WO2016125860A1 - 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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- WO2016125860A1 WO2016125860A1 PCT/JP2016/053368 JP2016053368W WO2016125860A1 WO 2016125860 A1 WO2016125860 A1 WO 2016125860A1 JP 2016053368 W JP2016053368 W JP 2016053368W WO 2016125860 A1 WO2016125860 A1 WO 2016125860A1
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- Prior art keywords
- dicarboxylic acid
- mol
- monomer unit
- preferable
- dimensional
- Prior art date
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- 239000002195 soluble material Substances 0.000 title claims abstract description 98
- 239000000178 monomer Substances 0.000 claims abstract description 171
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000000463 material Substances 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910001868 water Inorganic materials 0.000 claims abstract description 79
- 229920001225 polyester resin Polymers 0.000 claims abstract description 76
- 239000004645 polyester resin Substances 0.000 claims abstract description 76
- 230000007935 neutral effect Effects 0.000 claims abstract description 65
- 150000002009 diols Chemical class 0.000 claims abstract description 63
- 125000003118 aryl group Chemical group 0.000 claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 39
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 40
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 29
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012943 hotmelt Substances 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 30
- 239000007864 aqueous solution Substances 0.000 abstract description 19
- 238000004090 dissolution Methods 0.000 abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000002585 base Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract 1
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- 239000000203 mixture Substances 0.000 description 50
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- 238000003786 synthesis reaction Methods 0.000 description 29
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- 229910052757 nitrogen Inorganic materials 0.000 description 23
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
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- 239000010935 stainless steel Substances 0.000 description 19
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 17
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- 238000010438 heat treatment Methods 0.000 description 16
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- 238000005809 transesterification reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 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 10
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
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- 150000002148 esters Chemical class 0.000 description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 8
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- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 7
- 229960002479 isosorbide Drugs 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
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- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 4
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- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
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- LYSAMJWUSPMVCG-UHFFFAOYSA-N 2,8-dioxo-3,7-dioxabicyclo[7.3.1]trideca-1(13),9,11-triene-11-sulfonic acid Chemical compound S(=O)(=O)(O)C=1C=C2C=C(C(=O)OCCCOC2=O)C1 LYSAMJWUSPMVCG-UHFFFAOYSA-N 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
- B41J2/32—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material using thermal heads
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0838—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using laser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
- B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/251—Particles, powder or granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7166—Water-soluble, water-dispersible
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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.
- the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting the three-dimensional object when a three-dimensional object is manufactured by an FDM-type 3D printer, Aromatic dicarboxylic acid monomer unit A having a sulfonic acid group, a dicarboxylic acid monomer unit B having no sulfonic acid group, and a diol monomer unit, the aromatic dicarboxylic acid monomer unit with respect to the total of all dicarboxylic acid monomer units A polyester resin in which the ratio of A is 10 to 70 mol% is included.
- 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. It is a manufacturing method of the three-dimensional object by the FDM system which has a removal process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.
- the support material of the present invention is a support material for supporting a three-dimensional object when the three-dimensional object is manufactured by an FDM type 3D printer, and includes an aromatic dicarboxylic acid monomer unit A having a sulfonate group, a sulfonic acid
- the polyester resin has a dicarboxylic acid monomer unit B having no base and a diol monomer unit, and the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units is 10 to 70 mol%.
- the Japanese translation of PCT publication No. 2002-516346 uses a water-soluble poly (2-ethyl-2-oxazoline) as a support material and immerses the three-dimensional object precursor in water.
- a technique for removing material is disclosed.
- 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 invention is suitable for the production of a three-dimensional object by the FDM method, has moisture absorption resistance, has a high dissolution rate in neutral water, and can be rapidly produced from a three-dimensional object precursor without using a strong alkaline aqueous solution.
- a three-dimensional modeling soluble material for a support material that can be removed is provided.
- the present invention can suppress foaming by suppressing the deterioration of accuracy of a three-dimensional object even if it is used for production of a three-dimensional object by a 3D printer after being exposed to high humidity, and can be dissolved in neutral water.
- a method for producing a three-dimensional object which has a high speed and can quickly remove a support material from a three-dimensional object precursor without using a strong alkaline aqueous solution.
- the present invention can suppress foaming by suppressing the deterioration of accuracy of a three-dimensional object even if it is used for production of a three-dimensional object by a 3D printer after being exposed to high humidity, and can be dissolved in neutral water.
- a support material having a high speed and capable of quickly removing the support material from a three-dimensional object precursor without using a strong alkaline aqueous solution.
- the three-dimensional modeling soluble material of the present invention is a three-dimensional modeling soluble material used as a support material for supporting the three-dimensional object when a three-dimensional object is manufactured by an FDM-type 3D printer, Aromatic dicarboxylic acid monomer unit A having a sulfonic acid group, a dicarboxylic acid monomer unit B having no sulfonic acid group, and a diol monomer unit, the aromatic dicarboxylic acid monomer unit with respect to the total of all dicarboxylic acid monomer units A polyester resin in which the ratio of A is 10 to 70 mol% is included.
- 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. It is a manufacturing method of the three-dimensional object by the FDM system which has a removal process, Comprising: The material of the said support material is the said soluble material for three-dimensional modeling.
- the support material of the present invention is a support material for supporting a three-dimensional object when the three-dimensional object is manufactured by an FDM type 3D printer, and includes an aromatic dicarboxylic acid monomer unit A having a sulfonate group, a sulfonic acid
- the polyester resin has a dicarboxylic acid monomer unit B having no base and a diol monomer unit, and the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units is 10 to 70 mol%.
- the present invention it is suitable for production of a three-dimensional object by the FDM method, has moisture absorption resistance, has a high dissolution rate in neutral water, and can be used from a three-dimensional object precursor without using a strong alkaline aqueous solution. It is possible to provide a three-dimensional modeling soluble material for a support material that can be quickly removed.
- the present invention even if it is used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, it is possible to suppress foaming and suppress a decrease in accuracy of the three-dimensional object, and to neutral water.
- a method for producing a three-dimensional object capable of rapidly removing the support material from the three-dimensional object precursor without using a strong alkaline aqueous solution.
- the present invention even if it is used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, it is possible to suppress foaming and suppress a decrease in accuracy of the three-dimensional object, and to neutral water. Thus, it is possible to provide a support material capable of rapidly removing the support material from the three-dimensional object precursor without using a strong alkaline aqueous solution.
- the soluble material for 3D modeling according to the present embodiment is a soluble material for 3D modeling used as a support material for supporting the 3D object when a 3D object is manufactured by an FDM 3D printer.
- the aromatic dicarboxylic acid monomer unit A having a sulfonate group, the dicarboxylic acid monomer unit B having no sulfonate group, and the diol monomer unit, and the aromatic dicarboxylic acid monomer with respect to the total of all dicarboxylic acid monomer units A polyester resin having a unit A ratio of 10 to 70 mol% is included.
- the support material made of the soluble material for three-dimensional modeling has moisture absorption resistance and has a high dissolution rate in neutral water, so that it can be quickly developed from a three-dimensional object precursor without using a strong alkaline aqueous solution. Can be removed.
- the reason why the three-dimensional modeling soluble material has such an effect is not clear, but is considered as follows.
- the soluble material for three-dimensional modeling of this embodiment has a polyester resin having a specific amount of aromatic dicarboxylic acid having a sulfonate group as a monomer unit. Since the polyester resin has the sulfonate group, it has high solubility in neutral water. Moreover, since the said polyester resin has aromatic dicarboxylic acid as a monomer unit, its hygroscopic property is low. Since the three-dimensional modeling soluble material of this embodiment has such a polyester resin, the support material containing the three-dimensional modeling soluble material has moisture absorption resistance and is soluble in neutral water. It is considered that the speed is high and it can be quickly removed from the three-dimensional object precursor without using an alkaline aqueous solution.
- polyester resin [Aromatic dicarboxylic acid monomer unit A]
- the polyester resin has an aromatic dicarboxylic acid monomer unit having a sulfonate group.
- an aromatic dicarboxylic acid monomer unit having a sulfonate group is also referred to as an aromatic dicarboxylic acid monomer unit A.
- the aromatic dicarboxylic acid for deriving the aromatic dicarboxylic acid monomer unit A is also referred to as aromatic dicarboxylic acid A.
- the aromatic dicarboxylic acid A is a group consisting of 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid from the viewpoint of solubility in neutral water and moisture absorption resistance. At least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid is more preferable, and 5-sulfoisophthalic acid is still more preferable.
- the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units in the polyester resin is 10 mol% or more, preferably 15 mol% or more, and 18 mol % Or more, more preferably 20 mol% or more, and from the viewpoint of moisture absorption resistance, it is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, and more preferably 30 mol% or less. Even more preferred is 25 mol% or less.
- the composition of the dicarboxylic acid monomer unit in the polyester resin is measured by the method described in Examples.
- the content of the aromatic dicarboxylic acid monomer unit A in the polyester resin is preferably 5 mol% or more, more preferably 7.5 mol% or more, and even more preferably 9 mol% or more. 10 mol% or more is still more preferable, and from the viewpoint of moisture absorption resistance, 35 mol% or less is preferable, 30 mol% or less is more preferable, 25 mol% or less is more preferable, 20 mol% or less is more preferable, and 15 mol% or less is even more preferable. Preferably, 13 mol% or less is still more preferable.
