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WO2018025703A1 - Procédé de production d'un matériau fusible destiné à un moulage tridimensionnel - Google Patents

Procédé de production d'un matériau fusible destiné à un moulage tridimensionnel Download PDF

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Publication number
WO2018025703A1
WO2018025703A1 PCT/JP2017/026820 JP2017026820W WO2018025703A1 WO 2018025703 A1 WO2018025703 A1 WO 2018025703A1 JP 2017026820 W JP2017026820 W JP 2017026820W WO 2018025703 A1 WO2018025703 A1 WO 2018025703A1
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WO
WIPO (PCT)
Prior art keywords
soluble material
preferable
mol
dimensional modeling
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/026820
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English (en)
Japanese (ja)
Inventor
智也 坪井
丈士 平井
拓馬 木村
吉村　忠徳
昭弘 尾之上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017141058A external-priority patent/JP2018024849A/ja
Application filed by Kao Corp filed Critical Kao Corp
Priority to CN201780048859.1A priority Critical patent/CN109562534A/zh
Priority to US16/323,453 priority patent/US20190168447A1/en
Priority to EP17836809.8A priority patent/EP3495108A4/fr
Publication of WO2018025703A1 publication Critical patent/WO2018025703A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a method for producing a soluble material for three-dimensional modeling that is used as a support material for supporting a three-dimensional object when the three-dimensional object is produced by a 3D printer, in particular, 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.
  • 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 target three-dimensional object can be obtained (for example, JP-T-2008-507619).
  • the manufacturing method of the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a material for a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer.
  • a method for producing a material wherein the ratio of the length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is 0.20 ⁇ K / L ⁇
  • the three-dimensional modeling soluble material used as a support material for supporting the three-dimensional object is provided in the form of a filament wound around a supply reel, and is supplied from the supply reel to a hot melt lamination type 3D printer.
  • the filamentous three-dimensional modeling soluble material has a problem that it is easily broken when it is wound around the supply reel or when it is supplied to a 3D printer.
  • the present invention provides a method for producing a soluble material for three-dimensional modeling that has excellent mechanical properties and is difficult to break even when a filament is used.
  • the manufacturing method of the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a material for a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer.
  • a method for producing a material wherein the ratio of the length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is 0.20 ⁇ K / L ⁇
  • the manufacturing method of the soluble material for 3D modeling of the present embodiment is for 3D modeling used as a material for a support material that supports the 3D object when the 3D object is manufactured by a hot melt lamination type 3D printer.
  • a method for producing a soluble material wherein the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is 0.20 ⁇ K /
  • a base polymer having a kneading step of kneading with a screw configuration satisfying L ⁇ 0.70, wherein the temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is included in the raw material of the three-dimensional modeling soluble material Tg + 80 (° C.) ⁇ Tmix ⁇ Tg + 200 (° C.) with respect to the glass transition temperature Tg.
  • the manufacturing method of the soluble material for three-dimensional modeling of the present embodiment it is possible to provide a soluble material for three-dimensional modeling that is excellent in mechanical properties and is not easily broken even by a filament.
  • the reason why the manufacturing method of the soluble material for three-dimensional modeling of the present embodiment has such an effect is not clear, but is considered as follows.
  • an elastomer may be used as a raw material for the three-dimensional modeling soluble material. Even if the elastomer is included in the three-dimensional modeling soluble material, The effect of is difficult to obtain. This is because the elastomer is poorly compatible with the base polymer that is the base material of the three-dimensional modeling soluble material, so that even if a compatibilizer is used, the elastomer is sufficiently dispersed in the three-dimensional modeling soluble material. It is speculated that not.
  • the elastomer is sufficiently dispersed in the three-dimensional modeling soluble material, so that the design effect by the elastomer is obtained and the toughness is improved. It is considered that it is possible to provide a soluble material for three-dimensional modeling that is excellent in mechanical properties and is not easily broken even by a filament.
  • the raw material of the three-dimensional modeling soluble material includes a base polymer of the three-dimensional modeling soluble material, a compatibilizing agent, and an elastomer.
  • the base polymer of the three-dimensional modeling soluble material can be used without particular limitation as long as it is used as the base polymer of the three-dimensional modeling soluble material in the conventional FDM type three-dimensional object manufacturing method.
  • the base polymer include polyvinyl alcohol, polyoxazoline, polyacrylamide, acrylate (co) polymer, methacrylate (co) polymer, polyester resin, polyamide resin, and methacrylic resin.
  • the base polymer of the three-dimensional modeling soluble material is preferably a resin having a hydrophilic group that can be removed by neutral water having a pH of 6 to 8, which is not a strong alkaline aqueous solution.
  • a modeling material having high heat resistance has a high melting point, but the temperature when the modeling material is heated / melted and extruded and laminated by a 3D printer is significantly different from the temperature of the support material in contact with the modeling material. The accuracy of 3D objects may be impaired. Therefore, when a modeling material having a high melting point is heated / melted and extruded and laminated by a 3D printer, the three-dimensional modeling soluble material, which is a material of the support material, is also heated / melted and extruded to a temperature close to the temperature of the modeling material for lamination. To do. In such a case, a three-dimensional modeling soluble material that is a support material that can be removed by neutral water having a pH of 6 to 8 that is not a strong alkaline aqueous solution also preferably has a high melting point.
  • polyester resin having a hydrophilic group (Polyester resin having a hydrophilic group)
  • a polyester resin in which the ratio of the hydrophilic monomer unit A 1 to the total of the acid monomer units B 1 is 10 to 70 mol% can be exemplified.
  • the polyester resin has a hydrophilic monomer unit A 1 having a hydrophilic group.
  • the hydrophilic monomer unit A 1 is not particularly limited as long as the monomer unit having a hydrophilic group.
  • the monomer to induce the hydrophilic monomer unit A 1 is also referred to as a monomer A 1.
  • the hydrophilic group includes a primary amino group, a secondary amino group, a tertiary amino group, from the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of the polyester resin.
  • examples thereof include at least one selected from the group consisting of a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, a phosphate group, a phosphate group, a sulfonate group, and a sulfonate group.
  • the secondary amino group is —NHR 1 group (where R 1 is linear or branched, from the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of the polyester resin. At least one selected from the group consisting of a secondary amino group represented by (II) and a secondary amino group represented by —NH— group.
  • the tertiary amino group is a —NR 2 R 3 group (provided that R 2 is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester resin.
  • Jo of represents a number 1 to 14 alkyl group carbon
  • R 3 is a tertiary amino group represented by denotes a straight or branched carbon atoms 1 to 14 alkyl group.
  • -NR At least one selected from the group consisting of tertiary amino groups represented by a 4- group (wherein R 4 represents a linear or branched alkyl group having 1 to 14 carbon atoms) is preferred. .
  • the quaternary ammonium base is —N + ⁇ R 5 R 6 R 7 ⁇ ⁇ X ⁇ (where, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester resin.
  • R 5 , R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms
  • X ⁇ represents a hydroxy ion, a halogen ion, CH 3 SO 4 — or CH 3 CH 2 SO. 4 - at least one or more preferably selected from the group consisting of quaternary ammonium base represented by the illustrated).
  • the oxyethylene group is — ⁇ CH 2 CH 2 O ⁇ n1 — (where n1 represents an average number) from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester resin.
  • R 8 is Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 2 or more and 6 or less, and further preferably 3 or more and 5 or less. At least one selected from the group consisting of down group.
  • the carboxyl base is —COOM 1 (where M 1 represents a counter ion of the carboxyl group constituting the carboxyl base.
  • M 1 represents a counter ion of the carboxyl group constituting the carboxyl base.
  • Carboxyl base is preferably represented by Ri.
  • the phosphate group is —PO 4 M 2 2 , —PO 4 HM 2 , and —PO 4 M 2.
  • M 2 represents a counter ion of a phosphate group constituting a phosphate group, and from the viewpoint of solubility in neutral water, sodium ion, potassium ion, lithium ion, calcium ion, magnesium ion, ammonium ion, barium.
  • At least one selected from the group consisting of ions and zinc ions more preferably at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions, sodium ions, And at least one selected from the group consisting of potassium ions is more preferred.
  • the sodium ion is more preferable and more.
  • the sulfonate group is —SO 3 M 3 (where M 3 is a sulfonic acid constituting the sulfonate group).
  • M 3 is a sulfonic acid constituting the sulfonate group.
  • at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions and more preferably at least one selected from the group consisting of sodium ions and potassium ions.
