivity ratio of each monomer in the case of a copolymer composed of two types of monomers.
  • This reactivity ratio is calculated from the formula of Alfreey and Price (Chemist Doujin, Takayuki Otsu et al., “Experimental Method for Polymer Synthesis”, 1972, 8th edition, pages 192-193). It can be calculated using the intrinsic Q and e values (Wiley, J. Brandrup et al., Polymer Handbook, Fourth Edition, Volume 1, II309-II319).
  • Methacrylic acid (0.98-1.1)> acrylic acid (0.58-0.78)> itaconic acid (0.39-0.49)> (anhydrous) maleic acid ( ⁇ 0).
  • the hydrophilic monomer unit can be homogeneously dispersed in the alternating copolymer, the segregation of the hydrophobic monomer unit on the surface of the support material can be prevented, and the hydrophilicity of the support material surface can be increased. Since the combination of the hydrophilic monomer unit and the hydrophobic monomer unit in the copolymers (I) to (III) contained in the three-dimensional modeling soluble material of the present embodiment has a small rate constant, the hydrophilic monomer unit And the hydrophobic monomer units are homogeneously dispersed in the copolymers (I) to (III), and can prevent segregation of the hydrophobic monomer units on the surface of the support material and increase the hydrophilicity of the surface of the support material.
  • the copolymers (II) and (III) containing itaconic acid and (anhydride) maleic acid having a lower r 1 have a structure having higher alternating copolymerization properties than acrylic acid, and are more hydrophobic than acrylic acid units.
  • the chain of hydrophilic units sandwiched between the two tends to be short, and the chain of hydrophobic monomer units tends to be long. Therefore, the hydrophilic units in the copolymers (II) and (III) are more susceptible to the hydrophobic units. The higher the hydrophobicity of the hydrophobic units, the more difficult it is for water to approach the hydrophilic units and the dissolution rate. Is considered to decrease.
  • the support material obtained using the three-dimensional modeling soluble material of the present embodiment containing the copolymers (I) to (III) as a material is an alkaline aqueous solution suitable for manufacturing a three-dimensional object by the FDM method. It is considered that the rate of dissolution in the water is high, it can be quickly removed from the three-dimensional object precursor, and damage to the three-dimensional object can be suppressed or reduced.
  • the copolymer (I) is represented by the hydrophilic monomer unit represented by the general formula (1) (hereinafter also referred to as hydrophilic monomer unit A) and the general formulas (4) to (6).
  • the hydrophilic monomer unit A in the copolymer (I) having at least one or more hydrophobic monomer units selected from the group consisting of hydrophobic monomer units (hereinafter also referred to as hydrophobic monomer unit A). Is a copolymer having a content of 20 to 80% by mass.
  • the hydrophilic monomer unit A is a monomer unit derived by polymerizing acrylic acid.
  • Content of the said hydrophilic monomer unit A in the said copolymer (I) is 20 mass% or more from a viewpoint of the melt
  • the content of the hydrophilic monomer unit A in the copolymer (I) is 80 mass from the viewpoint of storage stability of the three-dimensional modeling soluble material and the support material using the three-dimensional modeling soluble material. % Or less, preferably 60% by mass or less, and more preferably 55% by mass or less. Summing up these viewpoints, the content of the hydrophilic monomer unit A in the copolymer (I) is 20 to 80% by mass, preferably 22 to 60% by mass, more preferably 30 to 55% by mass. preferable.
  • the monomer unit represented by the general formula (4) is a monomer unit derived by polymerizing a corresponding alkyl acrylate.
  • R 1 is composed of a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and a 2-ethylhexyl group. At least one selected from the group is preferred. Among these, at least one or more selected from the group consisting of a methyl group, an ethyl group, and an n-butyl group is more preferable from the viewpoint of improving the dissolution rate in an alkaline aqueous solution, and from the viewpoint of formability by a 3D printer, More preferred is an ethyl group.
  • the monomer unit represented by the general formula (5) is a monomer unit derived by polymerizing styrene.
  • the monomer unit represented by the general formula (6) is a monomer unit derived by polymerizing ⁇ -methylene- ⁇ -valerolactone corresponding thereto.
  • R 1 is a methyl group, an ethyl group, or n-butyl.
  • R 1 is a monomer group of a methyl group or an ethyl group, and represented by the general formula (5). More preferred are styrene monomer units.
  • the content of the hydrophobic monomer unit A in the copolymer (I) is 20% by mass from the viewpoint of the storage stability of the soluble material for three-dimensional modeling and the support material using the soluble material for three-dimensional modeling. The above is preferable, 40 mass% or more is more preferable, and 45 mass% or more is still more preferable.
  • the content of the hydrophobic monomer unit A in the copolymer (I) is preferably 80% by mass or less, more preferably 78% by mass or less, from the viewpoint of improving the dissolution rate in an alkaline aqueous solution, and 70% by mass. The following is more preferable. Summing up these viewpoints, the content of the hydrophobic monomer unit A in the copolymer (I) is preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and 45 to 70% by mass. Further preferred.
  • the copolymer (I) contains a monomer unit other than the hydrophilic monomer unit A and the hydrophobic monomer unit A as long as the effect of the three-dimensional modeling soluble material according to this embodiment is not impaired. Also good.