- At least one inorganic cation selected from the group consisting of lithium ion, sodium ion, potassium ion, magnesium ion and ammonium ion, monoethanolammonium ion examples include at least one organic cation selected from the group consisting of diethanolammonium ion and triethanolammonium ion. From the viewpoint of solubility in neutral water, sodium ion, potassium ion, magnesium ion, and ammonium ion At least one cation selected from the group consisting of, preferably at least one cation selected from the group consisting of sodium ions and potassium ions, more preferably sodium ions.
- the content of the sulfonate 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, 0.8 mmol / g or more is still more preferable, 0.9 mmol / g or more is more preferable, and from the viewpoint of moisture absorption resistance, 3.0 mmol / g or less is preferable, and 2.0 mmol / g or less is more preferable.
- 1.5 mmol / g or less is further preferable, 1.3 mmol / g or less is more preferable, and 1.2 mmol / g or less is still more preferable.
- content of a sulfonate group is measured by the method as described in an Example.
- the polyester resin has a dicarboxylic acid monomer unit having no sulfonate group.
- a monomer unit of dicarboxylic acid having no sulfonate group is also referred to as dicarboxylic acid monomer unit B.
- the dicarboxylic acid for deriving the dicarboxylic acid monomer unit B is also referred to as dicarboxylic acid B.
- Dicarboxylic acid B does not have a sulfonate group.
- the dicarboxylic acid B is at least selected from the group consisting of an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. One or more are preferred.
- the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-adamantanedicarboxylic acid At least one selected from the group consisting of terephthalic acid, 2,5-furandicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is more preferable.
- the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units in the polyester resin is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. 60 mol% or more is more preferable, 70 mol% or more is more preferable, 75 mol% or more is more preferable, and from the viewpoint of solubility in neutral water, 90 mol% or less is preferable, 85 mol% or less is more preferable, 82 mol % Or less is more preferable, and 80 mol% or less is still more preferable.
- the content of the dicarboxylic acid monomer unit B in the polyester resin is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, and even more preferably 30 mol% or more, from the viewpoint of moisture absorption resistance.
- 35 mol% or more is more preferable, 38 mol% or more is more preferable, and from the viewpoint of solubility in neutral water, 45 mol% or less is preferable, 43 mol% or less is more preferable, 41 mol% or less is more preferable, 40 mol%
- the following is even more preferable.
- the ratio of the total of the aromatic dicarboxylic acid monomer unit A and the dicarboxylic acid monomer unit B to the total of all the dicarboxylic acid monomer units in the polyester resin is determined by solubility in neutral water, moisture absorption resistance, and 3D printer. 80 mol% or more is preferable, 90 mol% or more is more preferable, 95 mol% or more is further preferable, 98 mol% or more is further more preferable, 100 mol% is still more preferable, and 100 mol% is more preferable. % Is even more preferred. In addition, in this specification, substantially 100 mol% means the state which inevitably contains a trace amount impurity.
- the molar ratio of the aromatic dicarboxylic acid monomer unit A to the dicarboxylic acid monomer unit B is determined by solubility in neutral water, moisture absorption resistance, and From the viewpoint of heat resistance required for modeling by a 3D printer, 10/90 or more is preferable, 15/85 or more is more preferable, 18/82 or more is further preferable, 20/80 or more is further more preferable, and the same viewpoint 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 still more preferable.
- the polyester resin has a diol monomer unit.
- the diol for deriving the diol monomer unit is also referred to as diol C.
- the diol C is not particularly limited, and aliphatic diols, aromatic diols, and the like can be used, but aliphatic diols are preferable from the viewpoint of the production cost of the polyester resin.
- the number of carbon atoms of the diol C is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable, 25 The following is more preferable, 20 or less is further preferable, and 15 or less is more preferable.
- Examples of the aliphatic diol include at least one selected from the group consisting of a chain diol and a cyclic diol, and are required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer. From the viewpoint of toughness (strength), a chain diol is preferred.
- the number of carbon atoms of the chain diol is preferably 2 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 6 or less is preferable. 4 or less is more preferable, and 3 or less is more preferable.
- the number of carbon atoms of the cyclic diol is preferably 6 or more from the viewpoint of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer, and from the same viewpoint, 31 or less is preferable. 25 or less is more preferable, 20 or less is further preferable, 15 or less is more preferable, 10 or less is still more preferable, and 8 or less is still more preferable.
- the diol C may have ether oxygen.
- the diol C is a chain aliphatic diol, it is required for solubility in neutral water, moisture absorption resistance, and modeling by a 3D printer.
- the number of ether oxygens is preferably 1 or less, and when the diol C is a cycloaliphatic diol, the number of ether oxygens is preferably 2 or less from the same viewpoint.
- the chain diol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. And preferably at least one selected from the group consisting of dipropylene glycol, more preferably at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, and 1,3-propanediol.
- diethylene glycol and dipropylene glycol may be charged as a raw material for the polymerization reaction, or may be by-produced during the polymerization reaction.
- the ratio of the diethylene glycol unit to the total of all diol monomer units in the polyester resin is the solubility in neutral water, moisture absorption resistance, and the heat resistance required for modeling by a 3D printer. From the viewpoint, 5 mol% or more is preferable, 10 mol% or more is more preferable, 15 mol% or more is further preferable, 20 mol% or more is further preferable, 25 mol% or more is further more preferable, 30 mol% or more is more preferable, and 60 mol%. The following is preferable, 55 mol% or less is more preferable, 50 mol% or less is more preferable, and 45 mol% or less is still more preferable.
- the cyclic diol is composed of 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene from the viewpoints of solubility in neutral water, moisture absorption resistance, and heat resistance required for modeling by a 3D printer. At least one selected from the group consisting of bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is preferred.
- Diol C is ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, bisque
- the total proportion of loulene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene is 80 mol% or more from the viewpoints of solubility in neutral water, moisture absorption resistance,
- composition of the diol monomer unit in the polyester resin is measured by the method described in Examples.
- the polyester resin is based on the total of all dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A.
- the ratio of the aromatic dicarboxylic acid monomer unit A and the ratio of the dicarboxylic acid monomer unit B are 15 to 40 mol% and 60 to 85 mol%, respectively, and the dicarboxylic acid B for obtaining the dicarboxylic acid monomer unit B is Polyester resin ⁇ which is 2,5-furandicarboxylic acid is preferred.
- polyester resin ⁇ The ratio of the aromatic dicarboxylic acid monomer unit A to the total of all the dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A in the polyester resin ⁇ is the solubility in neutral water, moisture absorption resistance, and From the viewpoint of heat resistance required for modeling by a 3D printer, 15 mol% or more is preferable, 20 mol% or more is more preferable, and from the same viewpoint, 40 mol% or less is preferable, 30 mol% or less is more preferable, and 25 mol% or less is still more preferable. .
- the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A in the polyester resin ⁇ is the solubility in neutral water, moisture absorption resistance, and 3D printer. From the viewpoint of the heat resistance required for modeling by the above, 60 mol% or more is preferable, 70 mol% or more is more preferable, 75 mol% or more is more preferable, and from the same viewpoint, 85 mol% or less is preferable, and 80 mol% or less is more preferable.
- the aromatic dicarboxylic acid A in the polyester resin ⁇ is 5-sulfoisophthalic acid and 2-sulfoisophthalic acid from the viewpoint 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 acids is preferred, and 5-sulfoisophthalic acid is more preferred.
- the diol C is ethylene glycol, diethylene glycol, 1,3-propanediol, dithiol 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 propylene glycol is preferable, and at least one selected from the group consisting of ethylene glycol and diethylene glycol is more preferable.
- the polyester resin ⁇ can be exemplified by the following general formulas (1) and (2).
- X represents the degree of polymerization of ethylene furanoate
- Y represents the number of degrees of polymerization of ethylene 5-sulfoisophthalate, provided that ethylene furanoate and ethylene 5-sulfoisophthalate are block bonds and / or Or a random bond, and a random bond is more preferable from the viewpoint of solubility in neutral water.
- X represents the degree of polymerization of 1,3-propylene furanoate
- Y represents the number of polymerization degrees of 1,3-propylene 5-sulfoisophthalate, where 1,3-propylene furanoate.
- 1,3-propylene 5-sulfoisophthalate 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 weight average molecular weight of the polyester resin is preferably 3000 or more, more preferably 8000 or more, still more preferably 10,000 or more, still more preferably 20000 or more, and more preferably 30000 from the viewpoint of improving toughness required for the three-dimensional modeling soluble material. More preferably, more preferably 40000 or more, more preferably 80000 or less, more preferably 70000 or less, still more preferably 60000 or less, even more preferably 50000 or less, and to neutral water from the viewpoint of formability by a 3D printer. From the viewpoint of the solubility, 60,000 or less is preferable, 50,000 or less is more preferable, and 40,000 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 of the polyester resin 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, from the same viewpoint, from the viewpoint of formability by a 3D printer. 180 ° C. or lower is preferable, 160 ° C. or lower is more preferable, 140 ° C. or lower is further preferable, and 120 ° C. or lower is still more preferable.
- a glass transition temperature is measured by the method as described in an Example.
- the polyester resin may have monomer units other than the aromatic dicarboxylic acid monomer unit A, the dicarboxylic acid monomer unit B, 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 polyester resin production method can be applied.
- the content of the polyester resin in the three-dimensional modeling soluble material can be adjusted within a range that does not impair the effects of the present embodiment, but is soluble in neutral water, moisture-absorbing, and depending on the 3D printer. From the viewpoint of heat resistance required for modeling, it is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 80% by mass or more. 90 mass% or more is still more preferable, 95 mass% or more is further more preferable, substantially 100 mass% is still more preferable, and 100 mass% is still 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, still more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of formability by a 3D printer. From the same viewpoint, 180 ° C. or lower is preferable, 160 ° C. or lower is more preferable, 140 ° C. or lower is further preferable, and 120 ° C. or lower is even more preferable.