  • More preferably, more sodium ions Sulfonate group is preferably represented by the preferred.) To.
  • the monomer A 1 At least one selected from the group consisting of acids, amines and amino acids is preferred, and carboxylic acids are more preferred.
  • carboxylic acids aromatic carboxylic acids are preferable from the same viewpoint, and hydroxy group-containing aromatic dicarboxylic acid, primary amino group-containing aromatic dicarboxylic acid, sulfonic acid group-containing aromatic dicarboxylic acid, and sulfonate group-containing At least one selected from the group consisting of aromatic dicarboxylic acids is more preferable.
  • 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6- At least one selected from the group consisting of naphthalenedicarboxylic acid is preferable, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is more preferable.
  • the content of the hydrophilic group in the polyester resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0.7 mmol / g or more. Is more preferable, and from the viewpoint of moisture absorption resistance, 3.0 mmol / g or less is preferable, 2.0 mmol / g or less is more preferable, and 1.5 mmol / g or less is still more preferable.
  • the content of the hydrophilic group in the polyester resin is preferably 0.5 to 3.0 mmol / g from the viewpoint of solubility in neutral water and moisture absorption resistance, and is preferably 0.6 to 2.0 mmol / g is more preferable, and 0.7 to 1.5 mmol / g is more preferable.
  • the proportion of a substance amount of the hydrophilic monomer unit A 1 is from the standpoint of solubility in neutral water, not less than 5 mol%, more than 7 mol%
  • 10 mol% or more is more preferable
  • 12 mol% or more is more preferable
  • it is 35 mol% or less, preferably 33 mol% or less, more preferably 32 mol% or less, and further preferably 30 mol% or less.
  • the proportion of a substance amount of the hydrophilic monomer unit A 1 is preferably 5 - 35 mol% from the viewpoint of solubility in neutral water, 7 ⁇ 33 mol% is more preferable, 10 to 32 mol% is still more preferable, 12 to 30 mol% is still more preferable, and 8 to 13 mol% is still more preferable from the viewpoint of solubility in neutral water and moisture absorption resistance.
  • the polyester resin has a hydrophobic dicarboxylic acid monomer units B 1.
  • the dicarboxylic acid monomer units B 1 represents no said hydrophilic groups.
  • the dicarboxylic acid to induce the hydrophobic dicarboxylic acid monomer units B 1 is also referred to as a dicarboxylic acid B 1.
  • the dicarboxylic acid B 1 is not particularly limited as long as it is a dicarboxylic acid, but from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, from the viewpoint of heat resistance required for modeling by a 3D printer, and when producing a polyester resin From the viewpoint of the ease of the polymerization reaction, at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids is preferred.
  • the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid At least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable.
  • the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B 1 of the polyester resin from the viewpoint of moisture resistance, or 15 mol% are preferred, 18 mol % Or more is more preferable, 20 mol% or more is more preferable, and from the viewpoint of solubility in neutral water, 45 mol% or less is preferable, 42 mol% or less is more preferable, and 40 mol% or less is more preferable.
  • the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B 1 of the polyester resin is, the moisture absorption resistance viewpoint, and to neutral water From the viewpoint of solubility, it is preferably 15 to 45 mol%, more preferably 20 to 42 mol%, still more preferably 30 to 40 mol%.
  • the molar ratio of the hydrophilic monomer unit A 1 to the hydrophobic dicarboxylic acid monomer unit B 1 is determined based on solubility in water and resistance to neutral water.
  • 10/90 or more is preferable, 15/85 or more is more preferable, 18/82 or more is more preferable, 20/80 or more is more preferable, and the same
  • 70/30 or less is preferable, 65/35 or less is more preferable, 60/40 or less is more preferable, 40/60 or less is still more preferable, and 26/74 or less is even more preferable.
  • the polyester resin has a diol monomer unit.
  • the diol for deriving the diol monomer unit is also referred to as diol C.
  • the diol C is not particularly limited, and aliphatic diols, aromatic diols, and the like can be used, but aliphatic diols are preferable from the viewpoint of the production cost of the polyester resin.
  • the number of carbon atoms of the diol C is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable, 25 The following is more preferable, 20 or less is further preferable, and 15 or less is more preferable.
  • Examples of the aliphatic diol include at least one selected from the group consisting of a chain diol and a cyclic diol, and are required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer. From the viewpoint of toughness (strength), a chain diol is preferred.
  • the number of carbon atoms of the chain diol is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 6 or less is preferable. 4 or less is more preferable, and 3 or less is more preferable.
  • the number of carbon atoms of the cyclic diol is preferably 6 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable. 30 or less is more preferable, and 27 or less is more preferable.
  • the diol C may have ether oxygen.
  • the diol C is a chain aliphatic diol, it is required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer.
  • the number of ether oxygens is preferably 1 or less, and when the diol C is a cycloaliphatic diol, the number of ether oxygens is preferably 2 or less from the same viewpoint.
  • the chain diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. And preferably at least one selected from the group consisting of dipropylene glycol, more preferably at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, and 1,3-propanediol.
  • diethylene glycol and dipropylene glycol may be charged as a raw material for the polymerization reaction, or may be by-produced during the polymerization reaction.
  • the ratio of the diethylene glycol unit to the total of all diol monomer units in the polyester resin is the solubility in neutral water, moisture absorption resistance, and the heat resistance required for modeling by a 3D printer. From the viewpoint, 5 mol% or more is preferable, 10 mol% or more is more preferable, 15 mol% or more is further preferable, 20 mol% or more is further preferable, 25 mol% or more is further more preferable, 30 mol% or more is more preferable, and 60 mol%. The following is preferable, 55 mol% or less is more preferable, 50 mol% or less is more preferable, and 45 mol% or less is still more preferable.
  • the cyclic diol is composed of 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. At least one selected from the group consisting of bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is preferred.
  • Diol C is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, bisque
  • the total proportion of loulene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is 80 mol% or more from the viewpoints of solubility in neutral water, moisture absorption resistance,
  • the polyester resin is solubility in neutral water, moisture absorption resistance, and a heat-resistant viewpoint required for shaping by 3D printers, to the total of all the dicarboxylic acid monomer units containing the hydrophilic monomer unit A 1, wherein the proportion of hydrophilic monomer units a 1, and the ratio of the dicarboxylic acid monomer units B 1 is, 10 ⁇ 70 mol%, respectively, and a 30 ⁇ 90 mol%, dicarboxylic acids for obtaining the dicarboxylic acid monomer units B 1 B 1 Polyester resin ⁇ in which is 2,6-naphthalenedicarboxylic acid is preferred.
  • polyester resin alpha to the total of all the dicarboxylic acid monomer units containing the hydrophilic monomer unit A 1, the ratio of the hydrophilic monomer unit A 1 is solubility in neutral water, moisture absorption resistance, and 3D printer From the viewpoint of the heat resistance required for modeling according to the above, 10 mol% or more is preferable, 20 mol% or more is more preferable, and from the same viewpoint, 70 mol% or less is preferable, 65 mol% or less is more preferable, 60 mol% or less is more preferable, 40 mol % Or less is still more preferable, and 27 mol% or less is still more preferable.
  • the ratio of the dicarboxylic acid monomer unit B 1 to the total of all dicarboxylic acid monomer units including the hydrophilic monomer unit A 1 in the polyester resin ⁇ is determined by solubility in neutral water, moisture absorption resistance, and 3D printer. From the viewpoint of the heat resistance required for modeling by, preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 65 mol% or more, still more preferably 73 mol% or more, the same viewpoint Therefore, 90 mol% or less is preferable, and 80 mol% or less is more preferable.
  • the monomer A 1 contains 5-sulfoisophthalic acid and 2-sulfoisophthalic acid from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer.
  • at least one selected from the group consisting of: 5-sulfoisophthalic acid is more preferable.
  • the diol C in the polyester resin ⁇ is ethylene glycol, 1,2-propanediol, diethylene glycol, 1 from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. At least one selected from the group consisting of 1,3-propanediol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene.
  • More than one species preferably a group consisting of ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene Ri least one and more preferably be selected.
  • the polyester resin ⁇ can be exemplified by the following general formulas (1) and (2).
  • p1 represents the polymerization degree of ethylene 2,6-naphthalene dicarboxylate
  • q1 represents the number of polymerization degrees of ethylene 5-sulfoisophthalate, where ethylene 2,6-naphthalene dicarboxylate And ethylene 5-sulfoisophthalate are block bonds and / or random bonds, and a random bond is more preferable from the viewpoint of solubility in neutral water.