  • monomer units other than the hydrophilic monomer unit A and the hydrophobic monomer unit A the monomer unit represented by the general formula (2), the monomer unit represented by the general formula (3), ⁇ -hydroxyacrylic From acid units, vinyl alcohol units, polyethylene glycol acrylate units, polyethylene glycol methacrylate units, methyl vinyl ether units, styrene sulfonic acid units, vinyl acetate units, vinyl propionate units, adamantyl methacrylate units, ethylene units, and propylene units
  • the copolymer (II) includes a hydrophilic monomer unit represented by the general formula (2) (hereinafter also referred to as a hydrophilic monomer unit B) and a hydrophobic monomer unit represented by the general formula (7). At least one hydrophobic monomer unit selected from the group consisting of (hereinafter also referred to as hydrophobic monomer unit B), and the content of the hydrophilic monomer unit B in the copolymer (II) is The copolymer is 20 to 80% by mass.
  • hydrophilic monomer unit B is a monomer unit derived by polymerizing itaconic acid.
  • the content of the hydrophilic monomer unit B in the copolymer (II) is 20% by mass or more, preferably 22% by mass or more, more preferably 30% by mass or more from the viewpoint of improving the dissolution rate in the aqueous alkali solution. Preferably, 35 mass% or more is more preferable.
  • the content of the hydrophilic monomer unit B in the copolymer (II) is 80 mass from the viewpoint of the storage stability of the three-dimensional modeling soluble material and the support material using the three-dimensional modeling soluble material. % Or less, preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.
  • the content of the hydrophilic monomer unit B in the copolymer (II) is 20 to 80% by mass, preferably 22 to 60% by mass, more preferably 30 to 55% by mass. Preferably, 35 to 50% by mass is more preferable.
  • Hydrophobic monomer unit B (Monomer unit represented by the general formula (7))
  • the hydrophobic monomer unit represented by the general formula (7) is a monomer unit derived by polymerizing a corresponding alkyl acrylate.
  • R 1 is at least one selected from the group consisting of a methyl group and an ethyl group, and among these, a methyl group is preferable from the viewpoint of improving the dissolution rate in an alkaline aqueous solution.
  • the content of the hydrophobic monomer unit B in the copolymer (II) is 20% by mass from the viewpoint of the storage stability of the three-dimensional modeling soluble material and the support material using the three-dimensional modeling soluble material.
  • the above is preferable, 40% by mass or more is more preferable, 45% by mass or more is further preferable, and 50% by mass or more is more preferable.
  • the content of the hydrophobic monomer unit B in the copolymer (II) is preferably 80% by mass or less, more preferably 78% by mass or less, from the viewpoint of improving the dissolution rate in an aqueous alkali solution, and 70% by mass. The following is more preferable, and 65% by mass or less is more preferable.
  • the content of the hydrophobic monomer unit B in the copolymer (II) is preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and 45 to 70% by mass. Further preferred is 50 to 65% by mass.
  • the copolymer (II) contains monomer units other than the hydrophilic monomer unit B and the hydrophobic monomer unit B as long as the effects of the soluble material for three-dimensional modeling according to this embodiment are not impaired. Also good.
  • monomer units other than the hydrophilic monomer unit B and the hydrophobic monomer unit B a monomer unit represented by the general formula (1), a monomer unit represented by the general formula (3), and the general formula ( 4) a monomer unit in which R 1 is a linear or branched alkyl group having 3 to 8 carbon atoms, a hydrophobic monomer unit represented by the general formula (5), Hydrophobic monomer unit represented by formula (6), ⁇ -hydroxyacrylic acid unit, vinyl alcohol unit, acrylic acid polyethylene glycol ester unit, methacrylic acid polyethylene glycol unit, methyl vinyl ether unit, styrene sulfonic acid unit, vinyl acetate unit, Vinyl propionate unit Methacrylic acid adamantyl units, ethylene units,
  • the copolymer (III) includes a hydrophilic monomer unit represented by the general formula (3) (hereinafter also referred to as a hydrophilic monomer unit C) and a hydrophobic monomer unit represented by the general formula (8). (Hereinafter also referred to as hydrophobic monomer unit C), and the content of the hydrophilic monomer unit C in the copolymer (III) is 20 to 80% by mass.
  • the hydrophilic monomer unit C is a monomer unit derived by polymerizing maleic acid and / or fumaric acid.
  • the content of the hydrophilic monomer unit C in the copolymer (III) is 20% by mass or more, preferably 22% by mass or more, more preferably 30% by mass or more from the viewpoint of improving the dissolution rate in the aqueous alkali solution. preferable. Further, the content of the hydrophilic monomer unit C in the copolymer (III) is 80 mass from the viewpoint of the storage stability of the three-dimensional modeling soluble material and the support material using the three-dimensional modeling soluble material. % Or less, preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and even more preferably 45% by mass or less.
  • the content of the hydrophilic monomer unit C in the copolymer (III) is 20 to 80% by mass, preferably 22 to 60% by mass, more preferably 30 to 55% by mass. 30 to 50% by mass is more preferable, and 30 to 45% by mass is even more preferable.
  • hydrophobic monomer unit C (Monomer unit represented by the general formula (8))
  • the hydrophobic monomer unit represented by the general formula (8) is a monomer unit derived by polymerizing methyl methacrylate.
  • the content of the hydrophobic monomer unit C in the copolymer (III) is 20% by mass or more from the viewpoint of the storage stability of the three-dimensional modeling soluble material and the support material using the three-dimensional modeling soluble material. 40 mass% or more is more preferable, 45 mass% or more is further more preferable, 50 mass% or more is further more preferable, and 55 mass% or more is still more preferable.
  • the content of the hydrophobic monomer unit C in the copolymer (III) is preferably 80% by mass or less, more preferably 78% by mass or less, from the viewpoint of improving the dissolution rate in an alkaline aqueous solution, and 70% by mass. The following is more preferable.
