WO2018139537A1 - 三次元造形用可溶性材料 - Google Patents
三次元造形用可溶性材料 Download PDFInfo
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- WO2018139537A1 WO2018139537A1 PCT/JP2018/002287 JP2018002287W WO2018139537A1 WO 2018139537 A1 WO2018139537 A1 WO 2018139537A1 JP 2018002287 W JP2018002287 W JP 2018002287W WO 2018139537 A1 WO2018139537 A1 WO 2018139537A1
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- BPHRVWNBDDMMSZ-UHFFFAOYSA-N 4-sulfonaphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=C(S(O)(=O)=O)C2=CC(C(=O)O)=CC=C21 BPHRVWNBDDMMSZ-UHFFFAOYSA-N 0.000 description 1
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- UDAVYLUZVUNEES-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.O(C1=CC=CC=C1)C(C)O Chemical compound C1=CC=CC=2C3=CC=CC=C3CC12.O(C1=CC=CC=C1)C(C)O UDAVYLUZVUNEES-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C(C)(C)C(c1cc(C(NCCCCCCCCCCNC)=O)cc(*)c1)=O)NC=CCCCCCCCCNC(c(cc1)ccc1C(C)=O)=O Chemical compound CC(C(C)(C)C(c1cc(C(NCCCCCCCCCCNC)=O)cc(*)c1)=O)NC=CCCCCCCCCNC(c(cc1)ccc1C(C)=O)=O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions
- the present invention relates to a soluble material for three-dimensional modeling used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a 3D printer, particularly a hot melt lamination type 3D printer.
- the 3D printer is a type of rapid prototyping and is a three-dimensional printer that forms a three-dimensional object based on 3D data such as 3D CAD, 3D CG, and the like.
- a 3D printer system a hot melt lamination system (hereinafter also referred to as an FDM system), an inkjet ultraviolet curing system, an optical modeling system, a laser sintering system, and the like are known.
- the FDM method is a modeling method for obtaining a three-dimensional object by heating / melting and extruding and laminating polymer filaments, and unlike other methods, does not use a material reaction.
- FDM 3D printers are small and inexpensive, and have become popular in recent years as devices with little post-processing.
- a three-dimensional object is formed by stacking a modeling material constituting the three-dimensional object and a support material for supporting the three-dimensional structure of the modeling material.
- Examples of the method for removing the support material from the three-dimensional object precursor include a method in which the support material is removed by immersing the three-dimensional object precursor in a strong alkaline aqueous solution using a methacrylic acid copolymer as the support material (for example, JP, 2008-507619, A). This method utilizes the fact that the carboxylic acid in the methacrylic acid copolymer is neutralized by an alkali and dissolved in a strong alkaline aqueous solution.
- JP-T-2002-516346 discloses a method of removing support material by using water-soluble poly (2-ethyl-2-oxazoline) as a support material and immersing a three-dimensional object precursor in water. It is disclosed. According to the technique described in JP-T-2002-516346, the support material for the three-dimensional object precursor can be removed without using a strong alkaline aqueous solution.
- (2-Ethyl-2-oxazoline) has a high affinity with moisture, so when soluble materials for 3D modeling containing poly (2-ethyl-2-oxazoline) are exposed to high humidity, Absorbs moisture.
- the present applicant is suitable for manufacturing a three-dimensional object by the FDM method, has a moisture absorption resistance, has a high dissolution rate in neutral water, and does not use a strong alkaline aqueous solution.
- a patent application Japanese Patent Application No. 2016-019789 was filed for an invention of a three-dimensional modeling soluble material for a support material that can be quickly removed from an object precursor.
- the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer.
- R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms
- n represents a number of 1 or 2
- n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion.
- X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.
- the three-dimensional object manufacturing method of the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material for removing the support material by bringing the three-dimensional object precursor into contact with neutral water.
- the support material is the soluble material for three-dimensional modeling.
- the support material of the present invention is a support material that supports a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer, and includes a thermoplastic resin having a hydrophilic group, and the following general formula: And an organic salt compound represented by (I). (R 1 —SO 3 ⁇ ) n X n + (I) (In the general formula (I), R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, n represents a number of 1 or 2, and when n is 1, n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion. When n is 2, X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.)
- the three-dimensional modeling soluble material has poor adhesion to the modeling material, and the support material related to the three-dimensional modeling soluble material tends to be peeled off from the modeling material.
- the support material is peeled off from the modeling material before the modeling material is sufficiently solidified, the three-dimensional structure of the modeling material cannot be sufficiently supported, and the accuracy of the three-dimensional object is reduced. There is.
- the present invention has a sufficient adhesion with a modeling material even when used for manufacturing a three-dimensional object by an FDM type 3D printer, has a high dissolution rate in neutral water, and does not use a strong alkaline aqueous solution.
- a three-dimensional modeling soluble material for a support material that can be quickly removed from an original object precursor.
- the present invention can suppress a decrease in accuracy of a three-dimensional object, has a high dissolution rate in neutral water, and can be quickly removed from a three-dimensional object precursor without using a strong alkaline aqueous solution.
- An original object manufacturing method is provided.
- the present invention provides a support material that has sufficient adhesiveness with a modeling material, has a high dissolution rate in neutral water, and can be quickly removed from a three-dimensional object precursor without using a strong alkaline aqueous solution. provide.
- the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer.
- R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms
- n represents a number of 1 or 2
- n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion.
- X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.
- the three-dimensional object manufacturing method of the present invention includes a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material, and a support material for removing the support material by bringing the three-dimensional object precursor into contact with neutral water.
- the support material is the soluble material for three-dimensional modeling.
- the support material of the present invention is a support material that supports a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer, and includes a thermoplastic resin having a hydrophilic group, and the following general formula: And an organic salt compound represented by (I). (R 1 —SO 3 ⁇ ) n X n + (I) (In the general formula (I), R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, n represents a number of 1 or 2, and when n is 1, n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion. When n is 2, X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.)
- a strong alkaline aqueous solution is used that has sufficient adhesion to a modeling material even when used for manufacturing a three-dimensional object by an FDM type 3D printer, and has a high dissolution rate in neutral water.
- a three-dimensional modeling soluble material for a support material that can be quickly removed from a three-dimensional object precursor.
- a method for manufacturing a three-dimensional object that can be provided can be provided.
- the support has sufficient adhesion with the modeling material, has a high dissolution rate in neutral water, and can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution.
- Material can be provided.
- the three-dimensional modeling soluble material of the present embodiment is a three-dimensional modeling soluble material that is used as a support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer.
- R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms
- n represents a number of 1 or 2
- n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion.
- X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.
- the support material made of the soluble material for three-dimensional modeling of the present embodiment has sufficient adhesion to the modeling material, has a high dissolution rate in neutral water, and is three-dimensional without using a strong alkaline aqueous solution. It can be quickly removed from the object precursor.
- the thermoplastic resin has a hydrophilic group from the viewpoint of solubility in neutral water having a pH of 6 to 8, which is not a strong alkaline aqueous solution.
- the hydrophilic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, an amide group, and a phosphate group. And one or more selected from the group consisting of a phosphate group, a sulfonate group, and a sulfonate group.
- the hydrophilic group is preferably at least one selected from the group consisting of a sulfonic acid group and a sulfonic acid group, and more preferably a sulfonic acid group.
- the content of the hydrophilic group in the thermoplastic resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0.7 mmol / g.
- the above 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 1.0 mmol / g or less is more preferable.
- the content of the hydrophilic group in the thermoplastic resin is preferably 0.5 to 3.0 mmol / g from the viewpoint of solubility in neutral water and moisture absorption resistance, and 0.6 More preferably, it is -2.0 mmol / g, and more preferably 0.7-1.5 mmol / g.
- a modeling material having high heat resistance has a high melting point or a high glass transition temperature, and the temperature at which the modeling material is heated / melted and extruded and laminated by a 3D printer and a support in contact with the modeling material. If the temperature of the material is significantly different, the accuracy of the three-dimensional object may be impaired. Therefore, when a modeling material having a high melting point or glass transition temperature is heated / melted and extruded and laminated by a 3D printer, the three-dimensional modeling soluble material, which is the material of the support material, is also heated to a temperature close to the temperature of the modeling material / Melt, extrude and laminate.
- the thermoplastic resin includes a polyester resin having the hydrophilic group, a polyamide resin having the hydrophilic group, an acrylic resin having the hydrophilic group, a polyvinyl alcohol resin having the hydrophilic group, and the hydrophilic group.
- a polyvinyl pyrrolidone resin having, an ester amide resin having the hydrophilic group, and a urethane resin having the hydrophilic group are preferable.
- the polyester resin has a hydrophilic group and a polyamide resin has a hydrophilic group. One or more selected from the group is more preferred.
- the polyester resin has a hydrophilic monomer unit A 1 having the hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B 1 , and a diol monomer unit, and the hydrophilic monomer unit A 1 and the hydrophobic monomer in the polyester resin.
- a polyester resin in which the ratio of the hydrophilic monomer unit A 1 to the total of the dicarboxylic 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. Also, the monomer to induce the hydrophilic monomer unit A 1 is also referred to as a monomer A 1.
- the hydrophilic group is a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium from the viewpoint of solubility in neutral water having a pH of 6 to 8 that is not a strong alkaline aqueous solution.
- One or more selected from the group consisting of a base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl group, a phosphate group, a phosphate group, a sulfonate group, and a sulfonate group are preferred, a sulfonate group, and a sulfonate
- One or more selected from the group consisting of bases is more preferred, and sulfonate groups are more preferred.
- the secondary amino group is —NHR 2 group (where 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. 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 3 R 4 group (provided that R 3 is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester resin.
- a tertiary amino group having a carbon number of 1 to 14 and R 4 is a straight chain or branched alkyl group having a carbon number of 1 to 14), and —NR
- At least one selected from the group consisting of tertiary amino groups represented by a 5- group (wherein R 5 represents a linear or branched alkyl group having 1 to 14 carbon atoms) is preferable. .
- the quaternary ammonium base is —N + ⁇ R 6 R 7 R 8 ⁇ ⁇ W ⁇ (wherein, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of the polyester resin.