  • p2 is the degree of polymerization of ethylene 2,6-naphthalenedicarboxylate
  • q2 is the degree of polymerization of ethylene 5-sulfoisophthalate
  • r2 is the amount of bisphenoxyethanol fluorene and 2,6-naphthalenedicarboxylic acid.
  • the degree of polymerization of the condensate, s2 represents the number of degrees of polymerization of the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid, provided that ethylene 2,6-naphthalenedicarboxylate, ethylene 5-sulfoisophthalate, bisphenoxyethanol
  • the condensate of fluorene and 2,6-naphthalenedicarboxylic acid, the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid are block bonds and / or random bonds, and are randomly bonded from the viewpoint of solubility in neutral water. Is more preferred.
  • the polyester resin may have a monomer unit other than the hydrophilic monomer unit A 1 , the dicarboxylic acid monomer unit B 1 , and the diol monomer unit as long as the effects of the present embodiment are not impaired.
  • the method for producing the polyester resin is not particularly limited, and a conventionally known method for producing a polyester resin can be applied.
  • the polyamide resin has a hydrophilic monomer unit A 2 having a hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B 2 , and a hydrophobic diamine monomer unit, and the hydrophilicity relative to the total of all monomer units in the polyamide resin.
  • polyamide resin proportion of sexual monomer unit a 2 is 2.5 ⁇ 40 mol% can be exemplified.
  • the polyamide resin has a hydrophilic monomer unit A 2 having a hydrophilic group.
  • the hydrophilic monomer unit A 2 is not particularly limited as long as the monomer unit having a hydrophilic group.
  • the monomer to induce the hydrophilic monomer unit A 2 is also referred to as monomer A 2.
  • the hydrophilic group includes a primary amino group, a secondary amino group, a tertiary amino group, from the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyamide resin.
  • examples thereof include at least one selected from the group consisting of a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, a phosphate group, a phosphate group, a sulfonate group, and a sulfonate group.
  • the secondary amino group is a —NHR 9 group (where R 9 is a linear or branched group). At least one selected from the group consisting of a secondary amino group represented by (II) and a secondary amino group represented by —NH— group.
  • the tertiary amino group is a —NR 10 R 11 group (provided that R 10 is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin.
  • a tertiary amino group having a carbon number of 1 to 14 and R 11 represents a linear or branched alkyl group having a carbon number of 1 to 14), and —NR At least one selected from the group consisting of a tertiary amino group represented by a 12 -group (wherein R 12 represents a linear or branched alkyl group having 1 to 14 carbon atoms) is preferred. .
  • the quaternary ammonium base is —N + ⁇ R 13 R 14 R 15 ⁇ ⁇ X ⁇ (where, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin.
  • R 13 , R 14 and R 15 each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms
  • X ⁇ represents a hydroxy ion, a halogen ion, CH 3 SO 4 — or CH 3 CH 2 SO. 4 - at least one or more preferably selected from the group consisting of quaternary ammonium base represented by the illustrated).
  • the oxyethylene group is — ⁇ CH 2 CH 2 O ⁇ n2 — (where n2 represents an average number) from the viewpoint of solubility in neutral water and the ease of polymerization reaction during the production of polyamide resin.
  • R 16 is 4 or more and 50 or less
  • the carboxyl base is —COOM 4 (where M 4 represents a counter ion of the carboxyl group constituting the carboxyl base, from the viewpoint of solubility in neutral water and the ease of the polymerization reaction during the production of the polyamide resin.
  • At least one selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium ions, magnesium ions, ammonium ions, barium ions, and zinc ions is preferable, sodium More preferably, at least one selected from the group consisting of ions, potassium ions, lithium ions, magnesium ions, and ammonium ions, more preferably at least one selected from the group consisting of sodium ions and potassium ions, sodium ions Gayo Further preferred.)
  • Carboxyl base is preferably represented by.
  • the phosphate group is, in view of the solubility in neutral water, and from the viewpoint of easiness of the polyamide resin during manufacture of the polymerization reaction, -PO 4 M 5 2, -PO 4 HM 5, and -PO 4 M 5 (However, M 5 represents a counter ion of the phosphate groups constituting the phosphoric acid salt, sodium from the viewpoint of solubility in neutral water ions, potassium ions, lithium ions, calcium ions, magnesium ions, ammonium ions, barium
  • At least one selected from the group consisting of potassium ions is more preferred.
  • Ku at least one or more preferably sodium ion is selected from the group consisting of phosphoric acid base represented by even more preferred.).
  • the sulfonate group is —SO 3 M 6 (where M 6 is a sulfonic acid constituting the sulfonate group).
  • M 6 is a sulfonic acid constituting the sulfonate group.
  • at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, magnesium ions, and ammonium ions and more preferably at least one selected from the group consisting of sodium ions and potassium ions. More preferably, sodium ions are more Preferred.
  • Sulfonate is preferably represented by.
  • the monomer A 2 is a carboxylic acid. At least one selected from the group consisting of acids, amines and amino acids is preferred, and carboxylic acids are more preferred.
  • carboxylic acids aromatic carboxylic acids are preferable from the same viewpoint, and hydroxy group-containing aromatic dicarboxylic acid, primary amino group-containing aromatic dicarboxylic acid, sulfonic acid group-containing aromatic dicarboxylic acid, and sulfonate group-containing Aromatic dicarboxylic acids are more preferred.
  • 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6- At least one selected from the group consisting of naphthalenedicarboxylic acid is preferable, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is more preferable.
  • the content of the hydrophilic group in the polyamide resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0.7 mmol / g or more. Is more preferable, and from the viewpoint of moisture absorption resistance, 3.0 mmol / g or less is preferable, 2.0 mmol / g or less is more preferable, and 1.5 mmol / g or less is still more preferable.
  • the content of the hydrophilic group in the polyamide resin is preferably 0.5 to 3.0 mmol / g from the viewpoint of solubility in neutral water and moisture absorption resistance, and preferably 0.6 to 2.0 mmol / g is more preferable, and 0.7 to 1.5 mmol / g is more preferable.
  • the proportion of a substance amount of the hydrophilic monomer unit A 2 from the viewpoint of solubility in neutral water, not less than 2.5 mol%, 4 mol%
  • 6 mol% or more is more preferable
  • 8 mol% or more is further preferable
  • 10 mol% or more is more preferable, and from the viewpoint of moisture absorption resistance, it is 40 mol% or less, preferably 35 mol% or less, and more preferably 31 mol% or less.
  • the ratio of the total for the substance amount of the hydrophilic monomer unit A 2 substance of the total monomer units of the polyamide resin is 2 in view of the solubility in neutral water, and in view of moisture absorption resistance. It is preferably 5 to 40 mol%, more preferably 4 to 35 mol%, still more preferably 6 to 31 mol%, still more preferably 8 to 20 mol%, still more preferably 8 to 15 mol%, and still more preferably 8 to 12 mol%.
  • the polyamide resin has a hydrophobic dicarboxylic acid monomer unit B 2.
  • the dicarboxylic acid monomer units B 2 has no the hydrophilic group.
  • the dicarboxylic acid to induce the hydrophobic dicarboxylic acid monomer units B 2 is also referred to as a dicarboxylic acid B 2.
  • the dicarboxylic acid B 2 is not particularly limited as long as it is a dicarboxylic acid, but from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, from the viewpoint of heat resistance required for modeling by a 3D printer, and at the time of producing a polyamide resin From the viewpoint of the ease of the polymerization reaction, at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids is preferred.
  • the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid More preferably, at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable, and terephthalic acid is still more preferable.
  • the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B 2 of the polyamide resin, from the viewpoint of moisture resistance preferably at least 10 mol%, 20 mol % Or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 42 mol% or more, and from the viewpoint of solubility in neutral water, 47. 5 mol% or less is preferable, 45 mol% or less is more preferable, 42 mol% or less is more preferable, and 40 mol% or less is still more preferable.
  • the proportion of the hydrophobic substance amount of the dicarboxylic acid monomer units B 2 of the polyamide resin is, the moisture absorption resistance viewpoint, and to neutral water From the viewpoint of solubility, it is preferably 10 to 47.5 mol%, more preferably 20 to 45 mol%, still more preferably 30 to 42 mol%.