- 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 still more preferable.
- the draw ratio in the drawing process is preferably 1.5 times or more, more preferably 2 times or more, more preferably 3 times or more, still more preferably 5 times or more, and the same viewpoint from the viewpoint of both toughness improvement and water solubility.
- stretching process has the preferable inside of the range of the temperature 60 degreeC higher than the said glass transition temperature from the temperature 20 degreeC lower than the glass transition temperature of the said soluble material for three-dimensional modeling.
- the lower limit of the stretching temperature is preferably 10 ° C. lower than the glass transition temperature from the viewpoint of toughness improvement and thermal stability, and more preferably the same temperature as the glass transition temperature.
- the upper limit of the stretching temperature is more preferably 40 ° C higher than the glass transition temperature, more preferably 30 ° C higher than the glass transition temperature, and still more preferably 20 ° C higher than the glass transition temperature.
- the heating method during stretching is not particularly limited, such as hot air or laser.
- stretching may be extended
- the soluble material for three-dimensional modeling may contain a polymer other than the polyester resin for the purpose of improving the physical properties of the soluble material for three-dimensional modeling within a range not impairing the effects of the present embodiment.
- polymers include water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, poly (ethylene glycol / propylene glycol), carboxymethylcellulose, and starch; hydrophobic polymers such as polymethyl methacrylate; hard segments and soft Segmented polyether ester, polyether ester amide, polyurethane and other elastomers, block copolymers of ionic monomers and water-soluble nonionic monomers and hydrophobic monomers, styrene-butadiene, alkyl methacrylates (1-18 carbon atoms) ) -A thermoplastic elastomer composed of alkyl acrylate (having 1 to 18 carbon atoms); a graft polymer obtained by grafting a polymer such as polyacrylic acid or N, N-d
- the three-dimensional modeling soluble material contains a polymer other than a polyester resin
- the affinity and compatibility between the polymer and the polyester resin are increased to improve the performance of the three-dimensional modeling soluble material and the three-dimensional modeling solubility.
- the three-dimensional modeling soluble material can contain a compatibilizing agent.
- the compatibilizer include (i) a monomer having a glycidyl group, an isocyanate group, and / or a monomer having an acid anhydride structure such as maleic anhydride, acrylic acid, alkyl methacrylate, ethylene, propylene, and vinyl acetate.
- 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 polyester resins other than the polyester resins, polymers other than polyester resins, plasticizers such as polyalkylene glycol diesters of benzoic acid, calcium carbonate, magnesium carbonate, glass balls, graphite, carbon black, carbon Examples thereof include fillers such as fiber, glass fiber, talc, wollastonite, mica, alumina, silica, kaolin, whisker, and silicon carbide.
- 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.
- foaming can be suppressed even when used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity, and a decrease in accuracy of the three-dimensional object can be suppressed.
- the support material can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution because of its high dissolution rate in neutral water. The reason why the manufacturing method of the three-dimensional object has such an effect is not clear, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.
- Step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material The step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material is performed in a three-dimensional manner using a known hot-melt lamination type 3D printer except that the material of the support material is the soluble material for three-dimensional modeling.
- a step of obtaining a three-dimensional object precursor including a three-dimensional object and a support material in the object manufacturing method can be used.
- the modeling material that is the material of the three-dimensional object can be used without particular limitation as long as it is a resin that is used as a modeling material in a conventional FDM three-dimensional object manufacturing method.
- the modeling material include thermoplastic resins such as ABS resin, polylactic acid resin, polycarbonate resin, and polyphenylsulfone resin.
- ABS resin and / or polylactic acid resin are preferable from the viewpoint of modeling by a 3D printer. Is more preferable, and ABS resin is more preferable.
- the support material removing step the support material is removed by bringing the three-dimensional object precursor into contact with neutral water.
- the method of bringing the three-dimensional object precursor into contact with neutral water is preferably a method of immersing the three-dimensional object precursor in neutral water from the viewpoint of cost and ease of work. From the viewpoint of improving the removability of the support material, it is possible to promote the dissolution of the support material by irradiating ultrasonic waves during the immersion.
- the neutral water examples include ion-exchanged water, pure water, tap water, and industrial water, but ion-exchanged water and tap water are preferable from the viewpoint of economy.
- the neutral water may contain the water-soluble organic solvent in the range which does not damage the shaped three-dimensional object.
- water-soluble organic solvents include lower alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether and diethylene glycol monobutyl ether, acetone and methyl ethyl ketone. And ketones.
- the content of the water-soluble organic solvent in the neutral water is preferably 0.1% by mass or more from the viewpoint of solubility and damage to the shaped three-dimensional object, 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, 3% by mass or more is further preferable, 50% by mass or less is preferable, 40% by mass or less is preferable, and 30% by mass or less is preferable. % Mass or less is preferred.
- the amount of the neutral water used is preferably 10 times by mass or more, more preferably 20 times by mass or more with respect to the support material from the viewpoint of solubility of the support material, and 10,000 from the support material from the viewpoint of economy.
- the mass times or less are preferable, the 5000 mass times or less are more preferable, the 1000 mass times or less are more preferable, and the 100 mass times or less are more preferable.
- the time for bringing the soluble material for 3D modeling into contact with neutral water is preferably 5 minutes or more from the viewpoint of the removability of the support material, and reducing damage to the 3D object by contacting with neutral water for a long time. From the viewpoint of viewpoint and economy, it is preferably 180 minutes or shorter, more preferably 120 minutes or shorter, and even more preferably 90 minutes or shorter.
- the cleaning temperature is preferably 15 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of removal of the support material, reduction of damage to the three-dimensional object, and economy, although it depends on the type of model material. More preferably, it is more preferably 40 ° C. or more, and more preferably 40 ° C. or more. From the same viewpoint, 85 ° C. or less is preferred, 70 ° C. or less is more preferred, and 60 ° C. or less is more preferred.
- the support material of the present embodiment is a support material that supports a three-dimensional object when the three-dimensional object is manufactured by a hot melt lamination type 3D printer, and includes the polyester resin.
- the support material can suppress foaming and suppress deterioration in accuracy of a three-dimensional object even when used for manufacturing a three-dimensional object by a 3D printer after being exposed to high humidity.
- the dissolution rate is high, and the support material can be quickly removed from the three-dimensional object precursor without using a strong alkaline aqueous solution.
- the reason why the support material has such an effect is not certain, but the same reason as the reason why the soluble material for three-dimensional modeling has the effect can be considered.
- the present specification further discloses the following composition and production method.
- the aromatic dicarboxylic acid A for deriving the aromatic dicarboxylic acid monomer unit A is selected from the group consisting of 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, and 4-sulfo-2,6-naphthalenedicarboxylic acid. At least one or more selected, preferably at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoterephthalic acid, more preferably 5-sulfoisophthalic acid, as described in ⁇ 1> above Soluble material for 3D modeling.
- the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units in the polyester resin is 10 mol% or more, preferably 15 mol% or more, more preferably 18 mol% or more, and 20 mol%. More preferably, it is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, still more preferably 30 mol% or less, and even more preferably 25 mol% or less, ⁇ 1 > Or ⁇ 2>
- the soluble material for three-dimensional modeling is 10 mol% or more, preferably 15 mol% or more, more preferably 18 mol% or more, and 20 mol%. More preferably, it is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, still more preferably 30 mol% or less, and even more preferably 25 mol% or less, ⁇
- the content of the aromatic dicarboxylic acid monomer unit A in the polyester resin is preferably 5 mol% or more, more preferably 7.5 mol% or more, still more preferably 9 mol% or more, and even more preferably 10 mol% or more. 35 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 13 mol% or less, ⁇ 1> to ⁇ 3>
- the three-dimensional modeling soluble material according to any one of the above.
- ⁇ 5> Inorganic cation, monoethanolammonium ion, diethanolammonium ion, triethanol wherein the sulfonate group constituting the sulfonate group is selected from lithium ion, sodium ion, potassium ion, magnesium ion, and ammonium ion
- An organic cation selected from ammonium ions is preferable, a cation selected from sodium ions, potassium ions, magnesium ions, and ammonium ions is more preferable, sodium ions and potassium ions are more preferable, and sodium ions are still more preferable.
- the soluble material for three-dimensional modeling according to any one of 1> to ⁇ 4>.
- the content of the sulfonate in the polyester resin is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, still more preferably 0.7 mmol / g or more, 0.8 mmol / g g or more is more preferable, 0.9 mmol / g or more is further more preferable, 3.0 mmol / g or less is preferable, 2.0 mmol / g or less is more preferable, 1.5 mmol / g or less is more preferable, 1.3 mmol
- the dicarboxylic acid B for deriving the dicarboxylic acid monomer unit B is preferably at least one selected from the group consisting of aromatic dicarboxylic acids and alicyclic dicarboxylic acids, such as terephthalic acid, isophthalic acid, 2 , 5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and at least one selected from the group consisting of 1,3-adamantanedicarboxylic acid are more preferable.
- aromatic dicarboxylic acids and alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2 , 5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and at least one selected from the group consisting of 1,3-adamantanedicarboxylic acid are more preferable.
- the three-dimensional modeling soluble material according to any one of ⁇ 1> to ⁇ 6>, wherein at least one selected from the group consisting of 5-furandicarboxylic acid and 2,6-naphthalenedicarboxylic acid is more preferable.