- R 6, R 7, R 8 each independently represent a hydrogen atom or a C 1 to 14 alkyl group carbon
- W - is 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 ⁇ j1 — (where j1 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 9 has 4 or more and 50 or less
- 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.
- 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 Carboxyl bases is preferably represented by the more preferred more.).
- 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 Preferred, sodium ions are more preferred 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, sodium ion is better Further preferred.
- Sulfonate is preferably represented by.
- 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, 1.5 mmol / g or less is more preferable, and 1.0 mmol / g or less is 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 1.5 mmol / g is more preferable, and 0.7 to 1.0 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 further preferable, 12 to 30 mol% is further more preferable, and 8 to 13 mol% is further 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 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 2,6-naphthalenedicarboxylic is more preferable. An acid is even more preferred.
- 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 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 more 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 more preferable, 20 mol% or more is further preferable, 25 mol% or more is 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 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 more preferable, and 27 mol% or less is 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 according to the above, 30 mol% or more is preferable, 35 mol% or more is more preferable, 40 mol% or more is more preferable, 65 mol% or more is more preferable, 73 mol% or more is more preferable, and 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 (II) and (III).
- p1 represents the degree of polymerization of ethylene 2,6-naphthalene dicarboxylate
- q1 represents the number of polymerization degrees of ethylene 5-sulfoisophthalate.
- Rate and ethylene 5-sulfoisophthalate are block bonds and / or random bonds, and random bonds are more preferable from the viewpoint of solubility in neutral water.
- p2 is the degree of polymerization of ethylene 2,6-naphthalene dicarboxylate
- q2 is the degree of polymerization of ethylene 5-sulfoisophthalate
- r2 is bisphenoxyethanol fluorene and 2,6-naphthalenedicarboxylic acid.
- S2 represents the number of polymerizations of the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid, provided that ethylene 2,6-naphthalenedicarboxylate, ethylene 5-sulfoisophthalate, bis
- the condensate of phenoxyethanol fluorene and 2,6-naphthalenedicarboxylic acid, and the condensate of bisphenoxyethanol fluorene and 5-sulfoisophthalic acid are block bonds and / or random bonds, and are random from the viewpoint of solubility in neutral water. Bonding 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. Also, 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 10 group (where R 10 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 11 R 12 group (provided that R 11 is linear or branched from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin.
- Jo of represents a number 1 to 14 alkyl group carbon
- R 12 is a tertiary amino group represented by denotes a straight or branched having 1 to 14 alkyl group carbon atoms.
- -NR It is preferably at least one selected from the group consisting of a tertiary amino group represented by a 13 -group (wherein R 13 represents a linear or branched alkyl group having 1 to 14 carbon atoms).
- the quaternary ammonium base is —N + ⁇ R 14 R 15 R 16 ⁇ ⁇ Z ⁇ (however, from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin.
- R 14 , R 15 , and R 16 each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and Z ⁇ 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 ⁇ j2 — (where j2 represents an average number) from the viewpoint of solubility in neutral water and ease of polymerization reaction during the production of polyamide resin.
- 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 But Risarani 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
- the sodium ion is more preferable and more.
- 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, more sodium ions Preferred et.) 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 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%
- the above is preferable, 6 mol% or more is more preferable, 8 mol% or more is more 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 even 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 is more preferable, 30 mol% or more is more preferable, 35 mol% or more is further more preferable, 40 mol% or more is further more preferable, 42 mol% or more is further more preferable, 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 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 with 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, 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, 20 or less 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 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 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 further more preferable, and 100 mol% is further 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 (IV) to (IX).
- 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 weight average molecular weight of the thermoplastic resin 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 the three-dimensional modeling soluble material. From the viewpoint of the formability by a 3D printer, 70000 or less is preferable, 50000 or less is more preferable, 30000 or less is further preferable, and 25000 or less is more preferable. In addition, in this specification, a weight average molecular weight is measured by the method as described in an Example.
- the glass transition temperature (Tg) of the thermoplastic resin is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. From the viewpoint, 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 content of the thermoplastic resin in the three-dimensional modeling soluble material is preferably 70% by mass or more, more preferably 80% by mass or more, and preferably 95% by mass or less, from the viewpoint of modeling by a 3D printer.
- the mass% or less is more preferable.
- the soluble material for three-dimensional modeling includes the organic salt compound represented by the general formula (I) from the viewpoint of improving the adhesion with the modeling material.
- R 1 is, in view of improving the adhesion to the molding material, in view of the solubility in neutral water, the moisture absorption resistance viewpoint, and heat resistance required for shaping by 3D printer From the viewpoint, a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent is shown.
- the hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
- the hydrocarbon group is an aliphatic hydrocarbon group
- the number of carbon atoms of the hydrocarbon group is improved from the viewpoint of improving adhesion with the molding material, from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, and From the viewpoint of heat resistance required for modeling by a 3D printer, 1 or more is preferable, 4 or more is more preferable, 8 or more is more preferable, 30 or less is preferable, 25 or less is more preferable, and 20 or less is more preferable.
- the number of carbon atoms of the hydrocarbon group is improved from the viewpoint of improving the adhesion with the modeling material, from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, 3 or more is preferable, 5 or more is more preferable, 6 or more is more preferable, 10 or more is further more preferable, 30 or less is preferable, and 25 or less is more preferable. The following is more preferable.
- the hydrocarbon group is an aromatic hydrocarbon group
- the number of carbon atoms of the hydrocarbon group is improved from the viewpoint of improving adhesion to the modeling material, from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, and From the viewpoint of heat resistance required for modeling by a 3D printer, 6 or more is preferable, 8 or more is more preferable, 10 or more is more preferable, 30 or less is preferable, and 25 or less is more preferable.
- hydrogen is used from the viewpoint of improving adhesion with a modeling material, from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, and from the viewpoint of heat resistance required for modeling by a 3D printer.
- Those containing at least one selected from the group consisting of an atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom are preferable.
- a hydrocarbon group having 1 to 22 carbon atoms or A halogenated alkyl group is preferred, a hydrocarbon group having 1 to 16 carbon atoms or a halogenated alkyl group is more preferred, a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group is further preferred, and a carbon atom having 1 to 12 carbon atoms is preferred.
- a hydrogen group is even more preferable.
- X n + is a heat-resistant element required for improving the adhesion with a modeling material, from a viewpoint of solubility in neutral water, from a viewpoint of moisture absorption resistance, and modeling by a 3D printer.
- tetraalkylphosphonium ions are used from the viewpoints of improving adhesion to modeling materials, from the viewpoint of solubility in neutral water, from the viewpoint of moisture absorption resistance, and from the viewpoint of heat resistance required for modeling by a 3D printer.
- tetrabutylphosphonium ions are more preferred.
- n is a viewpoint of improving adhesion with a modeling material, a viewpoint of solubility in neutral water, a viewpoint of moisture absorption resistance, and a viewpoint of heat resistance required for modeling by a 3D printer. 1 is preferred.
- the mass ratio of the organic salt compound to the thermoplastic resin is preferably 0.5 or more, more preferably 2 or more, still more preferably 6 or more, and dissolution in neutral water from the viewpoint of improving the adhesion with the modeling material. 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable from the viewpoint of heat resistance, the viewpoint of moisture absorption resistance, and the heat resistance required for modeling by a 3D printer.
- Ratio of substance amount (mol) of alkyl sulfonate ion (R 1 —SO 3 ⁇ ) of organic salt compound to substance amount (mol) of hydrophilic group of thermoplastic resin (alkyl sulfonate ion of organic salt compound) From the viewpoint of improving the adhesion to the molding material, 0.005 or more is preferable, 0.01 or more is more preferable, and 0.05 or more is preferable. More preferably, 0.15 or more is more preferable, and 1.0 or less is preferable 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. .9 or less is more preferable, and 0.7 or less is more preferable.
- the glass transition temperature of the soluble material for three-dimensional modeling is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of modeling by a 3D printer. From the same viewpoint, 250 ° C. or lower is preferable, 220 ° C. or lower is more preferable, and 200 ° C. or lower is further preferable.
- the soluble material for three-dimensional modeling may contain other components as long as the effects of the present embodiment are not impaired.
- the other components include polymers other than the thermoplastic resin, plasticizers such as polyalkylene glycol diester benzoate, calcium carbonate, magnesium carbonate, glass sphere, graphite, carbon black, carbon fiber, glass fiber, and talc. , Wollastonite, mica, alumina, silica, kaolin, whiskers, silicon carbide and other fillers, compatibilizers, elastomers and the like.
- the method for producing the three-dimensional modeling soluble material is not particularly limited, and can be produced by a known method.
- Examples of the method for producing the three-dimensional modeling soluble material include a method in which the raw materials are kneaded with a kneader such as a batch kneader or a twin screw extruder.
- the shape of the soluble material for three-dimensional modeling is not particularly limited, and examples thereof include a pellet shape, a powder shape, and a filament shape, but a filament shape is preferable from the viewpoint of modeling by a 3D printer.
- the diameter of the filament is preferably 0.5 mm or more, 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 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 improving toughness 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 more preferably 10 ° C. lower than the glass transition temperature from the viewpoints 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. It is a manufacturing method of the three-dimensional object by the hot melt lamination system which has a material removal process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.
- the method for producing a three-dimensional object it is possible to suppress a decrease in accuracy of the three-dimensional object, and the dissolution rate in neutral water is large, so that a three-dimensional object precursor can be quickly formed without using a strong alkaline aqueous solution. Can be removed.
- Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material The step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material is performed in a three-dimensional manner using a known hot-melt lamination type 3D printer, except that the material of the support material is the soluble material for three-dimensional modeling.
- a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the object manufacturing method can be used.
- the modeling material that is the material of the three-dimensional object can be used without particular limitation as long as it is a resin that is used as a modeling material in a conventional FDM three-dimensional object manufacturing method.
- the modeling material include ABS resin, PP resin, ASA resin, PS resin, HIPS resin, PVC resin, polylactic acid resin, polycarbonate resin, polyamide resin, polyetherimide resin, polyetheretherketone resin, and polyphenylsulfone resin.