  • the molar ratio of the hydrophilic monomer unit A 2 to the hydrophobic dicarboxylic acid monomer unit B 2 is determined based on solubility in neutral water and resistance to water. From the viewpoint of hygroscopicity and heat resistance required for modeling by a 3D printer, 10/90 or more is preferable, 15/85 or more is more preferable, 18/82 or more is more preferable, 20/80 or more is more preferable, and the same In view of the above, 50/50 or less is preferable, 40/60 or less is more preferable, 30/70 or less is more preferable, and 25/75 or less is even more preferable.
  • the polyamide resin has a hydrophobic diamine monomer unit.
  • the hydrophobic diamine monomer unit does not have the hydrophilic group.
  • the diamine for deriving the hydrophobic diamine monomer unit is also referred to as diamine C.
  • the diamine C is not particularly limited, and at least one selected from the group consisting of aliphatic diamines, alicyclic diamines, and aromatic diamines can be used, and the ease of the polymerization reaction during polyamide resin production. In view of the above, an aliphatic diamine is preferable.
  • the number of carbon atoms of the diamine C is from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, from the viewpoint of heat resistance required for modeling by a 3D printer, and from the viewpoint of ease of polymerization reaction when producing a polyamide resin. 2 or more, preferably 3 or more, more preferably 4 or more, from the viewpoint of solubility in neutral water, the viewpoint of moisture absorption resistance, and the heat resistance required for modeling by a 3D printer, 20 or less Is preferably 15 or less, more preferably 10 or less.
  • aliphatic diamine examples include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, and decane diamine.
  • hexamethylenediamine is preferable from the viewpoints of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer.
  • Examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine.
  • at least one selected from the group consisting of diamine cyclohexane and isophorone diamine is preferable from the viewpoint of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer. More preferred is at least one selected from the group consisting of diamine and cyclohexane.
  • aromatic diamine examples include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane.
  • phenylenediamine and diethyltoluenediamine are preferable from the viewpoints of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer.
  • phenylenediamine is more preferable.
  • the diamine C is at least selected from the group consisting of hexamethylenediamine, diaminecyclohexane, and phenylenediamine from the viewpoint of solubility in neutral water, moisture absorption resistance, and toughness (strength) required for modeling by a 3D printer.
  • One or more are preferable, at least one selected from the group consisting of hexamethylenediamine and phenylenediamine is more preferable, and hexamethylenediamine is still more preferable.
  • the diamine C is at least one selected from the group consisting of hexamethylene diamine, diamine cyclohexane, and phenylene diamine, hexamethylene diamine, diamine cyclohexane, phenylene with respect to the total amount of all diamine monomer units in the polyamide resin.
  • the total proportion of the diamine substances is preferably 50 mol% or more, more preferably 70 mol% or more, and 80 mol% from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. % Or more is more preferable, 90 mol% or more is more preferable, substantially 100 mol% is still more preferable, and 100 mol% is still more preferable.
  • substantially 100 mol% means the case where substances other than hexamethylene diamine, diamine cyclohexane, and phenylene diamine are inevitably mixed.
  • the polyamide resin can be exemplified by the following general formulas (3) to (8).
  • p3 and q3 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • p4 and q4 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • p5 and q5 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • p6 and q6 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • p7 and q7 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • p8 and q8 each represent the number of polymerization degrees. Each polymerization is a block bond and / or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water. )
  • the polyamide resin may have a monomer unit other than the monomer unit A 2 , the dicarboxylic acid monomer unit B 2 , and the hydrophobic diamine monomer unit as long as the effects of the present embodiment are not impaired.
  • the method for producing the polyamide resin is not particularly limited, and a conventionally known method for producing a polyamide resin can be applied.
  • the polyester resin and the polyamide resin can be removed by neutral water having a pH of 6 to 8 which is not a strong alkaline aqueous solution and have a high melting point, but have a hydrophilic group, so that they are used as a base polymer for a soluble material for three-dimensional modeling. There is a tendency that the compatibility with the elastomer is worse than that of a general resin used.
  • the polyester resin having the hydrophilic group and / or the polyamide resin having the hydrophilic group is used as a raw material for the soluble material for three-dimensional modeling.
  • a soluble material for three-dimensional modeling can be provided.
  • the weight average molecular weight of the base polymer is preferably 3000 or more, more preferably 3500 or more, still more preferably 4000 or more, and solubility in neutral water, from the viewpoint of improving toughness required for a soluble material for three-dimensional modeling. And 70000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 20000 or less, from the viewpoint of formability by a 3D printer.
  • a weight average molecular weight is measured by the method as described in an Example.
  • the glass transition temperature (Tg) of the base polymer is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. Therefore, it is 250 ° C. or lower, preferably 220 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 160 ° C. or lower, still more preferably 140 ° C. or lower, and still more preferably 120 ° C. or lower.
  • a glass transition temperature is measured by the method as described in an Example.
  • the melt flow rate of the base polymer is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and 2.5 g / min. 10 g or more is more preferable, and from the viewpoint of resin toughness, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is further preferable, and 5 g / 10 min or less is even more preferable.
  • the melt flow rate is measured by the method described in the examples.
  • the blending ratio of the base polymer is preferably 70% by mass or more and more preferably 80% by mass or more in the soluble material for three-dimensional modeling from the viewpoint of modeling by a 3D printer.
  • the blending ratio of the base polymer is preferably 95% by mass or less, more preferably 90% by mass or less, in the soluble material for three-dimensional modeling.
  • the compatibilizer can be used without particular limitation as long as it is a compatibilizer used for the three-dimensional modeling soluble material according to the FDM method. From the viewpoint of improving toughness, a compatibilizing agent containing at least one reactive group selected from the group consisting of an epoxy group, an acid anhydride group, an isocyanate group, an amino group, a carboxyl group, and an oxazoline group is preferable. A reactive compatibilizing agent having is more preferred.
  • Examples of reactive compatibilizers having an epoxy group include Bondfast (registered trademark) 7B, Bondfast 7M (manufactured by Sumitomo Chemical Co., Ltd.), Rotada (registered trademark) AX8840 (manufactured by Akema), JONCRYL (registered trademark) ADR4370S, JONCRYL Examples include ADR4368CS, JONCRYL ADR4368F, JONCRYL ADR4300S (above, manufactured by BASF), ARUFON (registered trademark) UG4035, ARUFON UG4040, ARUFON UG4070 (above, manufactured by Toagosei Co., Ltd.).
  • a reactive compatibilizing agent having an acid anhydride group As a reactive compatibilizing agent having an acid anhydride group, Yumex (registered trademark) 1010 (manufactured by Sanyo Chemical Co., Ltd.), Admer (registered trademark) (manufactured by Mitsui Chemicals), Modiper (registered trademark) A8200 (manufactured by NOF Corporation) ), OREVAC (registered trademark) (manufactured by Arkema), FG1901, FG1924 (above, Kraton Polymer), Tuftec (registered trademark) M1911, Tuftec M1913, and Tuftec M1943 (above, manufactured by Asahi Kasei Chemicals).
  • Examples of the reactive compatibilizer having an isocyanate group include “Carbodilite LA-1 (registered trademark)” manufactured by Nisshinbo.
  • the blending ratio of the compatibilizing agent is preferably 2 parts by mass or more and more preferably 3 parts by mass or more with respect to 100 parts by mass of the base polymer from the viewpoint of the formability by a 3D printer.
  • the blending ratio of the compatibilizer is preferably 20 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of the base polymer.
  • the elastomer can be used without particular limitation as long as it is an elastomer used for a three-dimensional modeling soluble material according to the FDM method, but a viewpoint of modeling by a 3D printer and a viewpoint of improving toughness of the three-dimensional modeling soluble material. Therefore, at least one selected from the group consisting of acrylic elastomers, olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and silicone elastomers is preferred, and acrylic elastomers are more preferred.
  • acrylic elastomer examples include Clarity (registered trademark) LA2250, Clarity LA2140, and Clarity LA4285 (above, manufactured by Kuraray Co., Ltd.).
  • olefin elastomer examples include Kraton (registered trademark) ERS polymer (manufactured by Kraton Polymer Co., Ltd.).
  • styrenic elastomer examples include Kraton A polymer, Kraton G polymer (manufactured by Kraton Polymer Co., Ltd.), “Tuftec H” series, “Tuftec P” series (produced by Asahi Kasei Chemicals), Septon (registered trademark), and Hibler (registered). Trademark) (Kuraray Plastics, Inc.).
  • the blending ratio of the elastomer is preferably 5 parts by mass or more and more preferably 10 parts by mass or more with respect to 100 parts by mass of the base polymer from the viewpoint of the formability by a 3D printer.