  • the content of the hydrophobic monomer unit C in the copolymer (III) is preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and 45 to 70% by mass. More preferably, 50 to 70% by mass is even more preferable, and 55 to 70% by mass is even more preferable.
  • the copolymer (III) contains a monomer unit other than the hydrophilic monomer unit C and the hydrophobic monomer unit C as long as the effects of the soluble material for three-dimensional modeling according to this embodiment are not impaired. Also good.
  • monomer units other than the hydrophilic monomer unit C and the hydrophobic monomer unit C the monomer unit represented by the general formula (1), the monomer unit represented by the general formula (2), the general formula ( 4), a monomer unit in which R1 is a linear alkyl group or a branched alkyl group having 2 to 8 carbon atoms, a monomer unit represented by the general formula (5), and the general formula (6) )
  • the glass transition temperatures of the copolymers (I) to (III) are preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, and 85 ° C. or higher from the viewpoint of formability by a 3D printer. More preferably, 90 degreeC or more is still more preferable. Further, the glass transition temperature of each of the copolymers (I) to (III) is preferably 200 ° C. or less, more preferably 180 ° C., still more preferably 160 ° C. or less, still more preferably 140 ° C. or less, from the same viewpoint. 130 degrees C or less is still more preferable.
  • the weight average molecular weights of the copolymers (I) to (III) are preferably 20000 or more, more preferably 50000 or more, and still more preferably 70000 or more from the viewpoint of formability by a 3D printer.
  • the weight average molecular weight of each of the copolymers (I) to (III) is preferably 500,000 or less, more preferably 470000 or less from the viewpoint of improving the dissolution rate in an alkaline aqueous solution and the formability by a 3D printer. 450,000 or less is still more preferable, 400,000 or less is still more preferable, and 350,000 or less is still more preferable.
  • the weight average molecular weights of the copolymers (I) to (III) are preferably 20,000 to 500,000, more preferably 20,000 to 470000, still more preferably 50,000 to 450,000, and more preferably 70,000 to 400,000. More preferably, 70,000-350,000 are even more preferable.
  • a weight average molecular weight is measured by the method as described in an Example.
  • the total content of the copolymers (I) to (III) in the three-dimensional modeling soluble material is preferably 50% by mass or more, more preferably 60% by mass or more from the viewpoint of improving the dissolution rate in an alkaline aqueous solution. Preferably, 70 mass% or more is still more preferable, and 80 mass% or more is still more preferable. From the same viewpoint, the total content of the copolymers (I) to (III) in the three-dimensional modeling soluble material is preferably 98% by mass or less, more preferably 95% by mass or less, and 92% by mass. The following is more preferable.
  • the total content of the copolymers (I) to (III) in the three-dimensional modeling soluble material is preferably 50 to 98% by mass, more preferably 70 to 98% by mass. 75 to 95% by mass is more preferable, and 80 to 92% by mass is even more preferable.
  • the soluble material for three-dimensional modeling contains a plasticizer from the viewpoint of facilitating modeling by lowering the viscosity during modeling by a 3D printer, and from the viewpoint of imparting toughness to the support material.
  • a polyester plasticizer a polyhydric alcohol ester plasticizer, a polyhydric acid from the viewpoint of facilitating modeling by lowering the viscosity during modeling by a 3D printer, and from the viewpoint of imparting toughness to the support material
  • a carboxylic acid ester plasticizer and a phosphoric acid ester plasticizer is preferable, and a polyvalent carboxylic acid ester plasticizer is more preferable.
  • the plasticizer include those disclosed in JP-A-2008-507619, paragraph 0036.
  • a polyvalent carboxylic acid ester plasticizer a polyvalent carboxylic acid, preferably 1 to 12 carbon atoms, more preferably carbon A mono-, di- or triester with a monoalcohol having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, or a (poly) oxyalkylene adduct thereof can be used.
  • the polyvalent carboxylic acid include succinic acid, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid.
  • the monoalcohol include methanol, ethanol, 1-propanol, and 1-butanol.
  • Examples of the phosphoric ester plasticizer include mono-, di- or triesters of phosphoric acid and the above monoalcohol or its (poly) oxyalkylene adduct. Specific examples include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, tricresyl phosphate, tris (ethoxyethoxyethyl) phosphate, and the like. it can.
  • the content of the plasticizer in the soluble material for three-dimensional modeling is the three-dimensional modeling from the viewpoint of facilitating modeling by lowering the viscosity during modeling by a 3D printer, and from the viewpoint of imparting toughness to the support material.
  • the soluble material for use it is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the content of the plasticizer in the three-dimensional modeling soluble material is preferably 30% by mass or less with respect to 100% by mass of the copolymer in the three-dimensional modeling soluble material from the viewpoint of modeling by a 3D printer. 25 mass% or less is more preferable, and 20 mass% or less is still more preferable. Taking these viewpoints together, the content of the plasticizer in the three-dimensional modeling soluble material is preferably 2 to 30% by mass, more preferably 5 to 25% by mass in the three-dimensional modeling soluble material, More preferably, it is 10 to 20% by mass.
  • the SP values of the copolymers (I) to (III) and the SP value of the plasticizer are the same as those of the copolymers (I) to (III). From the viewpoint of the compatibility of the plasticizer and the plasticizer, each is preferably 8 or more, more preferably 8.5 or more, and still more preferably 9 or more. Further, from the same viewpoint, the SP values of the copolymers (I) to (III) and the SP value of the plasticizer are preferably 13 or less, more preferably 12 or less, and further preferably 11.5 or less. preferable.
  • the SP value of the copolymers (I) to (III) and the SP value of the plasticizer are both preferably 8 to 13, more preferably 8.5 to 12, and 9 to 11 .5 is more preferred.