- the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units in the polyester resin is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and 60 mol% or more.
- the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 7>.
- the content of the dicarboxylic acid monomer unit B in the polyester resin is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, still more preferably 30 mol% or more, and even more preferably 35 mol% or more.
- the soluble material for three-dimensional modeling according to any one of the above.
- the ratio of the total of the aromatic dicarboxylic acid monomer unit A and the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units in the polyester resin is preferably 80 mol% or more, more preferably 90 mol% or more.
- the molar ratio of the aromatic dicarboxylic acid monomer unit A to the dicarboxylic acid monomer unit B is preferably 10/90 or more, and 15/85
- the above is more preferable, 18/82 or more is further 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 further preferable, and 25/75 or less is preferable.
- the diol C for inducing the diol monomer unit is preferably at least one selected from the group consisting of aliphatic diols and aromatic diols, and at least one selected from the group consisting of aliphatic diols. More preferably, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 11>.
- the number of carbon atoms of the diol C is preferably 2 or more, preferably 31 or less, more preferably 25 or less, still more preferably 20 or less, and even more preferably 15 or less, any of the above ⁇ 1> to ⁇ 12>
- the soluble material for three-dimensional modeling described in Crab is preferably at least one selected from the group consisting of aliphatic diols and aromatic diols, and at least one selected from the group consisting of aliphatic diols. More preferably, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 11>.
- the aliphatic diol is preferably at least one selected from the group consisting of a chain diol and a cyclic diol, more preferably a chain diol, according to any one of ⁇ 1> to ⁇ 13>.
- the number of carbon atoms of the cyclic diol is preferably 6 or more, preferably 31 or less, more preferably 25 or less, still more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less, and 8 or less. Is still more preferable, The soluble material for three-dimensional modeling according to ⁇ 14> or ⁇ 15>.
- the chain diol is preferably at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, and dipropylene glycol.
- the soluble material for three-dimensional modeling according to any one of ⁇ 14> to ⁇ 16>, wherein at least one selected from the group consisting of propanediol and 1,3-propanediol is more preferable.
- the diol monomer unit includes a diethylene glycol unit, and the ratio of the diethylene glycol unit to the total of all diol monomer units in the polyester resin is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more.
- the three-dimensional modeling soluble material according to any one of ⁇ 1> to ⁇ 17>, preferably. ⁇ 19>
- the cyclic diol is at least one selected from the group consisting of 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, isosorbide, bisphenoxyethanol fluorene, bisphenol fluorene, biscrezoxyethanol fluorene, and biscresol fluorene.
- the ratio of the aromatic dicarboxylic acid monomer unit A and the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A in the polyester resin are respectively ⁇ 1> to ⁇ 19>, preferably 15 to 40 mol% and 60 to 85 mol%, and the polyester resin ⁇ in which the dicarboxylic acid B for obtaining the dicarboxylic acid monomer unit B is 2,5-furandicarboxylic acid.
- the ratio of the aromatic dicarboxylic acid monomer unit A to the total of all dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A in the polyester resin ⁇ is preferably 15 mol% or more, and 20 mol% or more. More preferably, from the same viewpoint, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 20>, preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 25 mol% or less.
- the ratio of the dicarboxylic acid monomer unit B to the total of all dicarboxylic acid monomer units including the aromatic dicarboxylic acid monomer unit A in the polyester resin ⁇ is preferably 60 mol% or more, more preferably 70 mol% or more. 75 mol% or more is more preferable, and from the same viewpoint, 85 mol% or less is preferable, and 80 mol% or less is more preferable, the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 21>.
- the aromatic dicarboxylic acid A is preferably at least one selected from the group consisting of 5-sulfoisophthalic acid and 2-sulfoisophthalic acid, and more preferably 5-sulfoisophthalic acid.
- the diol C is preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, 1,3-propanediol and dipropylene glycol, and a group consisting of ethylene glycol and diethylene glycol.
- the weight average molecular weight of the polyester resin is preferably 3000 or more, more preferably 8000 or more, still more preferably 10,000 or more, still more preferably 20000 or more, still more preferably 30000 or more, still more preferably 40000 or more, 80000 or less is preferable, 70000 or less is more preferable, 60000 or less is further preferable, 50000 or less is more preferable, and 40000 or less is more preferable, 3D modeling solubility according to any one of ⁇ 1> to ⁇ 24> material.
- the glass transition temperature of the polyester resin is preferably 50 ° C.
- the soluble material for three-dimensional modeling according to any one of ⁇ 1> to ⁇ 25>, more preferably 140 ° C. or lower, further preferably 120 ° C. or lower.
- the content of the polyester resin in the three-dimensional modeling soluble material is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more.
- the glass transition temperature of the three-dimensional modeling soluble material is preferably 50 ° C or higher, more preferably 60 ° C or higher, still more preferably 70 ° C or higher, still more preferably 80 ° C or higher, and preferably 180 ° C or lower,
- the filamentous three-dimensional modeling soluble material preferably has a diameter of 0.5 mm or more, more preferably 1.0 mm or more, preferably 3.0 mm or less, more preferably 2.0 mm or less, and 1.8 mm.
- the three-dimensional modeling soluble material according to ⁇ 29> wherein the following is more preferable.
- the stretching ratio in the stretching process is preferably 1.5 times or more, more preferably 2 times or more, further preferably 3 times or more, still more preferably 5 times or more, preferably 200 times or less, and 150 times or less. Is more preferable, 100 times or less is still more preferable, and 50 times or less is still more preferable ⁇ 31>.
- the stretching temperature in the stretching process is within a range of a temperature 20 ° C.
- the lower limit of the stretching temperature in the stretching process is more preferably 10 ° C. lower than the glass transition temperature, the same temperature as the glass transition temperature is more preferable, and the upper limit of the stretching temperature in the stretching process is the glass transition temperature.
- a temperature higher by 40 ° C. is more preferable, a temperature higher by 30 ° C. than the glass transition temperature is further preferable, and a temperature higher by 20 ° C. than the glass transition temperature is more preferable.
- ⁇ 35> The three-dimensional modeling soluble material according to any one of ⁇ 1> to ⁇ 34>, further comprising a compatibilizer.
- 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 a material of the three-dimensional object is preferably a thermoplastic resin such as an ABS resin, a polylactic acid resin, a polycarbonate resin, and a polyphenylsulfone resin, more preferably an ABS resin and / or a polylactic acid resin,
- 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,
- the method for producing a three-dimensional object according to any one of ⁇ 36> to ⁇ 39> which is at least one selected from the group consisting of ketones such as acetone and methyl ethyl ketone.
- 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, still more preferably 1% by mass or more, and more preferably 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.
- ⁇ 42> A support material for supporting a three-dimensional object when a three-dimensional object is manufactured by a hot melt lamination type 3D printer, the aromatic dicarboxylic acid monomer unit A having a sulfonate group, and a sulfonate group.
- the ratio of the aromatic dicarboxylic acid monomer unit A to the total of the aromatic dicarboxylic acid monomer unit A and the dicarboxylic acid monomer unit B is 10 to 70 mol.
- ⁇ Analysis method> [Dicarboxylic acid composition, diol composition of polyester resin]
- the composition of the dicarboxylic acid monomer unit and the composition of the diol monomer unit were determined by proton NMR measurement using NMR and MR400 manufactured by Agilent. If it is difficult to determine the composition of the dicarboxylic acid monomer unit and the composition of the diol monomer unit from the NMR measurement because of overlapping peaks, etc., gas chromatography analysis is performed after the polyester is hydrolyzed with an alkali. Can be determined by
- ⁇ Mc Molecular weight of dicarboxylic acid other than isophthalate group (however, when there are a plurality of dicarboxylic acid species, the number average molecular weight)
- polyester compound 5 is heated at 188 ° C./25 kPa to 220 ° C./1 kPa for 1.7 hours, 220 ° C./56 Pa to 250 ° C./32 Pa for 2.2 hours, and further heated at 290 ° C./53 Pa to 295 ° C./31 Pa for 2.5 hours. Polycondensation was performed to obtain polyester compound 5 as a yellowish white solid (room temperature).
- polyester compound 6 was obtained as a white solid (room temperature).
- polyester compound 8 was obtained as a light brown white solid (room temperature).
- polyester compound 10 as a light brown white solid (room temperature).
- the temperature was raised from 0 ° C. to 240 ° C., and the ester exchange was performed by heating at 240 ° C. for 1 hour. Further, 20.6 mg of manganese (II) acetate tetrahydrate and 15.2 g of ethylene glycol were added, and the temperature was raised from 240 ° C. to 250 ° C. over 1 hour to perform transesterification. After adding 38.2 mg of 85% phosphoric acid and stirring for 15 minutes, the temperature was raised from 250 ° C. to 330 ° C. over 1.5 hours with a mantle heater, and at the same time stirring while reducing the pressure from 2.5 kPa to 30 Pa. Then, polycondensation was performed to obtain a polyester compound 11 as a light brown white solid (room temperature).
- polyester compound 13 was obtained as a light brown white solid (room temperature).
- polyester compound 14 was obtained by heating at 230 ° C. for 1 hour.
- the bath temperature was raised from 190 to 215 ° C. over 2 hours, and the pressure was reduced from 4 kPa to 455 Pa at the same time. Then, the temperature was raised from 190 ° C. to 275 ° C. over 2.5 hours with a mantle heater, and simultaneously from 200 Pa to 15 Pa.