  • the blending ratio of the elastomer is preferably 40 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the base polymer.
  • the raw material of the three-dimensional object precursor treating agent composition is water, a water-soluble organic solvent, a filler, a thickener, a pH adjuster, a preservative, as necessary, as long as the effects of the present embodiment are not impaired. Rust preventives, pigments, colorants and the like may be included.
  • the ratio of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is A kneading step of kneading with a screw configuration satisfying 0.20 ⁇ K / L ⁇ 0.70.
  • the effective screw means a screw having functions such as conveying, shearing, and compressing powder, and includes a kneading disk.
  • the total length L of the effective screw means the total length of the screw having functions such as conveying, shearing, and compressing powder, and specifically, the length from the hopper to the tip of the screw.
  • the total length of the kneading disc refers to the total length of the kneading disc in the axial direction.
  • the method of supplying the raw material of the three-dimensional modeling soluble material to the twin-screw extruder is not particularly limited, and a method of supplying the raw material mixed in advance to the twin-screw extruder by a feeder, The method of supplying to a screw extruder is mentioned.
  • the shape of the raw material of the three-dimensional modeling soluble material supplied to the twin-screw extruder may be any of powder, fine particles, flakes, and pellets.
  • the screw constitutes a kneading element by combining a screw-like full flight screw portion and a kneading disc portion which are feed portions.
  • Examples of the shape of the kneading disk include a forward twist type, a reverse twist type, an orthogonal type, and a neutral type.
  • Other parts including the full flight screw include a forward lead, a reverse lead, a seal ring, a pineapple screw, and the like.
  • the arrangement of the full flight screw and the kneading disk is not particularly limited.
  • the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material for the three-dimensional modeling soluble material is 0. Greater than .20, preferably greater than 0.25, more preferably greater than 0.30. From the viewpoint of production efficiency, the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the three-dimensional modeling soluble material is 0.70.
  • the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin screw extruder for kneading the raw material of the three-dimensional modeling soluble material is the viewpoint of the dispersibility of the elastomer, From the viewpoint of production efficiency, 0.20 ⁇ (K / L) ⁇ 0.70, preferably 0.25 ⁇ (K / L) ⁇ 0.60, and more preferably 0.30 ⁇ (K /L) ⁇ 0.5, and more preferably 0.30 ⁇ (K / L) ⁇ 0.4.
  • the ratio (L / D) of the effective screw overall length L to the screw diameter D of the twin screw extruder for kneading the three-dimensional modeling soluble material is larger than 25, preferably from the viewpoint of improving the dispersibility of the elastomer. Greater than 27, more preferably greater than 30.
  • the ratio (L / D) of the effective screw overall length L to the screw diameter D of the twin screw extruder for kneading the raw material for the three-dimensional modeling soluble material suppresses the decomposition and deterioration of the raw material for the three-dimensional modeling soluble material. From this viewpoint, it is preferably smaller than 120, more preferably smaller than 100, and still more preferably smaller than 80.
  • the ratio (L / D) of the effective screw total length L to the screw diameter D of the twin-screw extruder for kneading the raw material of the soluble material for three-dimensional modeling is the viewpoint of improving the dispersibility of the elastomer, and the three-dimensional modeling. 25 ⁇ (L / D), 25 ⁇ (L / D) ⁇ 120 is preferable, and 27 ⁇ (L / D) ⁇ 100 is more preferable, from the viewpoint of suppressing decomposition and deterioration of the raw material of the soluble material More preferably, 30 ⁇ (L / D) ⁇ 80.
  • the temperature Tmix of the three-dimensional modeling soluble material in the kneading step is based on the glass transition temperature Tg of the base polymer contained in the three-dimensional modeling soluble material. Greater than Tg + 80 (° C.), preferably greater than Tg + 90 (° C.), more preferably greater than Tg + 100 (° C.), even more preferably greater than Tg + 110 (° C.), even more preferably greater than Tg + 120 (° C.), even more preferably Is greater than Tg + 130 (° C.).
  • the temperature Tmix of the raw material of the three-dimensional modeling soluble material in the kneading step is a base included in the raw material of the three-dimensional modeling soluble material from the viewpoint of suppressing decomposition and deterioration of the raw material of the three-dimensional modeling soluble material. It is smaller than Tg + 200 (° C.), preferably smaller than Tg + 190 (° C.), more preferably smaller than Tg + 180 (° C.), and still more preferably smaller than Tg + 170 (° C.) with respect to the glass transition temperature Tg of the polymer.
  • the temperature Tmix of the raw material of the soluble material for three-dimensional modeling in the kneading step is the third order from the viewpoint of improving the dispersibility of the elastomer and suppressing the decomposition and deterioration of the raw material of the soluble material for three-dimensional modeling.
  • the glass transition temperature (Tg) of the three-dimensional modeling soluble material is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. More preferably, from the same viewpoint, 250 ° C or lower is preferable, 220 ° C or lower is more preferable, 180 ° C or lower is further preferable, 160 ° C or lower is further preferable, 140 ° C or lower is further preferable, and 120 ° C or lower is still higher. preferable.
  • the melt flow rate of the three-dimensional modeling soluble material is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, 2.5 g / 10 min or more is more preferable, and from the viewpoint of resin toughness, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is further preferable, and 5 g / 10 min or less is even more preferable.
  • the average particle size of the elastomer in the three-dimensional modeling soluble material is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and further preferably 1.7 ⁇ m or less. Preferably, 1.4 ⁇ m or less is even more preferable.
  • the average particle diameter of the elastomer in the soluble material for three-dimensional modeling is measured by the method described in the examples.
  • the three-dimensional modeling soluble material manufactured by the three-dimensional modeling soluble material manufacturing method is formed into a filament shape and used for manufacturing a three-dimensional object.
  • the diameter of the filament is preferably 0.5 mm or more, more preferably 1.0 mm or more, and preferably 3.0 mm or less from the same viewpoint, from the viewpoints of formability by a 3D printer and improvement of accuracy of a three-dimensional object. 0 mm or less is more preferable, and 1.8 mm or less is still more preferable.
  • the draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, more preferably 3 times or more, still more preferably 5 times or more, and the same viewpoint from the viewpoint of both toughness improvement and water solubility.
  • stretching process has the preferable inside of the range of the temperature 110 degreeC higher than the said glass transition temperature from the temperature 20 degreeC lower than the glass transition temperature of the said soluble material for three-dimensional modeling.
  • the lower limit of the stretching temperature is preferably 10 ° C. lower than the glass transition temperature from the viewpoint of toughness improvement and thermal stability, and more preferably the same temperature as the glass transition temperature.
  • the upper limit of the stretching temperature is more preferably 110 ° C. higher than the glass transition temperature, more preferably 100 ° C.
  • the stretching may be performed while air cooling when the resin is discharged from the extruder, or may be heated by hot air or a laser. Moreover, the said extending
  • the method for producing a three-dimensional object includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support for removing the support material by bringing the three-dimensional object precursor into contact with neutral water.
  • 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, except that the material of the support material is a three-dimensional modeling soluble material manufactured by the three-dimensional modeling soluble material manufacturing method.
  • a method of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in a known method for producing a three-dimensional object by a hot-melt lamination type 3D printer can be used.
  • the three-dimensional modeling soluble material manufactured by the method of manufacturing the three-dimensional modeling soluble material, which is the material of the support material is formed into the filament shape and supplied to the 3D printer.
  • 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 molding material includes ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, and polyetherimide.
  • ABS resin and / or polylactic acid resin are more preferable, and ABS resin is more preferable from the viewpoint of the formability by a 3D printer.
  • the support material removing step the support material is removed by bringing the three-dimensional object precursor into contact with neutral water.
  • the method of bringing the three-dimensional object precursor into contact with neutral water is preferably a method of immersing the three-dimensional object precursor in neutral water 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 neutral water examples include ion-exchanged water, pure water, tap water, and industrial water, but ion-exchanged water and tap water are preferable from the viewpoint of economy.
  • the neutral water may contain the water-soluble organic solvent in the range which does not damage the shaped three-dimensional object.
  • water-soluble organic solvents include lower alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether and diethylene glycol monobutyl ether, acetone and methyl ethyl ketone. And ketones.
  • the content of the water-soluble organic solvent in the neutral water is preferably 0.1% by mass or more from the viewpoint of solubility and damage to the shaped three-dimensional object, 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, 3% by mass or more is further preferable, 50% by mass or less is preferable, 40% by mass or less is preferable, and 30% by mass or less is preferable. % Mass or less is preferred.