  • SP value ( ⁇ E / V) 1/2 (cal 1/2 cm ⁇ 3/2 )
  • the three-dimensional modeling soluble material may include a polymer other than the copolymers (I) to (III) as long as the effects of the three-dimensional modeling soluble material according to this embodiment are not impaired.
  • polymers other than the copolymers (I) to (III) include water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, poly (ethylene glycol / propylene glycol), carboxymethyl cellulose, and starch, and hard and soft segments.
  • Polyether esters and polyether ester amides which are elastomers made from, graft polymers obtained by grafting a polymer such as polyacrylic acid having a hydrophilic group to hydrophobic rubber, graft polymers obtained by grafting polyoxazoline to silicone, ionic elastomers Hydrophilic thermoplastic elastomers such as styrene-butadiene copolymers, and thermoplastic elastomers such as polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate block copolymers It includes sexual polymers.
  • the SP value of the copolymers (I) to (III) and the copolymer (I ) To (III) is any from the viewpoint of the compatibility between the copolymers (I) to (III) and the polymers other than the copolymers (I) to (III). Is preferably 8 or more, more preferably 8.5 or more, and still more preferably 9 or more. In addition, from the same viewpoint, the SP value of the copolymers (I) to (III) and the SP value of polymers other than the copolymers (I) to (III) are preferably 13 or less.
  • the SP values of the copolymers (I) to (III) and the SP values of polymers other than the copolymers (I) to (III) are all 8 to 13. It is preferably 8.5 to 12, more preferably 9 to 11.5.
  • the shape of the soluble material for three-dimensional modeling is not particularly limited, and examples thereof include a pellet shape, a powder shape, and a filament shape, but a filament shape is preferable from the viewpoint of modeling by a 3D printer.
  • the diameter of the filament is preferably 0.5 mm or more, and more preferably 1.0 mm or more from the viewpoint of modeling by a 3D printer and improvement of the accuracy of a three-dimensional object. Further, the diameter of the filament is preferably 3.0 mm or less, more preferably 2.0 mm or less, and still more preferably 1.8 mm or less from the viewpoints of formability by a 3D printer and improvement of the accuracy of a three-dimensional object.
  • the glass transition temperature of the soluble material for three-dimensional modeling is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 75 ° C. or higher from the viewpoint of formability by a 3D printer.
  • the glass transition temperature of the three-dimensional modeling soluble material is preferably 200 ° C. or lower, more preferably 160 ° C. or lower, and still more preferably 140 ° C. or lower from the same viewpoint.
  • the soluble material for three-dimensional modeling may contain other components as long as the effects of the present embodiment are not impaired.
  • examples of such other components include calcium carbonate, magnesium carbonate, glass sphere, graphite, carbon black, carbon fiber, glass fiber, talc, wollastonite, mica, alumina, silica, kaolin, whiskers, silicon carbide, etc. Materials.
  • the three-dimensional object manufacturing method of the present embodiment includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material for removing the support material by bringing the three-dimensional object precursor into contact with an alkaline aqueous solution.
  • the support material is the soluble material for three-dimensional modeling. According to the method for producing a three-dimensional object, it can be quickly removed from the three-dimensional object precursor, and damage to the three-dimensional object can be suppressed or reduced. The reason why the manufacturing method of the three-dimensional object has such an effect is not clear, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.
  • Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material The step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material is performed in a three-dimensional manner using a known hot-melt lamination type 3D printer except that the material of the support material is the soluble material for three-dimensional modeling.
  • a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the object manufacturing method can be used.
  • the molding material that is a 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 the conventional FDM type three-dimensional object manufacturing method.
  • the modeling material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin. Among these, 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 support material removing step the support material is removed by bringing the three-dimensional object precursor into contact with an alkaline aqueous solution.
  • the method of bringing the three-dimensional object precursor into contact with the aqueous alkaline solution is preferably a method of immersing the three-dimensional object precursor in the aqueous alkaline solution from the viewpoint of cost and ease of work. 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 alkaline aqueous solution is an aqueous solution in which an alkaline agent is dissolved.
  • the alkali agent is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, and amines such as monoethanolamine and diethanolamine from the viewpoint of solubility of the support material.
  • One or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate and monoethanolamine is more preferred.
  • the alkaline aqueous solution is an alkylene glycol alkyl ether, R—OCH 2 CH (OH) CH 2 OH (R is a group selected from an alkyl group, an alkenyl group, a benzyl group, a phenyl group, a furfuryl group, and a furfurylmethyl group).
  • glyceryl ether 1 type or 2 or more types of water-soluble solvents, such as glyceryl ether, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant 1 type, or 2 or more types of interfaces
  • An activator may be included, and examples of such an alkaline aqueous solution include Magiclin (registered trademark, manufactured by Kao Corporation).
  • the pH of the alkaline aqueous solution is preferably 10 or more, more preferably 11 or more, from the viewpoint of solubility of the support material.
  • the pH of the aqueous alkali solution 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 aqueous alkaline solution is preferably 10 to 14, more preferably 10 to 13, and still more preferably 11 to 13.
  • the alkaline aqueous solution may further contain other components as long as the solubility of the support material is not impaired.
  • the other components include water-soluble polymers such as sodium polyacrylate.
  • the amount of the alkaline aqueous solution 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 alkaline aqueous solution used is preferably 10000 times by mass or less, more preferably 5000 times by mass or less, still more preferably 1000 times by mass or less, and even more preferably 100 times by mass or less with respect to the support material from the viewpoint of workability. .