- at least one selected from the group consisting of an ABS resin, a polylactic acid resin, a polycarbonate resin, and a polyamide resin is more preferable, and the ABS resin and the polycarbonate resin are more preferable.
- one or more selected from the group consisting of polyamide resins are more preferred.
- the glass transition temperature of the support material used in the process of obtaining the three-dimensional object precursor is from (the glass transition temperature of the molding material used—20 ° C.) to (the glass transition temperature of the modeling material used) from the viewpoint of modeling by a 3D printer. (Temperature + 20 ° C.) is preferable, and (Glass transition temperature of modeling material to be used ⁇ 15 ° C.) to (Glass transition temperature of modeling material to be used + 15 ° C.) is more preferable.
- 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 more 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. Mass times or less are preferable, 5000 times times or less are more preferable, 1000 times times or less are more preferable, and 100 times 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 washing temperature is preferably 15 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of removing the support material, reducing damage to the three-dimensional object, and economical efficiency, although it depends on the type of modeling material. More preferably, the temperature is more preferably 40 ° C. or more, more preferably 40 ° C. or more, and preferably 85 ° C. or less, more preferably 70 ° C. or less, and further preferably 60 ° C. or less from the same viewpoint.
- 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 thermoplastic resin having the hydrophilic group, And an organic salt compound represented by formula (I).
- the support material has sufficient adhesion with the modeling material, has a high dissolution rate in neutral water, and can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution.
- the present specification further discloses the following composition and production method.
- R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms
- n represents a number of 1 or 2
- n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion.
- X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.
- the hydrophilic group is a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, an oxyethylene group, a hydroxyl group, a carboxyl group, a carboxyl base, an amide group, phosphorus
- One or more selected from the group consisting of an acid group, a phosphate group, a sulfonic acid group, and a sulfonate group is preferable, and one or more selected from the group consisting of a sulfonic acid group and a sulfonate group is more preferable, and sulfonic acid
- the content of the hydrophilic group in the thermoplastic 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 1.0 mmol / g or less, more preferably 0.5 to 3.0 mmol / g, and even more preferably 0.6 to 2.0 mmol / g.
- the soluble material for three-dimensional modeling according to ⁇ 1> or ⁇ 2> further preferably 0.7 to 1.5 mmol / g.
- the thermoplastic resin is preferably at least one selected from the group consisting of a polyester resin, a polyamide resin, an acrylic resin, a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, an ester amide resin, and a urethane resin, from a polyester resin and a polyamide resin.
- the thermoplastic resin has a hydrophilic monomer unit A 1 having the hydrophilic group, a hydrophobic dicarboxylic acid monomer unit B 1 , and a diol monomer unit, and the hydrophilic monomer unit A in the polyester resin.
- the proportion of the hydrophilic monomer unit a 1 1 and to the total of the hydrophobic dicarboxylic acid monomer unit B 1 is a polyester resin is 10 - 70 mol%, the three-dimensional according to any one of ⁇ 1> to ⁇ 4> Soluble material for modeling.
- Monomer A 1 for guiding the hydrophilic monomer unit A 1 is hydroxy group-containing aromatic dicarboxylic acids, primary amino group-containing aromatic dicarboxylic acid, a sulfonic acid group-containing aromatic dicarboxylic acids, and sulfonic At least one selected from the group consisting of acid-base-containing aromatic dicarboxylic acids is preferred.
- 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. g or less is preferred, 1.5 mmol / g or less is more preferred, 1.0 mmol / g or less is more preferred, 0.5 to 3.0 mmol / g is preferred, 0.6 to 1.5 mmol / g is more preferred,
- the proportion of a substance amount of the hydrophilic monomer unit A 1 is not less than 5 mol%, preferably at least 7 mol%, more preferably at least 10 mol% 12 mol% or more, more preferably 35 mol% or less, preferably 33 mol% or less, more preferably 32 mol% or less, still more preferably 30 mol% or less, more preferably 5 to 35 mol%, even more preferably 7 to 33 mol%.
- at least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable, and 2,6-naphthalenedicarboxylic acid is still more preferable.
- the molar ratio of the hydrophilic monomer unit A 1 to the hydrophobic dicarboxylic acid monomer unit B 1 is preferably 10/90 or more. 15/85 or more is more preferable, 18/82 or more is more preferable, 20/80 or more is more preferable, 70/30 or less is preferable, 65/35 or less is more preferable, 60/40 or less is more preferable, 40
- 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 more preferable, 45 mol% or less is more preferable, ⁇ 5> to ⁇ 11>
- the soluble material for three-dimensional modeling according to any one of the above.
- 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 polyester resin to the total of all the dicarboxylic acid monomer units containing the hydrophilic monomer unit A 1, the ratio of the hydrophilic monomer units A 1, and the ratio of the dicarboxylic acid monomer units B 1 is, respectively 10
- the polyester resin ⁇ is preferably in the range of ⁇ 70 mol% and 30 to 90 mol%
- the dicarboxylic acid B 1 for obtaining the dicarboxylic acid monomer unit B 1 is 2,6-naphthalenedicarboxylic acid, ⁇ 5> to ⁇ 13>
- 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 total of all monomer units in the polyamide resin the ratio of the hydrophilic monomer unit a 2 is 2.5 - 40 mol%, ⁇ 4> 3D modeling for soluble material as claimed in any one of the ⁇ ⁇ 14> for.
- ⁇ 16> monomer A 2 for inducing the hydrophilic monomer unit A 2 are hydroxy group-containing aromatic dicarboxylic acids, primary amino group-containing aromatic dicarboxylic acid, a sulfonic acid group-containing aromatic dicarboxylic acids, and sulfonic More preferred are acid-base-containing aromatic dicarboxylic acids, such as 5-hydroxyisophthalic acid, 1,3,5-benzenetricarboxylic acid, 5-aminoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo- More preferably, at least one selected from the group consisting of 2,6-naphthalenedicarboxylic acid, more preferably at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid,
- 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, further preferably 0.7 mmol / g or more, 3.0 mmol / g. g or less is preferable, 2.0 mmol / g or less is more preferable, 1.5 mmol / g or less is more preferable, 0.5 to 3.0 mmol / g is preferable, and 0.6 to 2.0 mmol / g is more preferable.
- the proportion of a substance amount of the hydrophilic monomer unit A 2 is not less than 2.5 mol%, preferably at least 4 mol%, more than 6 mol% More preferably, 8 mol% or more is further preferable, 10 mol% or more is more preferable, 40 mol% or less is preferable, 35 mol% or less is preferable, 31 mol% or less is more preferable, 25 mol% or less is further preferable, and 20 mol% or less is still more preferable.
- 15 mol% or less is more preferable, 10 mol% or less is more preferable, 8 mol% or less is more preferable, 2.5 to 40 mol% is preferable, 4 to 35 mol% is more preferable, and 6 to 31 mol% is more preferable. 8-20 mol% is even more
- 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 is preferably at least 10 mol%, more not less than 20 mol%
- 30 mol% or more is more preferable, 35 mol% or more is more preferable
- 40 mol% or more is more preferable
- 42 mol% or more is more preferable
- 47.5 mol% or less is preferable
- 45 mol% or less is more preferable
- 42 mol% The following is more preferable, 40 mol% or less is more preferable, 10 to 47.5 mol% is preferable, 20 to 45 mol% is more preferable, and 30 to 42 mol% is further preferable, ⁇ 15> to ⁇ 19> Soluble material for 3D modeling.
- the molar ratio of the hydrophilic monomer unit A 2 to the hydrophobic dicarboxylic acid monomer unit B 2 is preferably 10/90 or more. 15/85 or more is more preferable, 18/82 or more is more preferable, 20/80 or more is more preferable, 50/50 or less is preferable, 40/60 or less is more preferable, 30/70 or less is more preferable, 25
- the weight average molecular weight of the thermoplastic resin is preferably 3000 or more, more preferably 3500 or more, further preferably 4000 or more, preferably 70000 or less, more preferably 50000 or less, further preferably 30000 or less, and 25000 or less. More preferably, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 21>.
- the glass transition temperature (Tg) of the thermoplastic resin is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, and 250 ° C. or lower, 220 ° C. The following is preferable, 180 ° C.
- thermoplastic resin in the three-dimensional modeling soluble material is preferably 70% by mass or more, more preferably 80% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less.
- the hydrocarbon group is an aliphatic hydrocarbon group
- the hydrocarbon group has preferably 1 or more, more preferably 4 or more, still more preferably 8 or more, preferably 30 or less, and preferably 25 or less.
- the hydrocarbon group preferably has 3 or more carbon atoms, more preferably 5 or more, still more preferably 6 or more, still more preferably 10 or more, The soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 25>, preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less.
- the hydrocarbon group is an aromatic hydrocarbon group
- the hydrocarbon group preferably has 6 or more carbon atoms, more preferably 8 or more, further preferably 10 or more, preferably 30 or less, and 25 or less. More preferably, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 26>.
- the substituent preferably contains one or more selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom.
- a hydrocarbon group having 1 to 22 carbon atoms or a halogenated alkyl group is more preferable, a hydrocarbon group having 1 to 16 carbon atoms or a halogenated alkyl group is more preferable, and a hydrocarbon group having 1 to 12 carbon atoms or a halogenated alkyl group is more preferable.
- X n + represents sodium ion, potassium ion, lithium ion, ammonium ion, phosphonium ion, magnesium ion, calcium ion, barium ion, zinc ion, or phosphonium ion, sodium ion , Potassium ion, lithium ion, magnesium ion, ammonium ion, or phosphonium ion is preferable, sodium ion, lithium ion, ammonium ion, or phosphonium ion is more preferable, lithium ion or phosphonium ion is more preferable, and phosphonium ion is further more preferable.
- ⁇ 30> The three-dimensional modeling soluble material according to ⁇ 29>, wherein the phosphonium ion is preferably a tetraalkylphosphonium ion, and more preferably a tetrabutylphosphonium ion.
- the mass ratio of the organic salt compound to the thermoplastic resin is preferably 0.5 or more, more preferably 2 or more, further preferably 6 or more, preferably 30 or less, more preferably 20 or less, and 15 or less. More preferably, the three-dimensional modeling soluble material according to any one of ⁇ 1> to ⁇ 30>.