- the polycondensation was carried out while stirring under reduced pressure to obtain polyester compound 14 as a light brown white solid (room temperature).
- polyester compound 18 was obtained as a yellow solid (room temperature).
- polyester compound 19 was obtained as a light brown white solid (room temperature).
- room temperature the composition of the diol unit in the polyester compound 19, since each component peak overlapped from proton NMR, it was not able to analyze.
- the temperature was raised from 260 to 290 ° C. over 20 minutes and simultaneously reduced from normal pressure to 3.5 kPa, then heated from 290 ° C. to 300 ° C. over 1.5 hours and simultaneously from 3.5 kPa.
- the polycondensation was carried out with stirring while reducing the pressure to 520 Pa to obtain a polyester compound 20 as a white yellow solid (room temperature).
- room temperature the temperature of the diol unit in the polyester compound 20 since each component peak overlapped from proton NMR, it was not able to analyze.
- the dicarboxylic acid composition, the diol composition, the amount of sulfonate group, the weight average molecular weight, and the glass transition temperature were determined by the above analysis method.
- the measurement results are shown in Tables 1 and 2.
- SIP (mol%) is the ratio (mol%) of 5-sulfoisophthalic acid monomer unit in all dicarboxylic acid monomer units
- FDCA (mol%) is the flange in all dicarboxylic acid monomer units.
- the proportion of carboxylic acid monomer units (mol%), TPA (mol%) is the proportion of terephthalic acid monomer units in all dicarboxylic acid monomer units (mol%), and NPDCA (mol%) is 2 in all dicarboxylic acid monomer units.
- 6-Naphthalenedicarboxylic acid monomer unit ratio (mol%), EG (mol%) is the ethylene glycol monomer unit ratio (mol%) in all diol monomer units, and DEG (mol%) is diethylene glycol in all diol monomer units.
- Monomer unit ratio ( ol%), 1,3 PD (mol%) is the ratio (mol%) of the 1,3-propanediol monomer unit in all diol monomer units, and DPG (mol%) is the dipropylene glycol monomer unit in all diol monomer units.
- the ratio (mol%), CHDM (mol%) is the ratio (mol%) of 1,4-cyclohexanedimethanol monomer unit in all diol monomer units, and IS (mol%) is the isosorbide monomer in all diol monomer units.
- Unit ratio (mol%), HBPA (mol%) is the ratio of hydrogenated bisphenol A monomer unit in all diol monomer units (mol%), and BPEF (mol%) is the ratio of bisphenoxyethanol fluorene in all diol monomer units.
- Mol%), O 3 (mmol / g) indicates the amount of sulfonate groups in the polyester (mmol / g).
- Dissolution rate (%) (polymer mass before dissolution ⁇ polymer mass remaining undissolved) / polymer mass before dissolution ⁇ 100
- composition 3 as a white mixture.
- the extruded composition was cooled with water, and then the filament was wound on a roll at a speed of 10.0 m / min, and further heated with hot air at 200 ° C. (actual filament temperature measurement value: 100 ° C.) to 18.0 m / min. Stretching (total draw ratio: 8.7 to 11 times) while winding on a roll at a speed to obtain a filament having a diameter of about 1.5 to 1.7 mm. It was found that the drawn filament of composition 2 was clearly tougher than the low draw ratio (1.8 times) filament of the same composition prepared from the capilograph as in Example 16.
- the extruded composition was cooled with water, and then the filament was wound on a roll at a speed of 8.0 m / min, and further heated with hot air at 195 ° C. (actual filament temperature measurement value: 100 ° C.) to 20.5 m / min. Stretching (total draw ratio: 8.7 to 9.8 times) while winding on a roll at a speed to obtain a filament having a diameter of about 1.6 to 1.7 mm. It was found that the stretched filaments of Composition 3 were clearly tougher than the low stretch ratio (1.8 times) filaments of the same composition made from the capilograph as in Example 16.
- Examples 1 to 23 and Comparative Examples 1 to 4 The polyester compounds 1 to 17 obtained in the synthesis examples, the compositions 1 to 3, and the following commercially available support materials 1 and 2 were evaluated for solubility in water and hygroscopicity by the above-described methods. The results are shown in Table 3 and Table 4. Further, the polyester compounds 18 to 20 obtained in the above synthesis examples and the following commercially available support material 1 and support material 2 were evaluated for solubility in neutral water containing a water-soluble organic solvent and hygroscopicity. The results are shown in Table 5. In addition, the commercial item 1 and the commercial item 2 in Table 3, Table 4, and Table 5 are as follows, respectively.
- -Commercial product 1 Natural PVA / 1.75 mm polyvinyl alcohol (manufactured by Kenville, number average molecular weight 30000, glass transition temperature: 80 ° C.)
- -Commercial product 2 Soluble Support Material P400SR (registered trademark), methacrylic acid / methyl methacrylate: 55/45% by weight copolymer (manufactured by Stratasys, composition is analyzed by proton NMR (DMSO-d6), weight average molecular weight : 130000, glass transition temperature: 100 ° C., plasticizer: containing triphenyl phosphate, etc.)
- Example 24 The polyester compound 6 was extruded from a capillary having a diameter of 2 mm and a length of 10 mm at a melting temperature of 180 ° C. and an extrusion speed of 10 mm / min using a capillograph (Capigraph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.). While being pulled lightly, it was processed into a filament having a diameter of 1.5 mm. After that, the filament was supplied to Genkei's Atom 3D Printer and extruded from a heat nozzle having a temperature of 230 ° C., and it was confirmed that the nozzle could be discharged without clogging, and the melt also solidified immediately. .