  • the time for contacting the three-dimensional modeling soluble material with the alkaline aqueous solution 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 alkaline aqueous solution is preferably 180 minutes or less, more preferably 120 minutes or less from the viewpoint of reducing damage to the three-dimensional object by contacting the alkaline aqueous solution for a long time. 90 minutes or less is more preferable.
  • the time for immersing the three-dimensional modeling soluble material in the alkaline aqueous solution is preferably 5 to 180 minutes, more preferably 5 to 120 minutes, and still more preferably 5 to 90 minutes.
  • the support material according to the present embodiment is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and includes the copolymers (I) to (III). At least one copolymer selected from the group consisting of:
  • the support material can be quickly removed from the three-dimensional object precursor, and damage to the three-dimensional object can be suppressed or reduced. The reason why the support material has such an effect is not certain, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.
  • the present specification further discloses the following composition and production method.
  • a soluble material for three-dimensional modeling used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer.
  • a soluble material for three-dimensional modeling comprising at least one copolymer selected from the group consisting of III).
  • a copolymer (I) having a content of the hydrophilic monomer unit in the copolymer of 20 to 80% by mass.
  • the content of the hydrophilic monomer unit represented by the general formula (1) in the copolymer (I) is 20 to 80% by mass, preferably 22 to 60% by mass, and preferably 30 to 55%.
  • R 1 is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and 2-ethylhexyl.
  • ⁇ 6> Total content of at least one hydrophobic monomer unit selected from the group consisting of the hydrophobic monomer units represented by the general formulas (4) to (6) in the copolymer (I)
  • the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 5> preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and still more preferably 45 to 70% by mass.
  • the hydrophobic monomer unit represented by the general formulas (4) to (6) is a monomer unit in which R 1 is a methyl group, an ethyl group, or an n-butyl group in the general formula (4), A styrene monomer unit represented by the formula (5) is preferable, and in the general formula (4), a monomer unit in which R 1 is a methyl group or an ethyl group, and a styrene monomer unit represented by the general formula (5) are more preferable.
  • the content of the hydrophilic monomer unit represented by the general formula (2) in the copolymer (II) is 20% by mass or more, preferably 22% by mass or more, and more preferably 30% by mass or more. More preferably, it is 35% by mass or more, more preferably 80% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less. Any one of the above items ⁇ 1> to ⁇ 7>
  • the content of the hydrophilic monomer unit represented by the general formula (2) in the copolymer (II) is 20 to 80% by mass, preferably 22 to 60% by mass, and preferably 30 to 55%.
  • R 1 is at least one selected from the group consisting of a methyl group and an ethyl group, and a methyl group is preferable.
  • the content of the hydrophobic monomer unit represented by the general formula (7) in the copolymer (II) is preferably 20% by mass or more, more preferably 40% by mass or more, and 45% by mass or more.
  • the content of the hydrophobic monomer unit represented by the general formula (7) in the copolymer (II) is preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and 45 to The soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 11>, further preferably 70% by mass, and further preferably 50 to 65% by mass.
  • the content of the hydrophilic monomer unit represented by the general formula (3) in the copolymer (III) is 20% by mass or more, preferably 22% by mass or more, and more preferably 30% by mass or more. More preferably, it is 80% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, and further preferably 45% by mass or less, more preferably 45% by mass or less.
  • the soluble material for three-dimensional modeling according to any one of the above.
  • the content of the hydrophilic monomer unit represented by the general formula (3) in the copolymer (III) is 20 to 80% by mass, preferably 22 to 60% by mass, and 30 to 55%.
  • the content of the hydrophobic monomer unit represented by the general formula (8) in the copolymer (III) is preferably 20% by mass or more, more preferably 40% by mass or more, and 45% by mass or more. Is more preferably 50% by mass or more, more preferably 55% by mass or more, more preferably 80% by mass or less, more preferably 78% by mass or less, and further preferably 70% by mass or less.
  • the content of the hydrophobic monomer unit represented by the general formula (8) in the copolymer (III) is preferably 20 to 80% by mass, more preferably 40 to 78% by mass, and 45 to The soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 15>, further preferably 70% by mass, more preferably 50 to 70% by mass, and still more preferably 55 to 70% by mass.
  • the glass transition temperature of the copolymers (I) to (III) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, still more preferably 85 ° C. or higher, 90 ° C.
  • the weight average molecular weight of the copolymers (I) to (III) is preferably 20,000 or more, more preferably 50,000 or more, further preferably 70,000 or more, preferably 500,000 or less, more preferably 470000 or less, and 450,000 or less.
  • the weight average molecular weight of the copolymers (I) to (III) is preferably 20000 to 500000, more preferably 20000 to 470000, further preferably 50000 to 450,000, still more preferably 70000 to 400000, and 70000 to The soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 18>, wherein 350,000 is even more preferable.
  • the total content of the copolymers (I) to (III) in the three-dimensional modeling soluble material is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. More preferably, 80% by mass or more is more preferable, 98% by mass or less is preferable, 92% by mass or less is more preferable, and 90% by mass or less is more preferable.
  • the total content of the copolymers (I) to (III) in the three-dimensional modeling soluble material is preferably 50 to 98% by mass, more preferably 70 to 98% by mass, and 75 to 95.
  • the plasticizer is preferably at least one selected from the group consisting of a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer.
  • the polyvalent carboxylic acid ester plasticizer is a polyvalent carboxylic acid, preferably a monoalcohol having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, or a monoalcohol thereof.
  • the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 23> which is a mono, di, or triester with a (poly) oxyalkylene adduct.
  • the content of the plasticizer in the three-dimensional modeling soluble material is preferably 2% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more in the three-dimensional modeling soluble material.
  • the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 24> preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.