- the amount of the sulfonate ion substance / the amount of the hydrophilic group of the thermoplastic resin is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.05 or more, and more preferably 0.15 or more.
- the glass transition temperature of the soluble material for three-dimensional modeling 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 preferably 250 ° C. or lower.
- ⁇ 34> The three-dimensional modeling soluble material according to any one of ⁇ 1> to ⁇ 33>, wherein the three-dimensional modeling soluble material preferably has a filament shape.
- 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
- the modeling material that is the material of the three-dimensional object is ABS resin, PP resin, ASA resin, PS resin, HIPS resin, PVC resin, polylactic acid resin, polycarbonate resin, polyamide resin, polyetherimide resin, polyether Thermoplastic resins such as ether ketone resins and polyphenyl sulfone resins are preferable, and at least one selected from the group consisting of ABS resins, polylactic acid resins, polycarbonate resins, and polyamide resins is more preferable.
- ABS resins, polycarbonate resins, and polyamides The method for producing a three-dimensional object according to ⁇ 35>, wherein one or more selected from the group consisting of resins is more preferable.
- the glass transition temperature of the support material used in the step of obtaining the three-dimensional object precursor is (glass transition temperature of the modeling material used ⁇ 20 ° C.) to (glass transition temperature of the modeling material used + 20 ° C.).
- 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,
- 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 3% by mass or more. More preferably, 50% or less is preferable, 40% or less is preferable, 30% or less is preferable, and 20% or less is preferable.
- 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 times by mass with respect to the support material.
- the 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, ⁇ 35> to ⁇ 42>.
- 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.
- R 1 represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms
- n represents a number of 1 or 2
- n + represents sodium ion, potassium ion, lithium ion, ammonium ion, or phosphonium ion.
- X n + represents magnesium ion, calcium ion, barium ion, or zinc ion.
- ⁇ 47> Use of the thermoplastic resin according to any one of ⁇ 1> to ⁇ 34> as a soluble material for three-dimensional modeling.
- composition of thermoplastic resin can be determined by proton NMR measurement using Agilent NMR and MR400.
- Measuring device HLC-8320GPC (manufactured by TOSOH) Eluent: HFIP / 0.5 mM sodium trifluoroacetate Flow rate: 0.2 mL / min Measurement temperature: 40 ° C
- Example 1 [Preparation of soluble materials for 3D modeling] 9. 84.4 g of polyester resin 1 obtained in Synthesis Example 1, Clarity LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 5 g, Bondfast (registered trademark) 7B as a compatibilizer, 4.2 g (manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer), ELECUT S-418 (manufactured by Takemoto Yushi Co., Ltd .: organic salt: dodecylbenzene) 0.8 g of sulfonic acid tetrabutylphosphonium salt) was dried at 60 ° C.
- Clarity LA2250 manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: poly
- Example 2 [Preparation of soluble materials for 3D modeling] 9. 81.6 g of polyester resin 1 obtained in Synthesis Example 1 and Clarity LA2250 (Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 2 g, Bondfast (registered trademark) 7B (commercially available from Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.1 g, Elecut S-418 (manufactured by Takemoto Yushi Co., Ltd .: organic salt: dodecylbenzene) 4.1 g of sulfonic acid tetrabutylphosphonium salt) is dried at 60 ° C.
- melt-kneaded at 230 ° C., 90 r / min, 10 minutes using a melt kneader (Toyo Seiki Seisakusho: Labo Plastic Mill 4C150), A three-dimensional modeling soluble material 2 which was a white mixture was obtained.
- Example 3 [Preparation of soluble materials for 3D modeling] 8. 88.4 g of polyester resin 1 obtained in Synthesis Example 1 and clarity LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 8 g, Bondfast (registered trademark) 7B as a compatibilizer 3.9 g (manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer), Elecut S-418 (manufactured by Takemoto Yushi Co., Ltd .: organic salt: dodecylbenzene) 7.8 g of tetrabutylphosphonium sulfonate) was dried at 60 ° C.
- Example 4 [Preparation of soluble materials for 3D modeling] 9. 84.4 g of polyester resin 1 obtained in Synthesis Example 1, Clarity LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 5 g, Bondfast (registered trademark) 7B (commercially available from Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.2 g, lithium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 g After drying at 60 ° C.
- Clarity LA2250 manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer
- the mixture is melt-kneaded at 230 ° C., 90 r / min for 10 minutes using a melt kneader (Toyo Seiki Seisakusho: Labo Plastic Mill 4C150), and is a white mixture, a soluble material for three-dimensional modeling 4 was obtained.
- a melt kneader Toyo Seiki Seisakusho: Labo Plastic Mill 4C150
- Example 5 [Preparation of soluble materials for 3D modeling] 9. 81.6 g of polyester resin 1 obtained in Synthesis Example 1 and Clarity LA2250 (Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 2 g, Bondfast (registered trademark) 7B (commercially available from Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.1 g, lithium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) 4.1 g After drying at 60 ° C.
- the mixture is melt-kneaded at 230 ° C., 90 r / min for 10 minutes using a melt kneader (Toyo Seiki Seisakusho: Labo Plastic Mill 4C150), and is a white mixture, a soluble material for three-dimensional modeling 5 was obtained.
- a melt kneader Toyo Seiki Seisakusho: Labo Plastic Mill 4C150
- Example 6 [Preparation of soluble materials for 3D modeling] 8. 78.4 g of polyester resin 1 obtained in Synthesis Example 1, Clarity LA2250 (manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 8 g, Bondfast (registered trademark) 7B (manufactured by Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 3.9 g, lithium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) 7.8 g After drying at 60 ° C.
- Clarity LA2250 manufactured by Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer
- the mixture is melt-kneaded at 230 ° C., 90 r / min for 10 minutes using a melt kneader (Toyo Seiki Seisakusho: Labo Plastic Mill 4C150), and is a white mixture, a soluble material for three-dimensional modeling 6 was obtained.
- a melt kneader Toyo Seiki Seisakusho: Labo Plastic Mill 4C150
- Example 7 [Preparation of soluble materials for 3D modeling] 9. 83.0 g of polyester resin 2 obtained in Synthesis Example 2, Clarity LA2250 (Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 4 g, Bondfast (registered trademark) 7B (commercially available from Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) 4.1 g, Elecut S-418 (manufactured by Takemoto Yushi Co., Ltd .: organic salt: dodecylbenzene) 2.5 g of sulfonic acid tetrabutylphosphonium salt) is dried at 60 ° C.
- Clarity LA2250 Kerray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-poly
- melt-kneaded at 230 ° C., 90 r / min for 10 minutes using a melt kneader (Toyo Seiki Seisakusho: Labo Plastic Mill 4C150), A three-dimensional modeling soluble material 8 which was a white mixture was obtained.
- Example 8 [Preparation of soluble materials for 3D modeling] 9. 81.6 g of polyester resin 2 obtained in Synthesis Example 2 and clarity LA2250 (Kuraray Co., Ltd .: thermoplastic elastomer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer) 2 g, Bondfast (registered trademark) 7B (commercially available from Sumitomo Chemical Co., Ltd .: ethylene-vinyl acetate-glycidyl methacrylate copolymer) as the compatibilizer, 4.1 g, ELECUT S-418 (manufactured by Takemoto Yushi Co., Ltd .: organic salt: dodecylbenzene) 4.1 g of sulfonic acid tetrabutylphosphonium salt) is dried at 60 ° C.
- [Adhesiveness with molding material] [Adhesiveness with ABS resin] (Examples 1 to 7 and Comparative Examples 1 and 2) Supply the resin filaments according to Examples 1 to 7 and Comparative Examples 1 and 2 and ABSP430 (manufactured by Stratasys: modeling material filament: ABS resin, glass transition temperature: 108 ° C.) formed by capillograph to the 3D printer Replicator 2X manufactured by Makerbot Then, the samples were alternately extruded from heat nozzles having temperatures of 250 ° C. and 230 ° C., respectively, and formed into evaluation samples according to Examples 1 to 7 and Comparative Examples 1 and 2, respectively.
- One photograph of the evaluation sample after modeling is shown in FIG. In FIG.
- an evaluation sample 1 has a support material 12 laminated on a modeling material 11.
- the difficulty in peeling when the resin interface between the modeling material 11 and the support material 12 was shaved with a spatula was evaluated according to the following criteria, The adhesion of was evaluated.
- the evaluation results are shown in Table 1.
- C It peels off when touched with a metal spatula.