- a capillograph Capigraph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd.
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Abstract
Description
本実施形態の三次元造形用可溶性材料は、FDM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、スルホン酸塩基を有する芳香族ジカルボン酸モノマーユニットA、スルホン酸塩基を有さないジカルボン酸モノマーユニットB、及びジオールモノマーユニットを有し、全ジカルボン酸モノマーユニットの合計に対する、前記芳香族ジカルボン酸モノマーユニットAの割合が10~70mol%であるポリエステル樹脂を含む。
[芳香族ジカルボン酸モノマーユニットA]
前記ポリエステル樹脂は、スルホン酸塩基を有する芳香族ジカルボン酸モノマーユニットを有する。本明細書において、スルホン酸塩基を有する芳香族ジカルボン酸のモノマーユニットを芳香族ジカルボン酸モノマーユニットAとも称する。また、当該芳香族ジカルボン酸モノマーユニットAを誘導するための芳香族ジカルボン酸を芳香族ジカルボン酸Aとも称する。
前記ポリエステル樹脂は、スルホン酸塩基を有しないジカルボン酸モノマーユニットを有する。本明細書においてスルホン酸塩基を有しないジカルボン酸のモノマーユニットをジカルボン酸モノマーユニットBとも称する。また、当該ジカルボン酸モノマーユニットBを誘導するためのジカルボン酸をジカルボン酸Bとも称する。ジカルボン酸Bはスルホン酸塩基を有しない。
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、前記芳香族ジカルボン酸モノマーユニットA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、前記芳香族ジカルボン酸モノマーユニットA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、15mol%以上が好ましく、20mol%以上がより好ましく、同様の観点から、40mol%以下が好ましく、30mol%以下がより好ましく、25mol%以下が更に好ましい。
(前記化学式(1)中、Xはエチレンフラノエートの重合度、Y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、エチレンフラノエートとエチレン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。)
(前記化学式(2)中、Xは1,3-プロピレンフラノエートの重合度、Yは1,3-プロピレン5-スルホイソフタレートの重合度の数を表す。ただし、1,3-プロピレンフラノエートとは1,3-プロピレン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。)
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、高湿度下に暴露された後に3Dプリンタによる三次元物体の製造に用いても発泡を抑制して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サポート材を速やかに除去することができる。当該三次元物体の製造方法がこの様な効果を奏する理由は定かでないが、前記三次元造形用可溶性材料が前記効果を奏する理由と同様の理由が考えられる。
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%以上が更に好ましく、3質量%以上が更に好ましく、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、前記ポリエステル樹脂を含む。当該サポート材は、高湿度下に暴露された後に3Dプリンタによる三次元物体の製造に用いても発泡を抑制して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サポート材を速やかに除去することができる。当該サポート材がこの様な効果を奏する理由は定かでないが、前記三次元造形用可溶性材料が前記効果を奏する理由と同様の理由が考えられる。
<2>芳香族ジカルボン酸モノマーユニットAを誘導するための芳香族ジカルボン酸Aが、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種以上がより好ましく、5-スルホイソフタル酸が更に好ましい、前記<1>に記載の三次元造形用可溶性材料。
<3>前記ポリエステル樹脂中の全ジカルボン酸モノマーユニットの合計に対する、前記芳香族ジカルボン酸モノマーユニットAの割合が、10mol%以上であり、15mol%以上が好ましく、18mol%以上がより好ましく、20mol%以上が更に好ましく、70mol%以下であり、60mol%以下が好ましく、50mol%以下がより好ましく、40mol%以下が更に好ましく、30mol%以下がより更に好ましく、25mol%以下がより更に好ましい、前記<1>又は<2>に記載の三次元造形用可溶性材料。
<4>前記ポリエステル樹脂中の前記芳香族ジカルボン酸モノマーユニットAの含有量が、5mol%以上が好ましく、7.5mol%以上がより好ましく、9mol%以上が更に好ましく、10mol%以上がより更に好ましく、35mol%以下が好ましく、30mol%以下がより好ましく、25mol%以下が更に好ましく、20mol%以下がより更に好ましく、15mol%以下がより更に好ましく、13mol%以下がより更に好ましい、前記<1>~<3>のいずれかに記載の三次元造形用可溶性材料。
<5>前記スルホン酸塩基を構成するスルホン酸基の対イオンが、リチウムイオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、アンモニウムイオンから選ばれる無機陽イオン、モノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン、トリエタノールアンモニウムイオンから選ばれる有機陽イオンが好ましく、ナトリウムイオン、カリウムイオン、マグネシウムイオン、及びアンモニウムイオンから選ばれる陽イオンがより好ましく、ナトリウムイオン、カリウムイオンが更に好ましく、ナトリウムイオンがより更に好ましい、前記<1>~<4>のいずれかに記載の三次元造形用可溶性材料。
<6>前記ポリエステル樹脂中の前記スルホン酸塩の含有量が、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以上が更に好ましく、0.8mmol/g以上がより更に好ましく、0.9mmol/g以上がより更に好ましく、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以下が更に好ましく、1.3mmol/g以下がより更に好ましく、1.2mmol/g以下がより更に好ましい、前記<1>~<5>のいずれかに記載の三次元造形用可溶性材料。
<7>前記ジカルボン酸モノマーユニットBを誘導するためのジカルボン酸Bが、芳香族ジカルボン酸、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種以上が更に好ましい、前記<1>~<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ジカルボン酸モノマーユニットの合計に対する、前記ジカルボン酸モノマーユニットBの割合が、30mol%以上が好ましく、40mol%以上がより好ましく、50mol%以上が更に好ましく、60mol%以上がより更に好ましく、70mol%以上がより更に好ましく、75mol%以上がより更に好ましく、90mol%以下が好ましく、85mol%以下がより好ましく、82mol%以下が更に好ましく、80mol%以下がより更に好ましい、前記<1>~<7>のいずれかに記載の三次元造形用可溶性材料。
<9>前記ポリエステル樹脂中の前記ジカルボン酸モノマーユニットBの含有量が、15mol%以上が好ましく、20mol%以上がより好ましく、25mol%以上が更に好ましく、30mol%以上がより更に好ましく、35mol%以上がより更に好ましく、38mol%以上がより更に好ましく、45mol%以下が好ましく、43mol%以下がより好ましく、41mol%以下が更に好ましく、40mol%以下がより更に好ましい、前記<1>~<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ジカルボン酸モノマーユニットの合計に対する、前記芳香族ジカルボン酸モノマーユニットAと前記ジカルボン酸モノマーユニットBの合計の割合が、80mol%以上が好ましく、90mol%以上がより好ましく、95mol%以上が更に好ましく、98mol%以上がより更に好ましく、実質的に100mol%がより更に好ましく、100mol%がより更に好ましい、前記<1>~<9>のいずれかに記載の三次元造形用可溶性材料。
<11>前記芳香族ジカルボン酸モノマーユニットAと前記ジカルボン酸モノマーユニットBのmol比(前記芳香族ジカルボン酸モノマーユニットA/前記ジカルボン酸モノマーユニットB)が、10/90以上が好ましく、15/85以上がより好ましく、18/82以上が更に好ましく、20/80以上がより更に好ましく、50/50以下が好ましく、40/60以下がより好ましく、30/70以下が更に好ましく、25/75以下がより更に好ましい、前記<1>~<10>のいずれかに記載の三次元造形用可溶性材料。
<12>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Cが、脂肪族ジオール、芳香族ジオール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、脂肪族ジオール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い、前記<1>~<11>のいずれかに記載の三次元造形用可溶性材料。
<13>前記ジオールCの炭素数が、2以上が好ましく、31以下が好ましく、25以下がより好ましく、20以下が更に好ましく、15以下がより更に好ましい、前記<1>~<12>のいずれかに記載の三次元造形用可溶性材料。
<14>前記脂肪族ジオールが、鎖式ジオール、及び環式ジオール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、鎖式ジオールがより好ましい、前記<1>~<13>のいずれかに記載の三次元造形用可溶性材料。
<15>前記鎖式ジオールの炭素数が、2以上が好ましく、6以下が好ましく、4以下がより好ましく、3以下が更に好ましい、前記<14>に記載の三次元造形用可溶性材料。
<16>前記環式ジオールの炭素数が、6以上が好ましく、31以下が好ましく、25以下がより好ましく、20以下が更に好ましく、15以下がより更に好ましく、10以下がより更に好ましく、8以下がより更に好ましい、前記<14>又は<15>に記載の三次元造形用可溶性材料。
<17>前記鎖式ジオールが、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、エチレングリコール、1,2-プロパンジオール、及び1,3-プロパンジオール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い、前記<14>~<16>のいずれかに記載の三次元造形用可溶性材料。
<18>前記ジオールモノマーユニットがジエチレングリコールユニットを含み、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が、5mol%以上が好ましく、10mol%以上がより好ましく、15mol%以上が更に好ましく、20mol%以上が更に好ましく、25mol%以上がより更に好ましく、30mol%以上がより更に好ましく、60mol%以下が好ましく、55mol%以下がより好ましく、50mol%以下が更に好ましく、45mol%以下がより更に好ましい、<1>~<17>のいずれかに記載の三次元造形用可溶性材料。
<19>前記環式ジオールが、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からなる群より選ばれる少なくとも1種以上が好ましい、前記<14>~<18>のいずれかに記載の三次元造形用可溶性材料。
<20>前記ポリエステル樹脂が、前記芳香族ジカルボン酸モノマーユニットA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、前記芳香族ジカルボン酸モノマーユニットAの割合、及び前記ジカルボン酸モノマーユニットBの割合が、それぞれ15~40mol%、及び60~85mol%であり、前記ジカルボン酸モノマーユニットBを得るためのジカルボン酸Bが2,5-フランジカルボン酸であるポリエステル樹脂αが好ましい、前記<1>~<19>のいずれかに記載の三次元造形用可溶性材料。