  • the content of the plasticizer in the three-dimensional modeling soluble material is preferably 2 to 30% by mass, more preferably 5 to 25% by mass in the three-dimensional modeling soluble material. % Is more preferable, The soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 25>.
  • the SP values of the copolymers (I) to (III) and the SP value of the plasticizer are preferably 8 or more. 8.5 or more is more preferable, 9 or more is more preferable, 13 or less is preferable, 12 or less is more preferable, and 11.5 or less is more preferable, 3D modeling according to any one of ⁇ 1> to ⁇ 26> Soluble material.
  • the SP value of the copolymers (I) to (III) and the SP value of the plasticizer are both 8 to 13.
  • the polymer other than the copolymers (I) to (III) is one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, poly (ethylene glycol / propylene glycol), carboxymethyl cellulose, and starch.
  • the SP values of the copolymers (I) to (III) and the SP values of polymers other than the copolymers (I) to (III) are preferably 8 or more, and 8.5. More preferably, 9 or more, more preferably 13 or less, more preferably 12 or less, still more preferably 11.5 or less, for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 30> Soluble material.
  • the SP values of the copolymers (I) to (III) and the SP values of polymers other than the copolymers (I) to (III) are preferably 8 to 13, respectively.
  • the filament has a diameter of preferably 0.5 mm or more, more preferably 1.0 mm or more, preferably 3.0 mm or less, more preferably 2.0 mm or less, and still more preferably 1.8 mm or less. Soluble material for three-dimensional modeling described in 1.
  • the glass transition temperature of the soluble material for three-dimensional modeling is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 75 ° C. or higher, preferably 200 ° C. or lower, more preferably 160 ° C. or lower, 140
  • a hot melt laminating method comprising a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material removing step of contacting the three-dimensional object precursor with an alkaline aqueous solution to remove the support material
  • the molding material as the material of the three-dimensional object is preferably at least one selected from the group consisting of ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin, and ABS resin and / or polylactic acid
  • the method of bringing the three-dimensional object precursor into contact with the alkaline aqueous solution is preferably a method of immersing the three-dimensional object precursor in the alkaline aqueous solution.
  • the alkaline aqueous solution is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, and amines such as monoethanolamine and diethanolamine,
  • the alkaline aqueous solution is an alkylene glycol alkyl ether, R—OCH 2 CH (OH) CH 2 OH (R is a group selected from an alkyl group, an alkenyl group, a benzyl group, a phenyl group, a furfuryl group, and a furfurylmethyl group) 1 type or 2 types or more of water-soluble solvents, anionic surfactants, cationic surfactants, nonionic surfactants or amphoteric surfactants such as glyceryl ether
  • R is a group selected from an alkyl group, an alkenyl group, a benzyl group, a phenyl group, a furfuryl group, and a furfurylmethyl group
  • anionic surfactants anionic surfactants
  • cationic surfactants cationic surfactants
  • nonionic surfactants nonionic surfactants or amphoteric surfactants
  • amphoteric surfactants such as
  • ⁇ 41> The three-dimensional object according to any one of ⁇ 36> to ⁇ 40>, wherein the pH of the alkaline aqueous solution is preferably 10 or more, more preferably 11 or more, preferably 14 or less, and more preferably 13 or less.
  • Method. ⁇ 42> The method for producing a three-dimensional object according to any one of ⁇ 36> to ⁇ 41>, wherein the pH of the alkaline aqueous solution is preferably 10 to 14, more preferably 10 to 13, and still more preferably 11 to 13.
  • the time for contacting the soluble material for three-dimensional modeling with an alkaline aqueous solution is preferably 5 minutes or more, preferably 180 minutes or less, more preferably 120 minutes or less, and still more preferably 90 minutes or less.
  • the time for immersing the three-dimensional modeling soluble material in an alkaline aqueous solution is preferably 5 to 180 minutes, more preferably 5 to 120 minutes, and still more preferably 5 to 90 minutes.
  • ⁇ 46> The support material according to ⁇ 45>, wherein the three-dimensional object is manufactured by the method for manufacturing a three-dimensional object according to any one of ⁇ 36> to ⁇ 44>.
  • ⁇ 47> Use of the soluble material for three-dimensional modeling described in ⁇ 1> to ⁇ 35> as a support material.
  • ⁇ Glass-transition temperature A portion of the amorphous film is cut out, accurately weighed 5 to 10 mg, sealed in an aluminum pan, and then increased from 25 ° C. to 250 ° C. at 10 ° C./min using a DSC device (DSC7020 manufactured by Seiko Instruments Inc.). After warming, it was rapidly cooled to 25 ° C. The glass transition temperature (° C.) was determined from the DSC curve obtained by raising the temperature again to 250 ° C. at 10 ° C./min.
  • hydrophilic monomer unit content The hydrophilic unit and hydrophobic unit contents were calculated by proton NMR measurement.
  • Formulation 1 200 g of acrylic acid (manufactured by Kanto Chemical Co., Inc.), 300 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 250 g of acetone, 250 g of ethanol Formulation 2: V-65B (manufactured by Wako Pure Chemical Industries, Ltd.) 7.17 g, acetone 100 g, ethanol 100 g
  • Synthesis Example 3 Polymer 3 was obtained in the same manner as in Synthesis Example 1 except that the amount of acrylic acid was changed to 250 g, the amount of methyl methacrylate to 250 g, and the amount of V-65B to 7.41 g in Synthesis Example 1.
  • Synthesis Example 4 Polymer 4 was obtained in the same manner as in Synthesis Example 2 except that the amount of acrylic acid in Synthesis Example 2 was changed to 15 g, the amount of methyl methacrylate to 10 g, and the amount of V-65B to 0.096 g.