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Abstract
Description
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
本実施形態の三次元造形用可溶性材料は、熱溶融積層方式の3Dプリンタによって三次元物体を製造する際に、当該三次元物体を支持するサポート材の材料として用いられる三次元造形用可溶性材料であって、親水性基を有する熱可塑性樹脂と、下記一般式(I)で示される有機塩化合物とを含有する。
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
前記熱可塑性樹脂は、強アルカリ水溶液ではないpHが6~8の中性水への溶解性の観点から、親水性基を有する。当該親水性基としては、第1級アミノ基、第2級アミノ基、第3級アミノ基、第4級アンモニウム塩基、オキシエチレン基、ヒドロキシル基、カルボキシル基、カルボキシル塩基、アミド基、リン酸基、リン酸塩基、スルホン酸基、及びスルホン酸塩基からなる群より選ばれる1種以上が例示できる。当該親水性基は、同様の観点から、スルホン酸基、及びスルホン酸塩基からなる群より選ばれる1種以上がより好ましく、スルホン酸塩基がさらに好ましい。
前記ポリエステル樹脂としては、前記親水性基を有する親水性モノマーユニットA1、疎水性ジカルボン酸モノマーユニットB1、及びジオールモノマーユニットを有し、前記ポリエステル樹脂中の親水性モノマーユニットA1及び疎水性ジカルボン酸モノマーユニットB1の合計に対する前記親水性モノマーユニットA1の割合が10~70mol%であるポリエステル樹脂が例示できる。
前記ポリエステル樹脂は、前記親水性基を有する親水性モノマーユニットA1を有する。前記親水性モノマーユニットA1は、前記親水性基を有するモノマーユニットであれば特に限定されない。また、当該親水性モノマーユニットA1を誘導するためのモノマーをモノマーA1とも称する。
前記ポリエステル樹脂は、疎水性ジカルボン酸モノマーユニットB1を有する。当該ジカルボン酸モノマーユニットB1は前記親水性基を有さない。本明細書において、当該疎水性ジカルボン酸モノマーユニットB1を誘導するためのジカルボン酸をジカルボン酸B1とも称する。
前記ポリエステル樹脂は、ジオールモノマーユニットを有する。前記ジオールモノマーユニットを誘導するためのジオールを、ジオールCとも称する。
前記ポリエステル樹脂αにおける、前記親水性モノマーユニットA1を含む全ジカルボン酸モノマーユニットの合計に対する、前記親水性モノマーユニットA1の割合は、中性水への溶解性、耐吸湿性、及び3Dプリンタによる造形に求められる耐熱性の観点から、10mol%以上が好ましく、20mol%以上がより好ましく、同様の観点から、70mol%以下が好ましく、65mol%以下がより好ましく、60mol%以下がさらに好ましく、40mol%以下がよりさらに好ましく、27mol%以下がよりさらに好ましい。
(前記一般式(II)中、p1はエチレン2,6-ナフタレンジカルボキシレートの重合度、q1はエチレン5-スルホイソフタレートの重合度の数を表す。ただし、エチレン2,6-ナフタレンジカルボキシレートとエチレン5-スルホイソフタレートはブロック結合及び/又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。)
(前記一般式(III)中、p2はエチレン2,6-ナフタレンジカルボキシレートの重合度、q2はエチレン5-スルホイソフタレートの重合度、r2はビスフェノキシエタノールフルオレンと2,6-ナフタレンジカルボン酸との縮合物の重合度、s2はビスフェノキシエタノールフルオレンと5-スルホイソフタル酸との縮合物の重合度の数を表す。ただし、エチレン2,6-ナフタレンジカルボキシレート、エチレン5-スルホイソフタレート、ビスフェノキシエタノールフルオレンと2,6-ナフタレンジカルボン酸との縮合物、ビスフェノキシエタノールフルオレンと5-スルホイソフタル酸との縮合物はブロック結合及び/又はランダム結合であり、中性水への溶解性の観点からランダム結合がより好ましい。)
前記ポリアミド樹脂としては、親水性基を有する親水性モノマーユニットA2、疎水性ジカルボン酸モノマーユニットB2、及び疎水性ジアミンモノマーユニットを有し、前記ポリアミド樹脂中の全モノマーユニットの合計に対する前記親水性モノマーユニットA2の割合が2.5~40mol%であるポリアミド樹脂が例示できる。
前記ポリアミド樹脂は、親水性基を有する親水性モノマーユニットA2を有する。前記親水性モノマーユニットA2は、親水性基を有するモノマーユニットであれば特に限定されない。また、当該親水性モノマーユニットA2を誘導するためのモノマーをモノマーA2とも称する。
前記ポリアミド樹脂は、疎水性ジカルボン酸モノマーユニットB2を有する。当該ジカルボン酸モノマーユニットB2は前記親水性基を有さない。本明細書において、当該疎水性ジカルボン酸モノマーユニットB2を誘導するためのジカルボン酸をジカルボン酸B2とも称する。
前記ポリアミド樹脂は、疎水性ジアミンモノマーユニットを有する。当該疎水性ジアミンモノマーユニットは、前記親水性基を有さない。前記疎水性ジアミンモノマーユニットを誘導するためのジアミンを、ジアミンCとも称する。
前記三次元造形用可溶性材料は、造形材との接着性を向上させる観点から、前記一般式(I)で示される有機塩化合物を含む。
本実施形態の三次元物体の製造方法は、三次元物体及びサポート材を含む三次元物体前駆体を得る工程、及び当該三次元物体前駆体を中性水に接触させ、サポート材を除去するサポート材除去工程を有する熱溶融積層方式による三次元物体の製造方法であって、前記サポート材の材料が、前記三次元造形用可溶性材料である。当該三次元物体の製造方法によれば、三次元物体の精度低下を抑制することができ、かつ、中性水への溶解速度が大きく、強アルカリ水溶液を用いること無く三次元物体前駆体から速やかに除去することができる。
三次元物体及びサポート材を含む三次元物体前駆体を得る工程は、前記サポート材の材料が前記三次元造形用可溶性材料である点を除けば、公知の熱溶融積層方式の3Dプリンタによる三次元物体の製造方法における三次元物体及びサポート材を含む三次元物体前駆体を得る工程を利用することができる。
前記サポート材除去工程において、サポート材の除去は三次元物体前駆体を中性水に接触させることによって行われる。三次元物体前駆体を中性水に接触させる手法は、コストの観点、及び作業の容易さの観点から、三次元物体前駆体を中性水に浸漬させる手法が好ましい。サポート材の除去性を向上させる観点から、浸漬中に超音波を照射し、サポート材の溶解を促すこともできる。
前記中性水としては、イオン交換水、純水、水道水、工業用水が挙げられるが、経済性の観点からイオン交換水、水道水が好ましい。また、中性水は造形した三次元物体にダメージを与えない範囲で水溶性有機溶媒を含んでいてもよい。水溶性有機溶媒としては、メタノール、エタノール、2-プロパノールなどの低級アルコール類、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノターシャリーブチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類、アセトン、メチルエチルケトンなどのケトン類が挙げられる。中性水が前記水溶性有機溶媒を含む場合、溶解性と造形した三次元物体へのダメージ性の観点から中性水中の前記水溶性有機溶媒の含有量は0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上がさらに好ましく、3質量%以上がさらに好ましく、また、50%質量以下が好ましく、40%質量以下が好ましく、30%質量以下が好ましく、20%質量以下が好ましい。
本実施形態のサポート材は、熱溶融積層方式の3Dプリンタによって三次元物体を製造する際に、当該三次元物体を支持するサポート材であって、前記親水性基を有する熱可塑性樹脂と、前記一般式(I)で示される有機塩化合物とを含有する。当該サポート材は、造形材と十分な接着性を有し、かつ、中性水への溶解速度が大きく、強アルカリ水溶液を用いること無く三次元物体前駆体から速やかに除去することができる。
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
<2>前記親水性基が、第1級アミノ基、第2級アミノ基、第3級アミノ基、第4級アンモニウム塩基、オキシエチレン基、ヒドロキシル基、カルボキシル基、カルボキシル塩基、アミド基、リン酸基、リン酸塩基、スルホン酸基、及びスルホン酸塩基からなる群より選ばれる1種以上が好ましく、スルホン酸基、及びスルホン酸塩基からなる群より選ばれる1種以上がより好ましく、スルホン酸塩基がさらに好ましい、<1>に記載の三次元造形用可溶性材料。
<3>前記熱可塑性樹脂中の前記親水性基の含有量が、0.5mmol/g以上が好ましく、0.6mmol/g以上がより好ましく、0.7mmol/g以上がさらに好ましく、3.0mmol/g以下が好ましく、2.0mmol/g以下がより好ましく、1.0mmol/g以下がさらに好ましく、0.5~3.0mmol/gが好ましく、0.6~2.0mmol/gがより好ましく、0.7~1.5mmol/gがさらに好ましい、<1>又は<2>に記載の三次元造形用可溶性材料。
<4>前記熱可塑性樹脂が、ポリエステル樹脂、ポリアミド樹脂、アクリル樹脂、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、エステルアミド樹脂、ウレタン樹脂からなる群より選ばれる1種以上が好ましく、ポリエステル樹脂及びポリアミド樹脂からなる群より選ばれる1種以上がより好ましい、<1>~<3>のいずれかに記載の三次元造形用可溶性材料。
<5>前記熱可塑性樹脂が、前記親水性基を有する親水性モノマーユニットA1、疎水性ジカルボン酸モノマーユニットB1、及びジオールモノマーユニットを有し、前記ポリエステル樹脂中の前記親水性モノマーユニットA1及び前記疎水性ジカルボン酸モノマーユニットB1の合計に対する前記親水性モノマーユニットA1の割合が10~70mol%であるポリエステル樹脂である、<1>~<4>のいずれかに記載の三次元造形用可溶性材料。
<6>前記親水性モノマーユニットA1を誘導するためのモノマーA1は、ヒドロキシ基含有芳香族ジカルボン酸、第1級アミノ基含有芳香族ジカルボン酸、スルホン酸基含有芳香族ジカルボン酸、及びスルホン酸塩基含有芳香族ジカルボン酸からなる群より選ばれる少なくとも1種以上が好ましく、5-ヒドロキシイソフタル酸、1,3,5-ベンゼントリカルボン酸、5-アミノイソフタル酸、5-スルホイソフタル酸、2-スルホテレフタル酸、及び4-スルホ-2,6-ナフタレンジカルボン酸からなる群より選ばれる少なくとも1種以上がより好ましく、5-スルホイソフタル酸、及び2-スルホテレフタル酸からなる群より選ばれる少なくとも1種以上がさらに好ましく、5-スルホイソフタル酸がよりさらに好ましい、<5>に記載の三次元造形用可溶性材料。
<7>前記ポリエステル樹脂中の前記親水性基の含有量は、0.5mmol/g以上が好ましく、0.6mmol/g以上がより好ましく、0.7mmol/g以上がさらに好ましく、3.0mmol/g以下が好ましく、1.5mmol/g以下がより好ましく、1.0mmol/g以下がさらに好ましく、0.5~3.0mmol/gが好ましく、0.6~1.5mmol/gがより好ましく、0.7~1.0mmol/gがさらに好ましい、<4>~<6>のいずれかに記載の三次元造形用可溶性材料。
<8>前記ポリエステル樹脂中の全モノマーユニットの物質量の合計に対する、前記親水性モノマーユニットA1の物質量の割合は、5mol%以上であり、7mol%以上が好ましく、10mol%以上がより好ましく、12mol%以上がさらに好ましく、35mol%以下であり、33mol%以下が好ましく、32mol%以下がより好ましく、30mol%以下がさらに好ましく、5~35mol%が好ましく、7~33mol%がより好ましく、10~32mol%がさらに好ましく、12~30mol%がよりさらに好ましく、8~13mol%がよりさらに好ましい、<5>~<7>のいずれかに記載の三次元造形用可溶性材料。