  • the amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more with respect to the support material from the viewpoint of solubility of the support material, and 10,000 from the support material from the viewpoint of economy.
  • the mass times or less are preferable, the 5000 mass times or less are more preferable, the 1000 mass times or less are more preferable, and the 100 mass times or less are more preferable.
  • the time for bringing the soluble material for 3D modeling into contact with neutral water is preferably 5 minutes or more from the viewpoint of the removability of the support material, and reducing damage to the 3D object by contacting with neutral water for a long time. From the viewpoint of viewpoint and economy, it is preferably 180 minutes or shorter, more preferably 120 minutes or shorter, and even more preferably 90 minutes or shorter.
  • the cleaning temperature is preferably 15 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of removal of the support material, reduction of damage to the three-dimensional object, and economy, although it depends on the type of model material. More preferably, the temperature is more preferably 40 ° C. or more, and further preferably 40 ° C. or more.
  • the support material of the present embodiment is a support material that supports the three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and the raw material of the support material is used for the three-dimensional modeling. It is the soluble material for three-dimensional modeling manufactured by the manufacturing method of a soluble material.
  • the present specification further discloses the following manufacturing method.
  • a temperature Tmix of the raw material for the three-dimensional modeling soluble material in the kneading step is Tg + 80 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material for the three-dimensional modeling soluble material.
  • Tg + 80 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material for the three-dimensional modeling soluble material.
  • Tg + 200 (° C.) A method for producing a soluble material for three-dimensional modeling.
  • the base polymer is selected from the group consisting of polyvinyl alcohol, polyoxazoline, polyacrylamide, acrylate (co) polymer, methacrylate (co) polymer, polyester resin, polyamide resin, and methacrylic resin.
  • One or more types are preferable,
  • ⁇ 4> The resin according to any one of ⁇ 1> to ⁇ 3>, wherein the base polymer is preferably a resin having a hydrophilic group, more preferably a polyester resin having a hydrophilic group and / or a polyamide resin having a hydrophilic group. Manufacturing method of soluble material for three-dimensional modeling.
  • the hydrophilic monomer unit A with respect to the sum of 1 The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 4>, wherein the ratio is from 10 to 70 mol%.
  • the hydrophilic monomer unit A 1 Monomer A for deriving 1 Is at least one selected from the group consisting of hydroxy group-containing aromatic dicarboxylic acids, primary amino group-containing aromatic dicarboxylic acids, sulfonic acid group-containing aromatic dicarboxylic acids, and sulfonate group-containing aromatic dicarboxylic acids.
  • it consists of 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid.
  • At least one selected from the group is more preferable, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is still more preferable, ⁇ 1
  • the content of the hydrophilic group in the polyester resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, further preferably 0.7 mmol / g or more, 3.0 mmol / g or less, preferably 2.0 mmol / g or less, more preferably 1.5 mmol / g or less, preferably 0.5 to 3.0 mmol / g, more preferably 0.6 to 2.0 mmol / g. 0.7 to 1.5 mmol / g is more preferable,
  • the hydrophilic monomer unit A relative to the total amount of all monomer units in the polyester resin 1
  • the ratio of the amount of the substance is 5 mol% or more, preferably 7 mol% or more, more preferably 10 mol% or more, still more preferably 12 mol% or more, 35 mol% or less, preferably 33 mol% or less, more preferably 32 mol% or less.
  • 30 mol% or less is more preferable, 5 to 35 mol% is preferable, 7 to 33 mol% is more preferable, 10 to 32 mol% is further preferable, 12 to 30 mol% is still more preferable, and 8 to 13 mol% is still more preferable.
  • the hydrophobic dicarboxylic acid monomer unit B 1 Dicarboxylic acid B to induce 1 are preferably at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and include terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene.
  • At least one selected from the group consisting of dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid, terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 8>, wherein at least one selected from the group consisting of dicarboxylic acids is further preferred.
  • the hydrophobic dicarboxylic acid monomer unit B in the polyester resin relative to the total amount of all monomer units in the polyester resin 1
  • the ratio of the amount of the substance is preferably 15 mol% or more, more preferably 18 mol% or more, further preferably 20 mol% or more, preferably 45 mol% or less, more preferably 42 mol% or less, still more preferably 40 mol% or less, and 15 to 45 mol %, Preferably 20 to 42 mol%, more preferably 30 to 40 mol%, and the method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 9>.
  • the hydrophilic monomer unit A 1 And the hydrophobic dicarboxylic acid monomer unit B 1 Mol ratio (the hydrophilic monomer unit A 1 / The hydrophobic dicarboxylic acid monomer unit B 1 ) Is preferably 10/90 or more, more preferably 15/85 or more, further preferably 18/82 or more, still more preferably 20/80 or more, preferably 70/30 or less, more preferably 65/35 or less, The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 10>, further preferably 60/40 or less, further preferably 40/60 or less, and still more preferably 26/74 or less.
  • the ratio of diethylene glycol units to the total of all diol monomer units in the polyester resin is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, further preferably 20 mol% or more, and 25 mol%.
  • the above is more preferable, 30 mol% or more is more preferable, 60 mol% or less is preferable, 55 mol% or less is more preferable, 50 mol% or less is further preferable, and 45 mol% or less is more preferable, ⁇ 1> to ⁇ 11
  • the manufacturing method of the soluble material for three-dimensional modeling in any one of> is more preferably 10 mol% or more, further preferably 15 mol% or more, further preferably 20 mol% or more, and 25 mol%.
  • 30 mol% or more is more preferable
  • 60 mol% or less is preferable
  • 55 mol% or less is more preferable
  • 50 mol% or less is further preferable
  • 45 mol% or less is
  • the total ratio of A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 98 mol% or more.
  • the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 12>, further preferably 100 mol%, further preferably 100 mol%, and still more preferably 100 mol%.
  • the polyester resin is the hydrophilic monomer unit A. 1
  • the hydrophilic monomer unit A with respect to the total of all dicarboxylic acid monomer units containing 1 And the dicarboxylic acid monomer unit B 1 Of the dicarboxylic acid monomer unit B are 10 to 70 mol% and 30 to 90 mol%, respectively.
  • Dicarboxylic acid B for obtaining 1 The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 13>, in which is a polyester resin ⁇ wherein 2,6 is naphthalenedicarboxylic acid.
  • Hydrophobic dicarboxylic acid monomer unit B 2 And the hydrophilic monomer unit A with respect to the total of all monomer units in the polyamide resin. 2
  • the hydrophilic monomer unit A 2 Monomer A for deriving 2 Is preferably a hydroxy group-containing aromatic dicarboxylic acid, a primary amino group-containing aromatic dicarboxylic acid, a sulfonic acid group-containing aromatic dicarboxylic acid, and a sulfonate group-containing aromatic dicarboxylic acid, such as 5-hydroxyisophthalic acid, 1, At least one selected from the group consisting of 3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid is more Preferably, at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is still more preferable.
  • the content of the hydrophilic group in the polyamide resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, still more preferably 0.7 mmol / g or more, 3.0 mmol / g or less is preferred, 2.0 mmol / g or less is more preferred, 1.5 mmol / g or less is more preferred, 0.5 to 3.0 mmol / g is preferred, 0.6 to 2.0 mmol / g is more preferred, The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 16>, wherein 0.7 to 1.5 mmol / g is more preferable.
  • the hydrophilic monomer unit A relative to the total amount of all monomer units in the polyamide resin 2
  • the ratio of the amount of the substance is 2.5 mol% or more, preferably 4 mol% or more, more preferably 6 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and 40 mol% or less, 35 mol % Or less, more preferably 31 mol% or less, still more preferably 25 mol% or less, still more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol% or less, and even more preferably 8 mol% or less.
  • the tertiary according to any one of ⁇ 1> to ⁇ 17> The method of manufacturing the shaped for the soluble material.
  • the hydrophobic dicarboxylic acid monomer unit B 2 Dicarboxylic acid B to induce 2 are preferably at least one selected from the group consisting of aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and include terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene.
  • At least one selected from the group consisting of dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid, terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalene The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 18>, wherein at least one selected from the group consisting of dicarboxylic acids is more preferable, and terephthalic acid is still more preferable.
  • the hydrophobic dicarboxylic acid monomer unit B in the polyamide resin relative to the total amount of all monomer units in the polyamide resin 2
  • the ratio of the amount of the substance is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 42 mol% or more.