  • Synthesis Example 5 Polymer 5 was obtained in the same manner as in Synthesis Example 1 except that methyl methacrylate was changed to ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and the amount of V-65B was changed to 6.71 g in Synthesis Example 1.
  • Synthesis Example 6 Polymer 6 was obtained in the same manner as in Synthesis Example 1 except that methyl methacrylate was changed to butyl methacrylate (Wako Pure Chemical Industries, Ltd.) and the amount of V-65B was changed to 6.07 g in Synthesis Example 1.
  • Synthesis Example 7 Polymer 7 was obtained in the same manner as in Synthesis Example 1 except that methyl methacrylate was changed to styrene (manufactured by Wako Pure Chemical Industries, Ltd.) and the amount of V-65B was changed to 7.03 g in Synthesis Example 1.
  • Synthesis Example 8 Synthesis Example 2 was the same as Synthesis Example 2 except that 10 g of acrylic acid, 15 g of methyl methacrylate were changed to 15 g of ⁇ -methylene- ⁇ -valerolactone (manufactured by Kanto Chemical Co., Ltd.), and the amount of V-65B was changed to 0.085 g. Thus, polymer 8 was obtained.
  • Synthesis Example 11 Polymer 11 was obtained in the same manner as in Synthesis Example 1 except that the amount of acrylic acid was changed to 50 g, the amount of methyl methacrylate was changed to 450 g, and the amount of V-65B was changed to 6.68 g in Synthesis Example 1.
  • Synthesis Example 12 A polymer 12 was obtained in the same manner as in Synthesis Example 1 except that the amount of acrylic acid was changed to 100 g, the amount of methyl methacrylate to 400 g, and the amount of V-65B to 6.90 g in Synthesis Example 1.
  • Synthesis Example 13 Polymer 13 was obtained in the same manner as in Synthesis Example 1 except that acrylic acid was changed to methacrylic acid (manufactured by Kanto Chemical Co., Inc.) and the amount of V-65B was changed to 0.083 g in Synthesis Example 2.
  • Synthesis Example 15 A polymer 15 was obtained in the same manner as in Synthesis Example 10 except that methyl methacrylate was changed to 30 g of butyl methacrylate in Synthesis Example 10.
  • Synthesis Example 16 Polymer 16 was obtained in the same manner as in Synthesis Example 8 except that ⁇ -methylene- ⁇ -valerolactone was changed to 2-ethylhexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) in Synthesis Example 8.
  • Synthesis Example 17 Polymer 17 was obtained in the same manner as in Synthesis Example 9 except that 20 g of itaconic acid in Synthesis Example 9 and 30 g of methyl methacrylate were changed to 30 g of ethyl methacrylate and the amount of initiator was changed to 0.26 g.
  • Synthesis Example 18 Polymer 18 was obtained in the same manner as in Synthesis Example 2 except that the amount of acrylic acid was changed to 6.25 g, the amount of methyl methacrylate was changed to 18.75 g, and the amount of V-65B was changed to 0.085 g in Synthesis Example 2.
  • Synthesis Example 19 Polymer 19 was obtained in the same manner as in Synthesis Example 2 except that the amount of acrylic acid was changed to 11.25 g, the amount of methyl methacrylate was changed to 13.75 g, and the amount of V-65B was changed to 0.091 g in Synthesis Example 2.
  • the weight average molecular weight, the glass transition temperature, the composition ratio (mass ratio) of the hydrophilic monomer unit and the hydrophobic monomer unit in the copolymer are collectively shown for the polymers 1 to 21 obtained by synthesis in Synthesis Examples 1 to 21. It is shown in 1.
  • the resulting polymer 22 had a weight average molecular weight of 94200 and a glass transition temperature of 114 ° C.
  • the acrylic acid unit content in the polymer was 33% by mass, and the methyl methacrylate unit content was 67% by mass.
  • Examples 1 to 15 and Comparative Examples 1 to 7 The polymers 1 to 20 and 22 obtained in the above synthesis examples were evaluated for solubility in an alkaline aqueous solution by the following method.
  • sample adjustment method of a commercial item is as follows.
  • Dissolution rate ((polymer weight before dissolution ⁇ polymer weight remaining undissolved) / polymer weight before dissolution) ⁇ 100
  • Example 16 The polymer 1 was processed into a filament having a diameter of 1.5 mm at a melting temperature of 195 ° C. and an extrusion speed of 75 mm / min using a capillograph (Capigraph 1D manufactured by Toyo Seiki Seisakusho). Using this filament, the dissolution rate was similarly measured and found to be 94%.
  • Comparative Example 8 When the filament-like commercially available support material evaluated in Comparative Example 6 was not pulverized with a coffee mill and remained in the form of a filament, the dissolution rate was measured in the same manner to be 3%.
  • Example 17 [Dissolution rate of support material containing elastomer]
  • Example 17 Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) obtained by dehydrating 19.76 g of diethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 84.39 g of 2-ethyl-2-oxazoline (manufactured by PCI Corporation) in a 2 L 4-neck flask equipped with a reflux tube. ) was dissolved in 211.46 g and heated to reflux for 8 hours under a nitrogen atmosphere to synthesize terminal-reactive poly (N-propionylethyleneimine) (polyoxazoline).
  • a calibration curve was prepared from standard polystyrene using the GPC method under the following conditions, and the weight average molecular weight (Mw) was 1050.
  • Mw weight average molecular weight
  • a 33% ethyl acetate solution of 307.50 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8003, manufactured by Shin-Etsu Silicone) was added all at once and heated to reflux for 10 hours.