<9>前記疎水性ジカルボン酸モノマーユニットB1を誘導するためのジカルボン酸B1は、芳香族ジカルボン酸、脂肪族ジカルボン酸、及び脂環式ジカルボン酸からなる群より選ばれる少なくとも1種以上が好ましく、テレフタル酸、イソフタル酸、2,5-フランジカルボン酸、2,6-ナフタレンジカルボン酸、1,4-シクロヘキサンジカルボン酸、及び1,3-アダマンタンジカルボン酸からなる群より選ばれる少なくとも1種以上がより好ましく、テレフタル酸、2,5-フランジカルボン酸、及び2,6-ナフタレンジカルボン酸からなる群より選ばれる少なくとも1種以上がさらに好ましく、2,6-ナフタレンジカルボン酸がよりさらに好ましい、<5>~<8>のいずれかに記載の三次元造形用可溶性材料。
<10>前記ポリエステル樹脂中の全モノマーユニットの物質量の合計に対する、前記ポリエステル樹脂中の前記疎水性ジカルボン酸モノマーユニットB1の物質量の割合は、15mol%以上が好ましく、18mol%以上がより好ましく、20mol%以上がさらに好ましく、45mol%以下が好ましく、42mol%以下がより好ましく、40mol%以下がさらに好ましく、15~45mol%が好ましく、20~42mol%がより好ましく、30~40mol%がさらに好ましい、<5>~<9>のいずれかに記載の三次元造形用可溶性材料。
<11>前記親水性モノマーユニットA1と前記疎水性ジカルボン酸モノマーユニットB1のmol比(前記親水性モノマーユニットA1/前記疎水性ジカルボン酸モノマーユニットB1)は、10/90以上が好ましく、15/85以上がより好ましく、18/82以上がさらに好ましく、20/80以上がよりさらに好ましく、70/30以下が好ましく、65/35以下がより好ましく、60/40以下がさらに好ましく、40/60以下がよりさらに好ましく、26/74以下がよりさらに好ましい、<5>~<10>のいずれかに記載の三次元造形用可溶性材料。
<12>前記ポリエステル樹脂中の全ジオールモノマーユニットの合計に対するジエチレングリコールユニットの割合は、5mol%以上が好ましく、10mol%以上がより好ましく、15mol%以上がさらに好ましく、20mol%以上がさらに好ましく、25mol%以上がよりさらに好ましく、30mol%以上がよりさらに好ましく、60mol%以下が好ましく、55mol%以下がより好ましく、50mol%以下がさらに好ましく、45mol%以下がよりさらに好ましい、<5>~<11>のいずれかに記載の三次元造形用可溶性材料。
<13>前記ポリエステル樹脂中の全ジオールモノマーユニットの合計に対する、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、ジエチレングリコール、ジプロピレングリコール、1,4-シクロヘキサンジメタノール、水添ビスフェノールA、イソソルバイド、ビスフェノキシエタノールフルオレン、ビスフェノールフルオレン、ビスクレゾキシエタノールフルオレン、及びビスクレゾールフルオレンの合計の割合は、80mol%以上が好ましく、90mol%以上がより好ましく、95mol%以上がさらに好ましく、98mol%以上がよりさらに好ましく、実質的に100mol%がよりさらに好ましく、100mol%がよりさらに好ましい、<5>~<12>のいずれかに記載の三次元造形用可溶性材料。
<14>前記ポリエステル樹脂は、前記親水性モノマーユニットA1を含む全ジカルボン酸モノマーユニットの合計に対する、前記親水性モノマーユニットA1の割合、及び前記ジカルボン酸モノマーユニットB1の割合が、それぞれ10~70mol%、及び30~90mol%であり、前記ジカルボン酸モノマーユニットB1を得るためのジカルボン酸B1が2,6-ナフタレンジカルボン酸であるポリエステル樹脂αが好ましい、<5>~<13>のいずれかに記載の三次元造形用可溶性材料。
<15>前記ポリアミド樹脂が、前記親水性基を有する親水性モノマーユニットA2、疎水性ジカルボン酸モノマーユニットB2、及び疎水性ジアミンモノマーユニットを有し、前記ポリアミド樹脂中の全モノマーユニットの合計に対する前記親水性モノマーユニットA2の割合が2.5~40mol%である、<4>~<14>のいずれかに記載の三次元造形用可溶性材料。
<16>前記親水性モノマーユニットA2を誘導するためのモノマーA2は、ヒドロキシ基含有芳香族ジカルボン酸、第1級アミノ基含有芳香族ジカルボン酸、スルホン酸基含有芳香族ジカルボン酸、及びスルホン酸塩基含有芳香族ジカルボン酸がより好ましく、5-ヒドロキシイソフタル酸、1,3,5-ベンゼントリカルボン酸、5-アミノイソフタル酸、5-スルホイソフタル酸、2-スルホテレフタル酸、及び4-スルホ-2,6-ナフタレンジカルボン酸からなる群より選ばれる少なくとも1種以上がより好ましく、5-スルホイソフタル酸、及び2-スルホテレフタル酸からなる群より選ばれる少なくとも1種以上がさらに好ましく、5-スルホイソフタル酸がよりさらに好ましい、<15>に記載の三次元造形用可溶性材料。
<17>前記ポリアミド樹脂中の前記親水性基の含有量は、0.5mmol/g以上が好ましく、0.6mmol/g以上がより好ましく、0.7mmol/g以上がさらに好ましく、3.0mmol/g以下が好ましく、2.0mmol/g以下がより好ましく、1.5mmol/g以下がさらに好ましく、0.5~3.0mmol/gが好ましく、0.6~2.0mmol/gがより好ましく、0.7~1.5mmol/gがさらに好ましい、<4>、<15>、<16>のいずれかに記載の三次元造形用可溶性材料。
<18>前記ポリアミド樹脂中の全モノマーユニットの物質量の合計に対する、前記親水性モノマーユニットA2の物質量の割合は、2.5mol%以上であり、4mol%以上が好ましく、6mol%以上がより好ましく、8mol%以上がさらに好ましく、10mol%以上がよりさらに好ましく、40mol%以下であり、35mol%以下が好ましく、31mol%以下がより好ましく、25mol%以下がさらに好ましく、20mol%以下がよりさらに好ましく、15mol%以下がよりさらに好ましく、10mol%以下がよりさらに好ましく、8mol%以下がよりさらに好ましく、2.5~40mol%が好ましく、4~35mol%がより好ましく、6~31mol%がさらに好ましく、8~20mol%がよりさらに好ましく、8~15mol%がよりさらに好ましく、8~12mol%がよりさらに好ましい、<15>~<17>のいずれかに記載の三次元造形用可溶性材料。
<19>前記疎水性ジカルボン酸モノマーユニットB2を誘導するためのジカルボン酸B2は、芳香族ジカルボン酸、脂肪族ジカルボン酸、及び脂環式ジカルボン酸からなる群より選ばれる少なくとも1種以上が好ましく、テレフタル酸、イソフタル酸、2,5-フランジカルボン酸、2,6-ナフタレンジカルボン酸、1,4-シクロヘキサンジカルボン酸、及び1,3-アダマンタンジカルボン酸からなる群より選ばれる少なくとも1種以上がより好ましく、テレフタル酸、2,5-フランジカルボン酸、及び2,6-ナフタレンジカルボン酸からなる群より選ばれる少なくとも1種以上がさらに好ましく、テレフタル酸がよりさらに好ましい、<15>~<18>のいずれかに記載の三次元造形用可溶性材料。
<20>前記ポリアミド樹脂中の全モノマーユニットの物質量の合計に対する、前記ポリアミド樹脂中の前記疎水性ジカルボン酸モノマーユニットB2の物質量の割合は、10mol%以上が好ましく、20mol%以上がより好ましく、30mol%以上がさらに好ましく、35mol%以上がよりさらに好ましく、40mol%以上がよりさらに好ましく、42mol%以上がよりさらに好ましく、47.5mol%以下が好ましく、45mol%以下がより好ましく、42mol%以下がさらに好ましく、40mol%以下がよりさらに好ましく、10~47.5mol%が好ましく、20~45mol%がより好ましく、30~42mol%がさらに好ましい、<15>~<19>のいずれかに記載の三次元造形用可溶性材料。
<21>前記親水性モノマーユニットA2と前記疎水性ジカルボン酸モノマーユニットB2のmol比(前記親水性モノマーユニットA2/前記疎水性ジカルボン酸モノマーユニットB2)は、10/90以上が好ましく、15/85以上がより好ましく、18/82以上がさらに好ましく、20/80以上がよりさらに好ましく、50/50以下が好ましく、40/60以下がより好ましく、30/70以下がさらに好ましく、25/75以下がよりさらに好ましい、<15>~<20>のいずれかに記載の三次元造形用可溶性材料。
<22>前記熱可塑性樹脂の重量平均分子量は、3000以上が好ましく、3500以上がより好ましく、4000以上がさらに好ましく、70000以下が好ましく、50000以下がより好ましく、30000以下がさらに好ましく、25000以下がよりさらに好ましい、<1>~<21>のいずれかに記載の三次元造形用可溶性材料。
<23>前記熱可塑性樹脂のガラス転移温度(Tg)は、50℃以上であり、60℃以上が好ましく、70℃以上がより好ましく、80℃以上がさらに好ましく、250℃以下であり、220℃以下が好ましく、180℃以下がより好ましく、160℃以下がさらに好ましく、140℃以下がよりさらに好ましく、120℃以下がよりさらに好ましい、<1>~<22>のいずれかに記載の三次元造形用可溶性材料。
<24>前記三次元造形用可溶性材料中の前記熱可塑性樹脂の含有量は、70質量%以上が好ましく、80質量%以上がより好ましく、95質量%以下が好ましく、90質量%以下がより好ましい、<1>~<23>のいずれかに記載の三次元造形用可溶性材料。
<25>前記炭化水素基が脂肪族炭化水素基の場合、当該炭化水素基の炭素数は、1以上が好ましく、4以上がより好ましく、8以上がさらに好ましく、30以下が好ましく、25以下がより好ましく、20以下がさらに好ましい、<1>~<24>のいずれかに記載の三次元造形用可溶性材料。
<26>前記炭化水素基が脂環式炭化水素基の場合、当該炭化水素基の炭素数は、3以上が好ましく、5以上がより好ましく、6以上がさらに好ましく、10以上がよりさらに好ましく、30以下が好ましく、25以下がより好ましく、20以下がさらに好ましい、<1>~<25>のいずれかに記載の三次元造形用可溶性材料。
<27>前記炭化水素基が芳香族炭化水素基の場合、当該炭化水素基の炭素数は、6以上が好ましく、8以上がより好ましく、10以上がさらに好ましく、30以下が好ましく、25以下がより好ましい、<1>~<26>のいずれかに記載の三次元造形用可溶性材料。
<28>前記置換基は、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子、及びケイ素原子、並びにハロゲン原子からなる群より選ばれる1種以上を含むものが好ましく、中でも炭素数1~22の炭化水素基又はハロゲン化アルキル基がより好ましく、炭素数1~16の炭化水素基又はハロゲン化アルキル基がさらに好ましく、炭素数1~12の炭化水素基又はハロゲン化アルキル基がよりさらに好ましく、炭素数1~12の炭化水素基がよりさらに好ましい、<1>~<27>のいずれかに記載の三次元造形用可溶性材料。
<29>前記一般式(I)中、Xn+は、ナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、ホスホニウムイオン、マグネシウムイオン、カルシウムイオン、バリウムイオン、亜鉛イオン、又はホスホニウムイオンを示し、ナトリウムイオン、カリウムイオン、リチウムイオン、マグネシウムイオン、アンモニウムイオン、又はホスホニウムイオンが好ましく、ナトリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンがより好ましく、リチウムイオン、又はホスホニウムイオンがさらに好ましく、ホスホニウムイオンがよりさらに好ましい、<1>~<28>のいずれかに記載の三次元造形用可溶性材料。
<30>前記ホスホニウムイオンは、テトラアルキルホスホニウムイオンが好ましく、テトラブチルホスホニウムイオンがより好ましい、<29>に記載の三次元造形用可溶性材料。