  • the hydrophilic monomer unit A 2 And the hydrophobic dicarboxylic acid monomer unit B 2 Mol ratio (the hydrophilic monomer unit A 2 / The hydrophobic dicarboxylic acid monomer unit B 2 ) Is preferably 10/90 or more, more preferably 15/85 or more, further preferably 18/82 or more, still more preferably 20/80 or more, preferably 50/50 or less, more preferably 40/60 or less, The method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 20>, further preferably 30/70 or less, and further preferably 25/75 or less.
  • the weight average molecular weight of the base polymer is preferably 3000 or more, more preferably 3500 or more, further preferably 4000 or more, preferably 70000 or less, more preferably 50000 or less, still more preferably 30000 or less, and more preferably 20000 or less. More preferably, the method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 21>.
  • the glass transition temperature (Tg) of the base polymer is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, 250 ° C. or lower, and 220 ° C. or lower. Is preferably 180 ° C.
  • the melt flow rate of the base polymer is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and further more preferably 2.5 g / 10 min or more.
  • 10 g / 10 min or less Preferably, 10 g / 10 min or less, more preferably 7 g / 10 min or less, more preferably 6 g / 10 min or less, still more preferably 5 g / 10 min or less, 3D modeling according to any one of ⁇ 1> to ⁇ 23> Of a soluble material for use.
  • the blending ratio of the base polymer is preferably 70% by mass or more, more preferably 80% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and any one of ⁇ 1> to ⁇ 24>
  • the mixing ratio of the compatibilizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the base polymer.
  • the compatibilizer includes at least one reactive group selected from the group consisting of an epoxy group, an acid anhydride group, an isocyanate group, an amino group, a carboxyl group, and an oxazoline group.
  • the elastomer is preferably at least one selected from the group consisting of acrylic elastomers, olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and silicone elastomers.
  • the blending ratio of the elastomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the base polymer.
  • the ratio (K / L) of the total length K of the kneading disk to the total length L of the effective screw of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is greater than 0.20, Preferably greater than 0.25, more preferably greater than 0.30, less than 0.70, preferably less than 0.60, more preferably less than 0.50, even more preferably less than 0.40, 0.20 ⁇ (K / L) ⁇ 0.70, preferably 0.25 ⁇ (K / L) ⁇ 0.60, more preferably 0.30 ⁇ (K / L) ⁇ 0.5.
  • the method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 29>.
  • ⁇ 31> The ratio (L / D) of the effective screw full length L to the screw diameter D of the twin-screw extruder for kneading the raw material for the three-dimensional modeling soluble material is larger than 25, preferably larger than 27, more preferably.
  • the method for producing a soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 30>. ⁇ 32>
  • the temperature Tmix of the raw material for the three-dimensional modeling soluble material in the kneading step is greater than Tg + 80 (° C.) with respect to the glass transition temperature Tg of the base polymer contained in the raw material for the three-dimensional modeling soluble material.
  • Tg + 90 (° C.), more preferably greater than Tg + 100 (° C.), even more preferably greater than Tg + 110 (° C.), even more preferably greater than Tg + 120 (° C.), even more preferably greater than Tg + 130 (° C.).
  • Tg + 200 (° C.), preferably smaller than Tg + 190 (° C.), more preferably smaller than Tg + 180 (° C.), still more preferably smaller than Tg + 170 (° C.), and Tg + 80 (° C.) ⁇ Tmix ⁇ 200 (° C.) Yes
  • Tg + 100 (° C.) ⁇ Tmix ⁇ Tg + 180 (° C.) more preferably Tg + 110 (° C.) ⁇ Tmix ⁇ Tg + 170 (° C.), more preferably Tg + 120 (° C.) ⁇ Tmix ⁇ Tg + 170 (° C.), Tg + 130 (° C.) ) ⁇ Tmix ⁇ Tg + 170 (° C.) is more preferable.
  • the glass transition temperature (Tg) of the three-dimensional modeling soluble material is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and 250 ° C. or lower.
  • the melt flow rate of the three-dimensional modeling soluble material is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, further preferably 2.0 g / 10 min or more, and 2.5 g / 10 min.
  • the above is more preferable, 10 g / 10 min or less is preferable, 7 g / 10 min or less is more preferable, 6 g / 10 min or less is more preferable, and 5 g / 10 min or less is more preferable, 3D according to ⁇ 33> or ⁇ 34> Soluble material for modeling.
  • the average particle size of the elastomer in the three-dimensional modeling soluble material is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, still more preferably 1.7 ⁇ m or less, and even more preferably 1.4 ⁇ m or less.
  • ⁇ 33>- ⁇ 35> The soluble material for three-dimensional modeling according to any one of the above.
  • ⁇ 37> The soluble material for 3D modeling according to any one of ⁇ 33> to ⁇ 36>, wherein the soluble material for 3D modeling is a filament.
  • 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, still more preferably 1.8 mm or less, ⁇ 33>
  • the draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, further preferably 3 times or more, still more preferably 5 times or more, preferably 200 times or less, and 150 times or less.
  • the soluble material for three-dimensional modeling according to any one of ⁇ 33> to ⁇ 39>, more preferably 100 times or less, and still more preferably 50 times or less.
  • the stretching temperature in the stretching process is preferably in the range of a temperature that is 20 ° C. lower than the glass transition temperature of the soluble material for three-dimensional modeling to a temperature that is 110 ° C. higher than the glass transition temperature. More preferably, the temperature is 10 ° C. lower than the glass transition temperature, more preferably the same temperature as the glass transition temperature, the upper limit of the stretching temperature is more preferably 110 ° C. higher than the glass transition temperature, and 100 ° C. higher than the glass transition temperature.
  • a hot melt lamination method having 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 bringing the three-dimensional object precursor into contact with neutral water and removing the support material 3D object manufacturing method according to claim 1, wherein the material of the support material is manufactured by the method of manufacturing a 3D modeling soluble material according to any one of ⁇ 1> to ⁇ 32>.
  • the modeling material that is the material of the three-dimensional object is ABS resin, polylactic acid resin, polycarbonate resin, 12-nylon, 6,6-nylon, 6-nylon, polyphenylsulfone resin, polyetheretherketone, And a thermoplastic resin such as polyetherimide is preferable, an ABS resin and / or a polylactic acid resin is more preferable, and an ABS resin is still more preferable.
  • a thermoplastic resin such as polyetherimide is preferable, an ABS resin and / or a polylactic acid resin is more preferable, and an ABS resin is still more preferable.
  • the water-soluble organic solvent is a lower alcohol such as methanol, ethanol or 2-propanol, a glycol ether such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether or diethylene glycol monobutyl ether,
  • a glycol ether such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether or diethylene glycol monobutyl ether
  • ketones such as acetone and methyl ethyl ketone are preferred.
  • the content of the water-soluble organic solvent in the neutral water is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 3% by mass or more.
  • the amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more, preferably 10,000 times by mass or less, more preferably 5000 times by mass or less, more preferably 1000 masses with respect to the support material.
  • Time for contacting the three-dimensional modeling soluble material with neutral water is preferably 5 minutes or more, preferably 180 minutes or less, more preferably 120 minutes or less, and even more preferably 90 minutes or less, ⁇ 42> to The method for producing a three-dimensional object according to any one of ⁇ 47>.
  • the temperature of the neutral water to be brought into contact with the three-dimensional modeling soluble material is preferably 15 ° C or higher, more preferably 25 ° C or higher, further preferably 30 ° C or higher, still more preferably 40 ° C or higher, 85 ° C.
  • composition of polyester resin [Analysis of base polymer] [Composition of polyester resin] The compositions of the polyester resins 1 to 3 were determined by proton NMR measurement using Agilent NMR and MR400.
  • the amount (unit: mmol / g) of the hydrophilic group (SO 3 ) in the polyester resin was determined from the compositions of the polyester resins 1 to 3 determined by the above method.
  • melt flow rate Resin that flows per 10 minutes at 240 ° C./5.0 kg of the polyester resins 1 to 3 using a melt flow rate measuring device “Semi-automatic melt flow index tester No. 120-SAS-2000” manufactured by Yasuda Seiki Seisakusho Co., Ltd. The mass of was measured.