  • the reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery semisolid (elastomer).
  • the content of the organopolysiloxane segments of the final product was 76% by mass determined by 1 H NMR measurement.
  • As a result of neutralization titration with hydrochloric acid using methanol as a solvent it was found that 20% by mass of amino groups remained.
  • the filament After irradiating with ultrasonic waves for a predetermined time shown in Table 4, the filament is taken out, wiped off with a paper towel, and then held by the hand at the center of the filament 90 ° back and forth at intervals of once per second. And the filament was broken. At this time, the number of times until the filament broke was measured, and the average value at the time of measurement of five was calculated to be the number of times of bending test breakage. The smaller this value, the greater the damage to the filament. In the molding material not treated with the cleaning agent, the number of breaks in the bending test was 36. P400SC was a 2.4% aqueous solution, and magicrin was used for the test without diluting the stock solution. The evaluation results are shown in Table 4.
  • Example 19 Filaments prepared by polymer 6 in the same manner as in Example 15 were supplied to an Atom 3D Printer manufactured by Genkei, and extruded from a heat nozzle having a temperature of 230 ° C. to perform molding.
  • the extruded polymer 1 creates a support having a width of about 0.4 mm and a height (slice interval) of about 0.25 mm, and continues to form a shaped object on the support.
  • a model was made from an ABS resin having a glass transition temperature of 104 ° C. The support was laminated, and the shape (ABS thermoplastic resin) was kept on the support (polymer 1) without slipping.
  • plasticizer (Examples 20 to 25)
  • plasticizers Daifati 101 (Methyl diglycol adipate / benzyl alcohol 1: 1 mixed ester, manufactured by Daihachi Chemical Industry Co., Ltd., sp value 10.0) and Ecola A1010 (methyl triglycol disuccinate, manufactured by Kao Corporation) , Sp value 9.57)
  • polymer 1 SP value 10.3 100 g obtained in Synthesis Example 1 and a melt kneader (Labo Plasmill 4C150 manufactured by Toyo Seiki Seisakusho Co., Ltd.), conditions of 190 ° C. and 90 r / min For 10 minutes.
  • press molding (laboratory press P2-30T manufactured by Toyo Seiki Seisakusho Co., Ltd.) is performed at 190 ° C. to form a film (thickness 0.4 mm), and the compatibility between the polymer and the plasticizer and the plasticizer are visually observed. The bleed-out was judged. When the film was transparent, it was determined that it was compatible, and when it was cloudy, it was determined that it was not compatible. The bleed-out of the plasticizer was determined by the presence or absence of wetting of the film surface. Table 5 shows the amounts of plasticizer blended and the evaluation results. A transparent resin was obtained by adding any plasticizer, and no bleed-out of the plasticizer was confirmed.

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Abstract

La présente invention concerne un matériau soluble destiné à un moulage tridimensionnel et utilisé en tant que matériau pour un matériau de support qui supporte un objet tridimensionnel lorsque ledit objet tridimensionnel est produit par une imprimante 3D de modelage par dépôt en fusion. Le matériau soluble destiné à un moulage tridimensionnel comprend au moins un copolymère comprenant un motif monomère hydrophile spécifique et un motif monomère hydrophobe spécifique. La présente invention présente une température de transition vitreuse appropriée pour le procédé FDM, présente un taux de dissolution élevé dans une solution aqueuse alcaline, peut être enlevée rapidement d'un précurseur d'un objet tridimensionnel et permet de réduire au minimum ou de réduire l'endommagement à un objet tridimensionnel.
PCT/JP2015/078113 2014-10-14 2015-10-02 Matériau soluble destiné à un moulage tridimensionnel WO2016059987A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP15850615.4A EP3208073B1 (fr) 2014-10-14 2015-10-02 Matériau soluble destiné à un moulage tridimensionnel
US15/518,812 US10738142B2 (en) 2014-10-14 2015-10-02 Soluble material for three-dimensional molding
CN201580044372.7A CN106660266B (zh) 2014-10-14 2015-10-02 三维造型用可溶性材料

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JP2014210080 2014-10-14
JP2014-210080 2014-10-14
JP2014250054A JP6491467B2 (ja) 2014-10-14 2014-12-10 三次元造形用可溶性材料
JP2014-250054 2014-12-10

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WO2016059987A1 true WO2016059987A1 (fr) 2016-04-21

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WO2017199324A1 (fr) * 2016-05-17 2017-11-23 花王株式会社 Composition d'agent de traitement pour précurseur d'objet tridimensionnel
WO2017199323A1 (fr) * 2016-05-17 2017-11-23 花王株式会社 Composition d'agent de traitement pour précurseur d'objet tridimensionnel
CN108349157A (zh) * 2016-08-26 2018-07-31 瓦克化学股份公司 生产成型体的方法

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WO2017199324A1 (fr) * 2016-05-17 2017-11-23 花王株式会社 Composition d'agent de traitement pour précurseur d'objet tridimensionnel
WO2017199323A1 (fr) * 2016-05-17 2017-11-23 花王株式会社 Composition d'agent de traitement pour précurseur d'objet tridimensionnel
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JPWO2017199324A1 (ja) * 2016-05-17 2019-03-22 花王株式会社 三次元物体前駆体処理剤組成物
CN109153187B (zh) * 2016-05-17 2021-04-30 花王株式会社 三维物体前体处理剂组合物
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CN108349157A (zh) * 2016-08-26 2018-07-31 瓦克化学股份公司 生产成型体的方法
CN108349157B (zh) * 2016-08-26 2020-03-27 瓦克化学股份公司 生产成型体的方法

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