<31>前記有機塩化合物の前記熱可塑性樹脂に対する質量比は、0.5以上が好ましく、2以上がより好ましく、6以上がさらに好ましく、30以下が好ましく、20以下がより好ましく、15以下がさらに好ましい、<1>~<30>のいずれかに記載の三次元造形用可溶性材料。
<32>前記有機塩化合物のアルキルスルホン酸イオン(R1-SO3 -)の物質量(mol)と前記熱可塑性樹脂の親水性基の物質量(mol)の比(前記有機塩化合物のアルキルスルホン酸イオンの物質量/前記熱可塑性樹脂の親水性基の物質量)は、0.005以上が好ましく、0.01以上がより好ましく、0.05以上がさらに好ましく、0.15以上がよりさらに好ましく、1.0以下が好ましく、0.9以下がより好ましく、0.7以下がさらに好ましい、<1>~<31>のいずれかに記載の三次元造形用可溶性材料。
<33>前記三次元造形用可溶性材料のガラス転移温度は、50℃以上が好ましく、60℃以上がより好ましく、70℃以上がさらに好ましく、80℃以上がよりさらに好ましく、250℃以下が好ましく220℃以下がより好ましく、200℃以下がさらに好ましい、<1>~<32>のいずれかに記載の三次元造形用可溶性材料。
<34>前記三次元造形用可溶性材料の形状は、フィラメント状が好ましい、<1>~<33>のいずれかに記載の三次元造形用可溶性材料。
<35>三次元物体及びサポート材を含む三次元物体前駆体を得る工程、及び当該三次元物体前駆体を中性水に接触させ、サポート材を除去するサポート材除去工程を有する熱溶融積層方式による三次元物体の製造方法であって、前記サポート材の材料が、<1>~<34>のいずれかに記載の三次元造形用可溶性材料である、三次元物体の製造方法。
<36>前記三次元物体の材料である造形材は、ABS樹脂、PP樹脂、ASA樹脂、PS樹脂、HIPS樹脂、PVC樹脂、ポリ乳酸樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂及びポリフェニルスルフォン樹脂等の熱可塑性樹脂が好ましく、ABS樹脂、ポリ乳酸樹脂、ポリカーボネート樹脂、及びポリアミド樹脂からなる群より選ばれる1種以上がより好ましく、ABS樹脂、ポリカーボネート樹脂、及びポリアミド樹脂からなる群より選ばれる1種以上がさらに好ましい、<35>に記載の三次元物体の製造方法。
<37>前記三次元物体前駆体を得る工程に使用するサポート材のガラス転移温度は、(使用する造形材のガラス転移温度-20℃)~(使用する造形材のガラス転移温度+20℃)が好ましく、(使用する造形材のガラス転移温度-15℃)~(使用する造形材のガラス転移温度+15℃)がさらに好ましい、<35>又は<36>に記載の三次元物体の製造方法。
<38>前記三次元物体前駆体を中性水に浸漬し、前記サポート材を溶解させて除去するサポート材除去工程を含む、<35>~<37>のいずれかに記載の三次元物体の製造方法。
<39>前記中性水が、水溶性有機溶媒を含む、<35>~<38>のいずれかに記載の三次元物体の製造方法。
<40>前記水溶性有機溶媒が、メタノール、エタノール、2-プロパノールなどの低級アルコール類、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノターシャリーブチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類、アセトン、メチルエチルケトンなどのケトン類が好ましい、<39>に記載の三次元物体の製造方法。
<41>前記中性水中の前記水溶性有機溶媒の含有量が、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上がさらに好ましく、3質量%以上がさらに好ましく、また、50%質量以下が好ましく、40%質量以下が好ましく、30%質量以下が好ましく、20%質量以下が好ましい、<39>又は<40>に記載の三次元物体の製造方法。
<42>前記中性水の使用量が、前記サポート材に対して10質量倍以上が好ましく、20質量倍以上がより好ましく、10000質量倍以下が好ましく、5000質量倍以下がより好ましく、1000質量倍以下がさらに好ましく、100質量倍以下がよりさらに好ましい、<35>~<41>のいずれかに記載の三次元物体の製造方法。
<43>前記三次元造形用可溶性材料を中性水に接触させる時間が、5分以上が好ましく、180分以下が好ましく、120分以下がより好ましく、90分以下がさらに好ましい、<35>~<42>のいずれかに記載の三次元物体の製造方法。
<44>前記三次元造形用可溶性材料に接触させる中性水の温度が、15℃以上が好ましく、25℃以上がより好ましく、30℃以上がさらに好ましく、40℃以上がよりさらに好ましく、85℃以下が好ましく、70℃以下がより好ましく、60℃以下がさらに好ましい、<35>~<43>のいずれかに記載の三次元物体の製造方法。
<45>熱溶融積層方式の3Dプリンタによって三次元物体を製造する際に、当該三次元物体を支持するサポート材であって、親水性基を有する熱可塑性樹脂と、下記一般式(I)で示される有機塩化合物とを含有する、サポート材。
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。)
<46>前記サポート材の原料が、<1>~<34>のいずれかに記載の前記三次元造形用可溶性材料である、<45>のサポート材。
<47><1>~<34>のいずれかに記載の熱可塑性樹脂の、三次元造形用可溶性材料としての使用。
〔合成例1〕
100Lステンレス製反応器(撹拌機、窒素導入管付)に2,6-ナフタレンジカルボン酸ジメチル(BP社製)、4.09kg、エチレングリコール(和光純薬工業社製、特級)3.20kg、5-スルホイソフタル酸ジメチルナトリウム(竹本油脂社製)1.69kg、チタンテトラブトキシド(東京化成工業社製、一級)1.71g、酢酸ナトリウム・三水和物(和光純薬工業社製、特級)42.0gを仕込み、常圧、窒素雰囲気下、1.5時間かけて温度を230℃に昇温し、230℃で360分加熱してエステル交換を行った。85%リン酸(シグマアルドリッチジャパン社製、特級)を637mg添加し、10分間撹拌した後、150分かけて260℃まで昇温し、同時に30mmHgまで減圧しながら撹拌して重縮合を行い、薄茶白色固体(室温)のポリエステル樹脂1を得た。
酢酸ナトリウム・三水和物を74.1gに変更し、ポリエステル樹脂2を得た以外は前記合成例1と同様に行った。
〔熱可塑性樹脂の組成〕
Agilent社製NMR、MR400を用いたプロトンNMR測定により、前記ポリエステル樹脂1の組成を求めることができる。
前記方法により求めた前記ポリエステル樹脂1の組成から、前記ポリエステル樹脂1中の親水性基(SO3)の量(単位:mmol/g)を求めることができる。
前記ポリエステル樹脂1各10mgをHFIP(1,1,1,3,3,3-Hexafluoro-2-propanol 和光純薬社製)3gに8時間溶解させ、下記条件に従ってゲル浸透クロマトグラフィー(GPC)により測定した。前記ポリエステル樹脂1の重量平均分子量は22000だった。
測定装置:HLC-8320GPC(TOSOH製)
溶離液:HFIP/0.5mMトリフルオロ酢酸ナトリウム
流量:0.2mL/min
測定温度:40℃
分析カラム:TSK-Gel Super AWM-H(TOSOH社製)
検量線:ShodexSTANDARD M-75
標準物質:ポリメチルメタクリレート(PMMA)
プレス機(東洋精機製作所社製 ラボプレスP2-30T)を用い、前記ポリエステル樹脂1をそれぞれ230℃、0.5MPaで2分間、続いて230℃、20MPaで2分間、プレスを行った。その後急冷することにより厚み0.4mmのシートを作成した。このシートから5~10mgのサンプルをハサミで切り出し、アルミパンに精秤して封入し、DSC装置(セイコーインスツル株式会社製DSC7020)を用い、30℃から250℃まで10℃/minで昇温させた後、急速に30℃まで冷却した。再び10℃/minで250℃まで昇温させて得られたDSC曲線より、ガラス転移温度(℃)を求めた。
〔実施例1〕
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を84.4g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.5g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.2g、エレカットS-418(竹本油脂株式会社製:有機塩:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩)0.8gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料1を得た。
前記三次元造形用可溶性材料1を細かく砕いたサンプル片を、キャピログラフ(東洋精機製作所社製:Capilograph 1D)を用いて、溶融温度180℃、押し出し速度10mm/minで直径2.0mm、長さ10mmのキャピラリーから押し出し、先端をピンセットではさみ、手で軽く引っ張りながら、直径1.7mmのフィラメントに加工した。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を81.6g、クラリティLA2250(株式会社クラレ社:製熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.2g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.1g、エレカットS-418(竹本油脂株式会社製:有機塩:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩)4.1gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料2を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料2に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を78.4g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 9.8g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)3.9g、エレカットS-418(竹本油脂株式会社製:有機塩:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩)7.8gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料3を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料3に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を84.4g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.5g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.2g、トリフルオロメタンスルホン酸リチウム(和光純薬株式会社製)0.8gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料4を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料4に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を81.6g、クラリティLA2250(株式会社クラレ社:製熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.2g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.1g、トリフルオロメタンスルホン酸リチウム(和光純薬株式会社製)4.1gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料5を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料5に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を78.4g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 