  • Measuring device HLC-8320GPC (manufactured by TOSOH) Eluent: HFIP / 0.5 mM sodium trifluoroacetate Flow rate: 0.2 mL / min Measurement temperature: 40 ° C
  • SIP mol%) is the ratio (mol%) of 5-sulfoisophthalic acid monomer unit in all dicarboxylic acid monomer units
  • NPDCA mol%) is 2,6- Ratio of naphthalenedicarboxylic acid monomer units (mol%)
  • EG mol%) is the ratio of ethylene glycol monomer units in all diol monomer units (mol%)
  • DEG mol% is diethylene glycol monomer units in all diol monomer units. The ratio (mol%) is shown.
  • Example 1 80.0 kg of the polyester compound 3 and Clarity (registered trademark) LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 10.0 kg, compatibilized Bondfast (registered trademark) 7B (manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.0 kg as an agent was dried at 60 ° C.
  • Clarity (registered trademark) LA2250 manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer
  • compatibilized Bondfast registered trademark
  • 7B manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidy
  • a twin screw extruder ( TOSHIBA MACHINE CO., LTD .: TEM-41SS, screw diameter 41 mm, two-row type) was melt kneaded at a cylinder temperature of 220 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h to obtain a white mixture composition.
  • the configuration of the screw of the twin screw extruder in Example 1 was as follows.
  • Example 2 8.0 kg of the above-mentioned polyester compound 2 and 1.0 kg of Clarity (registered trademark) LA2250 and 0.4 kg of Bondfast (registered trademark) 7B as a compatibilizer were dried at 60 ° C. under reduced pressure, and these were premixed in a Henschel mixer. Thereafter, the mixture was melt kneaded at a cylinder temperature of 210 ° C., a screw rotation speed of 200 rpm, and a discharge speed of 3 kg / h using a twin-screw extruder (manufactured by Ikegai Co., Ltd .: PCM30, screw diameter 29 mm, Sanjo type), and was a white mixture composition I got a thing.
  • Clarity registered trademark
  • Bondfast registered trademark
  • the configuration of the screw of the twin screw extruder in Example 2 was as follows. Four kneading discs (neutral type), two kneading discs (forward twist type), and one kneading disc (reverse twist type) at a distance of 250 mm to 365.5 mm from the starting point 410.5 mm to the starting point One kneading disc (forward twist type) at 443.5 mm and one kneading disc (reverse twist type) A kneading disc (forward twist type) 488.5 mm to 521.5 mm from the starting point 1 piece, 1 kneading disc (reverse twist type) 1 kneading disc (forward twist type), 1 kneading disc (reverse twist type) from the start point 566.5 mm to 599.5 mm Start point From 614.5 mm to 649.5 mm from the seal ring From the starting point to 749.5 mm to 799.5 mm Lee Nappuru screw It
  • Example 3 Except for changing the cylinder temperature to 230 ° C., the same operation as in Example 2 was performed to obtain a composition which was a white mixture.
  • Example 4 Except for changing the cylinder temperature to 190 ° C., the same operation as in Example 2 was performed to obtain a composition which was a white mixture.
  • Example 5 40.0 kg of the polyester compound 3 and 5.0 kg of Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemicals Corporation: thermoplastic elastomer having acid anhydride group: maleic anhydride-modified SEBS) were dried at 60 ° C. under reduced pressure, and weight Using a feeder, melt kneading using a twin screw extruder (Toshiba Machine Co., Ltd .: TEM-41SS, screw diameter 41 mm, double thread type) at a cylinder temperature of 230 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h. The composition which is a white mixture was obtained.
  • the screw configuration, total screw length, and total kneading disc length of the twin screw extruder in Example 5 were the same as in Example 1.
  • Example 6 40.0 kg of the above-mentioned polyester compound 3 and 7.0 kg of Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemicals: thermoplastic elastomer having an acid anhydride group: maleic anhydride-modified SEBS) were dried at 60 ° C. under reduced pressure, and weight Using a feeder, melt kneading using a twin screw extruder (Toshiba Machine Co., Ltd .: TEM-41SS, screw diameter 41 mm, double thread type) at a cylinder temperature of 230 ° C., a screw rotation speed of 250 rpm, and a discharge speed of 70 kg / h. The composition which is a white mixture was obtained.
  • the screw configuration, total screw length, and total kneading disc length of the twin screw extruder in Example 6 were the same as in Example 1.
  • the extruded composition is wound with air in a first roll while winding the filament at a speed of 12.0 m / min (resin temperature 80 ° C. behind the first roll), and further heated with hot air of 90 ° C., Stretching was performed while winding with a second roll at a speed of 37.0 m / min to obtain a filament having a diameter of about 1.4 to 1.6 mm (total stretching ratio: 10 to 13 times). The elongation at break of this stretched filament was 12%, and the toughness was higher than that of a filament having the same composition prepared from a capillograph and having a low stretch ratio (stretch ratio of 1.8).
  • the filament was supplied to the makerbot 3D printer Replicator 2X and extruded from a heat nozzle having a temperature of 230 ° C. As a result, the nozzle could be discharged without clogging, and it was confirmed that the melt also solidified immediately. .
  • Glass transition temperature of soluble materials for 3D modeling The analysis was performed in the same manner as the method for analyzing the glass transition temperature of the base polymer.
  • a finely crushed sample piece is extruded from a capillary having a diameter of 2.0 mm and a length of 10 mm at a melting temperature of 210 ° C. and an extrusion speed of 10 mm / min using a capillograph (Capigraph 1D manufactured by Toyo Seiki Seisakusho), and the tip is pinched with tweezers. While being pulled lightly by hand, it was processed into a filament having a diameter of 1.5 mm (stretching ratio 1.8 times).
  • the sample was taken out from ethyl acetate and dried under reduced pressure at 60 ° C. for 1 hour. After vacuum drying, the fracture surface of the sample was observed with an SEM (VE-8800 manufactured by Keyence), and the equivalent circle diameter of the voids found in the cross section of the sample was determined using image analysis software WINROOF. The voids were counted in a 61 ⁇ m ⁇ 46 ⁇ m photograph, the average value was calculated, and the average particle size was obtained.
  • SEM VE-8800 manufactured by Keyence
  • the fracture surface of the sample was observed with an SEM (VE-8800 manufactured by Keyence), and the equivalent circle diameter of the voids found in the cross section of the sample was determined using image analysis software WINROOF.
  • the voids were counted in a 61 ⁇ m ⁇ 46 ⁇ m photograph, the average value was calculated, and the average particle size was obtained.

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Abstract

La présente invention concerne un procédé de production d'un matériau fusible pour moulage tridimensionnel à utiliser, lors de la production d'un objet tridimensionnel à l'aide d'une imprimante 3D à mode de dépôt en fusion, en tant que matériau pour un élément de support qui supporte ledit objet tridimensionnel. Le procédé de production d'un matériau fusible pour moulage tridimensionnel comporte une étape de malaxage pour le malaxage avec une configuration de vis telle que le rapport de la longueur totale (K) des disques de malaxage par rapport à la longueur de vis effective totale (L) d'une extrudeuse à deux vis, qui malaxe un matériau de départ pour le matériau fusible pour moulage tridimensionnel, est de 0,20 < K/L < 0,70. La température (Tmix) du matériau de départ pour le matériau fusible pour moulage tridimensionnel à l'étape de malaxage par rapport à la température de transition vitreuse (Tg) d'un polymère de base compris dans le matériau de départ pour ledit matériau fusible pour moulage tridimensionnel est Tg + 80 (°C) < Tmix < Tg + 200 (°C). La présente invention est apte à fournir un procédé de production d'un matériau fusible pour moulage tridimensionnel qui comporte d'excellentes propriétés mécaniques et, même lorsqu'il est fabriqué en filaments, n'est pas susceptible de se casser.
PCT/JP2017/026820 2016-08-05 2017-07-25 Procédé de production d'un matériau fusible destiné à un moulage tridimensionnel Ceased WO2018025703A1 (fr)

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CN201780048859.1A CN109562534A (zh) 2016-08-05 2017-07-25 三维造型用可溶性材料的制造方法
US16/323,453 US20190168447A1 (en) 2016-08-05 2017-07-25 Method for producing fusible material for three-dimensional molding
EP17836809.8A EP3495108A4 (fr) 2016-08-05 2017-07-25 Procédé de production d'un matériau fusible destiné à un moulage tridimensionnel

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JP2016154649 2016-08-05
JP2016-154649 2016-08-05
JP2017-141058 2017-07-20
JP2017141058A JP2018024849A (ja) 2016-08-05 2017-07-20 三次元造形用可溶性材料の製造方法

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CN118434568A (zh) * 2022-03-29 2024-08-02 花王株式会社 层叠体

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* Cited by examiner, † Cited by third party
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