9.8g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)3.9g、トリフルオロメタンスルホン酸リチウム(和光純薬株式会社製)7.8gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料6を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料6に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例1で得られたポリエステル樹脂1を85.1g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.6g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.3gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料7を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料7、溶融温度を210℃に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例2で得られたポリエステル樹脂2を83.0g、クラリティLA2250(株式会社クラレ社:製熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.4g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.1g、エレカットS-418(竹本油脂株式会社製:有機塩:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩)2.5gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料8を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料8に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例2で得られたポリエステル樹脂2を81.6g、クラリティLA2250(株式会社クラレ社:製熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.2g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.1g、エレカットS-418(竹本油脂株式会社製:有機塩:ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩)4.1gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料9を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料9に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
[三次元造形用可溶性材料の調製]
合成例2で得られたポリエステル樹脂2を85.1g、クラリティLA2250(株式会社クラレ社製:熱可塑性エラストマー:ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルトリブロック共重合体) 10.6g、相溶化剤としてBondfast(登録商標) 7B(住友化学社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)4.3gを減圧下60℃で乾燥後、溶融混練機(東洋精機製作所社製:Labo Plastmill 4C150)を用いて230℃、90r/min、10分間溶融混練を行い、白色混合物である三次元造形用可溶性材料10を得た。
三次元造形用可溶性材料1を三次元造形用可溶性材料10、溶融温度を210℃に変えた以外は前記実施例1に係るフィラメントの製造と同様に行った。その後、フィラメントをMakerbot社製3DプリンタReplicator2Xに供給し、250℃の温度を有するヒートノズルから押し出したところ、ノズルが閉塞することなく吐出することができ、溶融物も、直ちに固化することを確認した。
〔ガラス転移温度〕
前記ベースポリマーのガラス転移温度の分析方法と同様に行った。評価結果を表1に示す。
容量1Lのビーカーに水を1L入れ、マグネットスターラーで300rpmで撹拌しながらヒーターで70℃まで加熱した。そこに上部から、キャピログラフで成形した樹脂フィラメント(直径約1.7mm、長さ13cm)を吊るして浸漬させ、フィラメントが溶解して切れるまでの時間をストップウォッチで測定した。評価結果を表1に示す。
[ABS樹脂との接着性]
(実施例1~7、及び比較例1、2)
キャピログラフで成形した実施例1~7、及び比較例1、2に係る樹脂フィラメントとABSP430(ストラタシス社製:造形材フィラメント:ABS樹脂,ガラス転移温度:108℃)をMakerbot社製3DプリンタReplicator2Xに供給し、それぞれ、250℃、230℃の温度を有するヒートノズルから交互に押し出し、造形して実施例1~7、及び比較例1、2にかかる評価サンプルをそれぞれ作成した。造形後の評価サンプルの1つの写真を図1に示す。図1において、評価サンプル1は造形材11の上にサポート材12が積層されている。実施例1~7、及び比較例1、2にかかる評価サンプルについてそれぞれ造形材11とサポート材12との樹脂界面をスパーテルで削った時の剥離しにくさを下記基準で評価してABS樹脂との接着性を評価した。評価結果を表1に示す。
A:金属製のスパーテルで界面を削っても剥離しない
B:金属製のスパーテルで界面を強く削ると剥離する
C:金属製のスパーテルで触れると剥離する
D:造形時に剥離する
(実施例7、8及び比較例2)
キャピログラフで成形した実施例7、8及び比較例2に係る樹脂フィラメントとFDM Nylon12(ストラタシス社製:造形材フィラメント:ポリアミド樹脂,結晶化温度:148℃,融点:178℃)をMakerbot社製3DプリンタReplicator2Xに供給し、それぞれ、250℃、255℃の温度を有するヒートノズルから交互に押し出し、造形して実施例7、8及び比較例2にかかる評価サンプルをそれぞれ作成した以外は、ABS樹脂との接着性と同様にしてポリアミド樹脂との接着性を評価した。評価結果を表1に示す。
(実施例7、8及び比較例2)
キャピログラフで成形した実施例7、8及び比較例2に係る樹脂フィラメントとPC-10(ストラタシス社製:造形材フィラメント:ポリカーボネート樹脂, ガラス転移温度:145℃)をMakerbot社製3DプリンタReplicator2Xに供給し、それぞれ、250℃、255℃の温度を有するヒートノズルから交互に押し出し、造形して実施例7、8及び比較例2にかかる評価サンプルをそれぞれ作成した以外は、ABS樹脂との接着性と同様にしてポリカーボネート樹脂との接着性を評価した。評価結果を表1に示す。
11造形材
12 サポート材
Claims (16)
- 熱溶融積層方式の3Dプリンタによって三次元物体を製造する際に、当該三次元物体を支持するサポート材の材料として用いられる三次元造形用可溶性材料であって、
親水性基を有する熱可塑性樹脂と、下記一般式(I)で示される有機塩化合物とを含有する、三次元造形用可溶性材料。
(R1-SO3 -)nXn+ (I)
(前記一般式(I)中、R1は置換基を有していてもよい炭素数1~30の炭化水素基を示し、nは1又は2の数を示し、nが1のとき、Xn+はナトリウムイオン、カリウムイオン、リチウムイオン、アンモニウムイオン、又はホスホニウムイオンを示し、nが2のとき、Xn+はマグネシウムイオン、カルシウムイオン、バリウムイオン、又は亜鉛イオンを示す。) - 前記熱可塑性樹脂中の前記親水性基の含有量が、0.5mmol/g以上3.0mmol/g以下である、請求項1に記載の三次元造形用可溶性材料。
- 前記熱可塑性樹脂が、ポリエステル樹脂、ポリアミド樹脂、アクリル樹脂、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、ポリエステルアミド樹脂、ポリウレタン樹脂からなる群より選ばれる1種以上である、請求項1又は2に記載の三次元造形用可溶性材料。
- 前記親水基が、スルホン酸塩基である、請求項1~3のいずれか1項に記載の三次元造形用可溶性材料。
- 形状がフィラメント状である、請求項1~4のいずれか1項に記載の三次元造形用可溶性材料。
- 前記ポリエステル樹脂が、前記親水性基を有する親水性モノマーユニットA1、疎水性ジカルボン酸モノマーユニットB1、及びジオールモノマーユニットを有し、前記ポリエステル樹脂中の前記親水性モノマーユニットA1及び前記疎水性ジカルボン酸モノマーユニットB1の合計に対する前記親水性モノマーユニットA1の割合が10mol%以上70mol%以下である、請求項3~5のいずれか1項に記載の三次元造形用可溶性材料。
- 前記ポリアミド樹脂が、前記親水性基を有する親水性モノマーユニットA2、疎水性ジカルボン酸モノマーユニットB2、及び疎水性ジアミンモノマーユニットを有し、前記ポリアミド樹脂中の全モノマーユニットの合計に対する前記親水性モノマーユニットA2の割合が2.5mol%以上40mol%以下である、請求項3~6のいずれか1項に記載の三次元造形用可溶性材料。
- 前記ポリアミド樹脂中の前記親水性基の含有量は、0.5mmol/g以上3.0mmol/g以下である、請求項3~7のいずれか1項に記載の三次元造形用可溶性材料。
- 前記熱可塑性樹脂の重量平均分子量が、3000以上70000以下である、請求項3~8のいずれか1項に記載の三次元造形用可溶性材料。
- 前記ホスホニウムイオンが、テトラアルキルホスホニウムイオンである、請求項1~9のいずれか1項に記載の三次元造形用可溶性材料。
- 前記有機塩化合物の前記熱可塑性樹脂に対する質量比が、0.5以上30以下である、請求項1~10のいずれか1項に記載の三次元造形用可溶性材料。
- 前記有機塩化合物のアルキルスルホン酸イオン(R1-SO3 -)の物質量(mol)と前記熱可塑性樹脂の親水性基の物質量(mol)の比(前記有機塩化合物のアルキルスルホン酸イオンの物質量/前記熱可塑性樹脂の親水性基の物質量)は、0.005以上1.0以下である、請求項1~11のいずれか1項に記載の三次元造形用可溶性材料。
- 三次元物体及びサポート材を含む三次元物体前駆体を得る工程、及び当該三次元物体前駆体を中性水に接触させ、サポート材を除去するサポート材除去工程を有する熱溶融積層方式による三次元物体の製造方法であって、
前記サポート材の材料が、請求項1~12のいずれか1項に記載の三次元造形用可溶性材料である、三次元物体の製造方法。 - 前記三次元物体の材料である造形材は、ABS樹脂、PP樹脂、ASA樹脂、PS樹脂、HIPS樹脂、PVC樹脂、ポリ乳酸樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂及びポリフェニルスルフォン樹脂からなる群より選ばれる1種以上である、請求項13に記載の三次元物体の製造方法。
- 前記三次元物体前駆体を中性水に浸漬し、前記サポート材を溶解させて除去するサポート材除去工程を含む、請求項13又は14に記載の三次元物体の製造方法。
- 請求項1~12のいずれか1項に記載の熱可塑性樹脂の、三次元造形用可溶性材料としての使用。
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