<21>前記ポリエステル樹脂αにおける、前記芳香族ジカルボン酸モノマーユニットA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、前記芳香族ジカルボン酸モノマーユニットAの割合が、15mol%以上が好ましく、20mol%以上がより好ましく、同様の観点から、40mol%以下が好ましく、30mol%以下がより好ましく、25mol%以下が更に好ましい、前記<1>~<20>のいずれかに記載の三次元造形用可溶性材料。
<22>前記ポリエステル樹脂αにおける、前記芳香族ジカルボン酸モノマーユニットA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、前記ジカルボン酸モノマーユニットBの割合が、60mol%以上が好ましく、70mol%以上がより好ましく、75mol%以上が更に好ましく、同様の観点から、85mol%以下が好ましく、80mol%以下がより好ましい、前記<1>~<21>のいずれかに記載の三次元造形用可溶性材料。
<23>前記ポリエステル樹脂αにおける、前記芳香族ジカルボン酸Aが、5―スルホイソフタル酸、及び2―スルホイソフタル酸からなる群より選ばれる少なくとも1種以上が好ましく、5―スルホイソフタル酸がより好ましい、前記<1>~<22>のいずれかに記載の三次元造形用可溶性材料。
<24>前記ポリエステル樹脂αにおける、前記ジオールCが、エチレングリコール、ジエチレングリコール、1,3-プロパンジオール、ジプロピレングリコール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、エチレングリコール、及びジエチレングリコール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い、前記<1>~<25>のいずれかに記載の三次元造形用可溶性材料。
<25>前記ポリエステル樹脂の重量平均分子量が、3000以上が好ましく、8000以上がより好ましく、10000以上が更に好ましく、20000以上がより更に好ましく、30000以上がより更に好ましく、40000以上がより更に好ましく、80000以下が好ましく、70000以下がより好ましく、60000以下が更に好ましく、50000以下がより更に好ましく、40000以下がより更に好ましい、前記<1>~<24>のいずれかに記載の三次元造形用可溶性材料。
<26>前記ポリエステル樹脂のガラス転移温度が、50℃以上が好ましく、60℃以上がより好ましく、70℃以上が更に好ましく、80℃以上がより更に好ましく、180℃以下が好ましく、160℃以下がより好ましく、140℃以下が更に好ましく、120℃以下がより更に好ましい、前記<1>~<25>のいずれかに記載の三次元造形用可溶性材料。
<27>前記三次元造形用可溶性材料中の前記ポリエステル樹脂の含有量が、30質量%以上が好ましく、50質量%以上がより好ましく、60質量%以上が更に好ましく、70質量%以上がより更に好ましく、80質量%以上がより更に好ましく、90質量%以上がより更に好ましく、95質量%以上がより更に好ましく、実質的に100質量%がより更に好ましく、100質量%がより更に好ましい、前記<1>~<26>のいずれかに記載の三次元造形用可溶性材料。
<28>前記三次元造形用可溶性材料のガラス転移温度が、50℃以上が好ましく、60℃以上がより好ましく、70℃以上が更に好ましく、80℃以上がより更に好ましく、180℃以下が好ましく、160℃以下がより好ましく、140℃以下が更に好ましく、120℃以下がより更に好ましい、前記<1>~<27>のいずれかに記載の三次元造形用可溶性材料。
<29>前記三次元造形用可溶性材料の形状が、ペレット状、粉末状、フィラメント状が好ましく、フィラメント状がより好ましい、前記<1>~<28>のいずれかに記載の三次元造形用可溶性材料。
<30>前記フィラメント状の三次元造形用可溶性材料の直径が、0.5mm以上が好ましく、1.0mm以上がより好ましく、3.0mm以下が好ましく、2.0mm以下がより好ましく、1.8mm以下が更に好ましい、前記<29>に記載の三次元造形用可溶性材料。
<31>前記フィラメント状の三次元造形用可溶性材料が、延伸加工された三次元造形用可溶性材料が好ましい<29>又は<30>に記載の三次元造形用可溶性材料。
<32>前記延伸加工における延伸倍率が、1.5倍以上が好ましく、2倍以上がより好ましく、3倍以上が更に好ましく、5倍以上がより更に好ましく、200倍以下が好ましく、150倍以下がより好ましく、100倍以下が更に好ましく、50倍以下がより更に好ましい<31>に記載の三次元造形用可溶性材料。
<33>前記延伸加工における延伸温度が、前記三次元造形用可溶性材料のガラス転移温度より20℃低い温度から当該ガラス転移温度より60℃高い温度の範囲内で行うことが好ましい<31>又は<32>に記載の三次元造形用可溶性材料。
<34>前記延伸加工における延伸温度の下限が、前記ガラス転移温度より10℃低い温度がより好ましく、前記ガラス転移温度と同じ温度が更に好ましく、前記延伸加工における延伸温度の上限が前記ガラス転移温度より40℃高い温度がより好ましく、前記ガラス転移温度より30℃高い温度が更に好ましく、前記ガラス転移温度より20℃高い温度が更に好ましい<31>~<33>のいずれかに記載の三次元造形用可溶性材料。
<35>更に、相溶化剤を含有する<1>~<34>いずれかに記載の三次元造形用可溶性材料。
<36>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<1>~<37>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。
<37>三次元物体の材料である造形材が、ABS樹脂、ポリ乳酸樹脂、ポリカーボネート樹脂、及びポリフェニルサルフォン樹脂等の熱可塑性樹脂が好ましく、ABS樹脂及び/又はポリ乳酸樹脂がより好ましく、ABS樹脂が更に好ましい、前記<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、前記<36>又は<37>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、前記<36>~<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からなる群より選ばれる1種以上である、前記<36>~<39>のいずれか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%以上が更に好ましく、3質量%以上が更に好ましく、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、前記<39>又は<40>に記載の三次元物体の製造方法。
<42>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、スルホン酸塩基を有する芳香族ジカルボン酸モノマーユニットA、スルホン酸塩基を有さないジカルボン酸モノマーユニットB、及びジオールモノマーユニットを有し、前記芳香族ジカルボン酸モノマーユニットA及び前記ジカルボン酸モノマーユニットBの合計に対する、前記芳香族ジカルボン酸モノマーユニットAの割合が10~70mol%であるポリエステル樹脂を含む、サポート材。
<43>前記ポリエステル樹脂が、前記<1>~<35>のいずれかに記載の三次元造形用可溶性材料に用いられるポリエステル樹脂である、前記<42>に記載のサポート材。
<44>前記<1>~<35>のいずれかに記載の三次元造形用可溶性材料のサポート材の材料としての使用。
〔ポリエステル樹脂のジカルボン酸組成、ジオール組成〕
Agilent社製NMR、MR400を用いたプロトンNMR測定により、ジカルボン酸モノマーユニットの組成、及びジオールモノマーユニットの組成を求めた。なお、NMR測定からはピークが重なる等の理由によりジカルボン酸モノマーユニットの組成、及びジオールモノマーユニットの組成を求めることが困難である場合には、ポリエステルをアルカリで加水分解後、ガスクロマトグラフィ分析を行うことによって求めることができる。
上記方法で求めたイソフタル酸塩基モノマーユニットの組成からポリエステル中のスルホン酸塩基量(mmol/g)を下式に従い算出した。但し、全ジカルボン酸モノマーユニットのmol数と全ジオールモノマーユニットのmol数は等しいと仮定した。
スルホン酸塩基量(mmol/g)=A×1000/(A×(Ms+Mo)+(100-A)×(Mc+Mo)-2×18.0×100)
・A:全ジカルボン酸モノマーユニット中のイソフタル酸塩基モノマーユニットの割合(mol%)
・Ms:スルホイソフタル酸塩(遊離ジカルボン酸型)の分子量
・Mo:ジオールの分子量(ただし、ジオール種が複数の場合は数平均分子量)
・Mc:イソフタル酸塩基以外のジカルボン酸の分子量(ただし、該ジカルボン酸種が複数の場合は数平均分子量)
下記条件により、ゲルパーミエーションクロマトグラフ(GPC)法を用いて標準ポリスチレンから校正曲線を作成し、重量平均分子量(Mw)を求めた。
(測定条件)
・装置:HLC-8320 GPC(東ソー株式会社製、検出器一体型)
・カラム:α-M×2本(東ソー株式会社製、7.8mmI.D.×30cm)
・溶離液:60mmol/lリン酸+50mmol/l臭素化リチウムジメチルホルムアミド溶液
・流量:1.0ml/min
・カラム温度:40℃
・検出器:RI検出器
・標準物質:ポリスチレン
プレス機(東洋精機製作所社製 ラボプレスP2-30T)を用い、サンプルを200℃/20MPaの温度/圧力で2分間プレスした後、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。
〔合成例1〕
2Lステンレス製セパラブルフラスコ(脱水管、撹拌機、窒素導入管付)に2,5-フランジカルボン酸239g(V&V PHARMA INDUSTRIES社製)、エチレングリコール209g(和光純薬工業社製、特級)、オクチル酸スズ0.224g(日東化成社製)、没食子酸0.022g(和光純薬工業社製)を仕込み、常圧、窒素雰囲気下、マントルヒータで200℃、20時間加熱し、エステル化を行った。室温まで冷却後、5-スルホイソフタル酸ジメチルナトリウム118g(和光純薬工業社製)、エチレングリコール54g、チタンテトライソプロポキド0.058g(和光純薬工業社製、一級)、没食子酸0.006gを添加して昇温し、185℃、常圧で4時間撹拌し、エステル交換を行った。215℃に昇温後、4時間かけて12kPaから400Paまで減圧し、さらに240℃、660Paで7時間撹拌して重縮合を行い、黒褐色固体(室温)のポリエステル化合物1を得た。
1Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)に2,5-フランジカルボン酸125g、エチレングリコール149gを仕込み、常圧、窒素雰囲気下、バス温205℃で5時間加熱し、エステル化を行った。140℃まで冷却後、5-スルホイソフタル酸ジメチルナトリウム116gを添加し、140℃で0.5時間撹拌した。100℃に冷却後、チタンテトライソプロポキド0.364gを添加して昇温し、210℃/常圧で1時間、140℃/3kPa~210℃/2kPaで1.5時間、210℃/1360Pa~250℃/90Paで1時間加熱して重縮合を行い、黄色固体(室温)のポリエステル化合物2を得た。
1Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)に2,5-フランジカルボン酸125g、エチレングリコール149gを仕込み、常圧、窒素雰囲気下、バス温205℃で5時間加熱し、エステル化を行った。100℃まで冷却後、5-スルホイソフタル酸ジメチルナトリウム61.6gを添加し、160℃で0.5時間撹拌した。50℃に冷却後、チタンテトライソプロポキド0.364gを添加して昇温し、205℃/常圧で1時間、144℃/2.1kPa~233℃/1.88kPaで1時間、201℃/556Pa~234℃/410Paで1時間、さらに232℃/113Pa~240℃/141Paで1時間加熱して重縮合を行い、黄色固体(室温)のポリエステル化合物3を得た。
1Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)に2,5-フランジカルボン酸125g、1,3-プロパンジオール183g(和光純薬工業社製、特級)を仕込み、常圧、窒素雰囲気下、バス温205℃で6時間加熱し、エステル化を行った。100℃まで冷却後、5-スルホイソフタル酸ジメチルナトリウム67.3gを添加した。さらに75℃まで冷却後、チタンテトライソプロポキド0.364gを添加して昇温し、235℃/常圧で1時間、190℃/11kPa~208℃/3kPaで0.5時間、235℃/74Pa~234℃/26Paで1時間、さらに245℃/30Paで1.5時間加熱して重縮合を行い、黄色固体(室温)のポリエステル化合物4を得た。
2Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル583g(和光純薬工業社製、一級)、エチレングリコール559g、およびチタンテトライソプロポキド1.364gを仕込んで昇温し、常圧、窒素雰囲気下、バス温210℃で2時間加熱し、エステル交換を行った。120℃まで冷却後、5-スルホイソフタル酸ジメチルナトリウム242gを添加して昇温し、211~230℃/常圧で2時間反応させた。その後、188℃/25kPa~220℃/1kPaで1.7時間、220℃/56Pa~250℃/32Paで2.2時間、さらに290℃/53Pa~295℃/31Paで2.5時間加熱して重縮合を行い、黄白色固体(室温)のポリエステル化合物5を得た。
1Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル194g、エチレングリコール186g、およびチタンテトライソプロポキド0.455gを仕込んで昇温し、常圧、窒素雰囲気下、バス温210℃で2時間加熱してエステル交換を行った。90℃まで冷却後、5-スルホイソフタル酸ジメチルナトリウム80.7gを添加して昇温し、190~210℃/常圧で2時間反応させた。その後、200℃/2kPa~240℃/200Paで2.5h、235℃/270Pa~245℃/12Paで2.5h加熱して重縮合を行い、白色固体(室温)のポリエステル化合物6を得た。
0.5Lステンレス製セパラブルフラスコ(脱水管、撹拌機、窒素導入管付)に2,5-フランジカルボン酸101g、エチレングリコール88.8g、オクチル酸スズ0.095g、没食子酸0.010gを仕込み、常圧、窒素雰囲気下、マントルヒータで200℃、20時間加熱してエステル化を行った。室温まで冷却後、5-スルホイソフタル酸ジメチルナトリウム19.3g、エチレングリコール9g、チタンテトライソプロポキド0.022g、没食子酸0.002gを添加して昇温し、200℃、常圧で4時間反応させた。200℃のまま、7.5時間かけて670Paから133Paまで減圧しながら撹拌して重縮合を行い、黒褐色固体(室温)のポリエステル化合物7を得た。
1Lステンレス製セパラブルフラスコ(K字管、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40.5g(東京化成工業社製、一級)、エチレングリコール31.8g、5-スルホイソフタル酸ジメチルナトリウム16.9g、酢酸マンガン(II)・四水和物(和光純薬工業社製、特級)14.6mg、酢酸ナトリウム・三水和物(和光純薬工業社製、特級)465mgを仕込み、常圧、窒素雰囲気下、1.5時間かけてバス温209℃から250℃に昇温し、250℃で1時間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7.3mg添加し、10分間撹拌した後、三酸化アンチモン(和光純薬工業社製、99.9%)13.1mgを加え、マントルヒータで2時間かけて外温270℃から300℃まで昇温し、同時に3.3kPaから30Pa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)のポリエステル化合物8を得た。
1Lステンレス製セパラブルフラスコ(K字管、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48.8g、エチレングリコール43.4g、5-スルホイソフタル酸ジメチルナトリウム30.2g、チタンテトラブトキシド(東京化成工業社製、一級)20.4mg、酢酸ナトリウム502mgを仕込み、常圧、窒素雰囲気下、2.5時間かけてバス温190℃から250℃に昇温し、250℃で0.5時間加熱してエステル交換を行った。85%リン酸を7.6mg添加し、10分間撹拌した後、マントルヒータで1.5時間かけて外温250℃から330℃まで昇温し、同時に2.5kPaから30Pa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)のポリエステル化合物9を得た。
2Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル388g、エチレングリコール298g、1,4-シクロヘキサンジメタノール(cis-,trans-混合物)(和光純薬工業社製、一級)173g、チタンテトライソプロポキド910mgを仕込み、常圧、窒素雰囲気下、2.5時間かけてバス温190℃から200℃に昇温し、200℃で0.5時間加熱してエステル交換を行った。5-スルホイソフタル酸ジメチルナトリウム253gを添加し、2時間かけてバス温200℃から230℃まで昇温し、230℃で0.5時間加熱してエステル交換を行った。マントルヒータで5時間かけて外温190℃から290℃まで昇温し、同時に2.4kPaから20Pa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)のポリエステル化合物10を得た。
1Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル65.6g、2,6-ナフタレンジカルボン酸ジメチル68.4g、5-スルホイソフタル酸ジメチルナトリウム76.5g、エチレングリコール84.8g、1,4-シクロヘキサンジメタノール(cis-, trans-混合物)(和光純薬工業社製、一級)59.9g、酢酸マンガン(II)・四水和物41.2mg、酢酸ナトリウム・三水和物2.11g、酢酸コバルト(II)・四水和物(和光純薬工業社製、特級)12.2mgを仕込み、常圧、窒素雰囲気下、4時間かけてバス温190℃から240℃に昇温し、240℃で1時間加熱してエステル交換を行った。さらに、酢酸マンガン(II)・四水和物20.6mg、エチレングリコール15.2gを添加し、1時間かけてバス温240℃から250℃に昇温してエステル交換を行った。85%リン酸を38.2mg添加し、15分間撹拌した後、マントルヒータで1.5時間かけて外温250℃から330℃まで昇温し、同時に2.5kPaから30Pa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)のポリエステル化合物11を得た。
2Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル234.1g、5-スルホイソフタル酸ジメチルナトリウム164.4g、エチレングリコール186.2g、イソソルバイド(東京化成工業社製、一級)131.5g、酢酸マンガン(II)・四水和物88.2mg、酢酸ナトリウム・三水和物4.53g、酢酸コバルト(II)・四水和物26.2mgを仕込み、常圧、窒素雰囲気下、2時間かけてバス温190℃から230℃に昇温し、230℃で0.5時間加熱してエステル交換を行った。85%リン酸を50.7mg添加し、15分間撹拌した後、三酸化アンチモン118mgを添加し、マントルヒータで5時間かけて外温230℃から310℃まで昇温し、同時に4.1kPaから30Pa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)のポリエステル化合物12を得た。
2Lステンレス製セパラブルフラスコ(K字管、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97.7g、5-スルホイソフタル酸ジメチルナトリウム62.2g、エチレングリコール77.2g、イソソルバイド23.4g、チタンテトラブトキシド40.8mg、酢酸ナトリウム0.517gを仕込み、常圧、窒素雰囲気下、マントルヒータで2時間かけて外温190℃から250℃に昇温し、250℃で1時間加熱してエステル交換を行った。85%リン酸を15.2mg添加し、15分間撹拌した後、マントルヒータで2時間かけて外温250℃から340℃まで昇温し、同時に3.2kPaから50Pa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)のポリエステル化合物13を得た。
2Lステンレス製セパラブルフラスコ(K字管、撹拌機、窒素導入管付)にテレフタル酸ジメチル388g、水添ビスフェノールA(和光純薬工業社製、一級)361g、エチレングリコール279g、チタンテトライソプロポキド910mgを仕込み、常圧、窒素雰囲気下、2.5時間、バス温190℃に維持した後、0.5時間かけて200℃に昇温してエステル交換を行った。5?スルホイソフタル酸ジメチルナトリウム338gを添加し、1時間かけてバス温200℃から230℃まで昇温し、230℃で1時間加熱してエステル交換を行った。2時間かけてバス温190から215℃まで昇温し、同時に4kPaから455Paまで減圧した後、マントルヒータで2.5時間かけて外温190℃から275℃まで昇温し、同時に200Paから15Pa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)のポリエステル化合物14を得た。
1Lステンレス製セパラブルフラスコ(K字管、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60.3g、エチレングリコール45.4g、5-スルホイソフタル酸ジメチルナトリウム24.9g、チタンテトラブトキシド14mg、酢酸ナトリウム104mgを仕込み、常圧、窒素雰囲気下マントルヒータで外温240℃/7時間エステル交換反応を行った。続いてマントルヒータで外温280℃まで昇温し、同時に0.9kPaまで減圧しながら撹拌して2.25時間重縮合を行い、微黄色透明(室温)のポリエステル化合物15を得た。
30Lステンレス製セパラブルフラスコ(K字管、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2770g、エチレングリコール2086g、5-スルホイソフタル酸ジメチルナトリウム1144g、チタンテトラブトキシド643mg、酢酸ナトリウム4.78gを仕込み、常圧、窒素雰囲気下内温230℃/6.2時間エステル交換反応を行った。続いて内温265℃まで昇温し、同時に0.9kPa(7mmHg)まで減圧しながら撹拌して2時間重縮合を行い、微黄色透明(室温)のポリエステル化合物16を得た。なお、本合成例は、組成物2及び3の調製、及びフィラメント作成を行うため7バッチ実施した。これらは再現性良く合成できた。
2Lステンレス製セパラブルフラスコ(K字管、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244g、エチレングリコール216g、5-スルホイソフタル酸ジメチルナトリウム101g、チタンテトラブトキシド57mg、酢酸ナトリウム211mgを仕込み、常圧、窒素雰囲気下マントルヒータで外温235℃/6.2時間エステル交換反応を行った。続いてマントルヒータで外温270℃まで昇温し、同時に4.9kPaまで減圧しながら撹拌して2時間重縮合を行い、微黄色透明(室温)のポリエステル化合物17を得た。
2Lステンレス製セパラブルフラスコ(K字管、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97.7g、5?スルホイソフタル酸ジメチルナトリウム30g、エチレングリコール71.6g、チタンテトラブトキシド81mg、酢酸ナトリウム374mgを仕込み、常圧、窒素雰囲気下、マントルヒータで45分かけて、外温190℃から260℃まで昇温し、そのまま6.5時間加熱撹拌してエステル交換反応を行った。20分かけて外温260から290℃まで昇温し、同時に常圧から4.1kPaまで減圧した後、2.8時間かけて外温290℃から300℃まで昇温し、同時に4.1kPaから80Paまで減圧しながら撹拌して重縮合を行い、黄色固体(室温)のポリエステル化合物18を得た。
2Lステンレス製セパラブルフラスコ(K字管、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37.1g、5?スルホイソフタル酸ジメチルナトリウム51.5g、ビスフェノキシエタノールフルオレン(東京化成工業社製)99.9g、エチレングリコール32.4g、チタンテトラブトキシド31mg、酢酸ナトリウム642mgを仕込み、常圧、窒素雰囲気下、マントルヒータで2.5時間かけて、外温200℃から260℃まで昇温し、そのまま6.5時間加熱撹拌してエステル交換反応を行った。1時間かけて外温260から290℃まで昇温し、同時に常圧から5.2kPaまで減圧した後、1時間かけて外温290℃から300℃まで昇温し、同時に550Paから290Pa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)のポリエステル化合物19を得た。なお、ポリエステル化合物19中のジオールユニットの組成については、プロトンNMRからは各成分ピークが重なったため分析することができなかった。
2Lステンレス製セパラブルフラスコ(K字管、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61.4g、5?スルホイソフタル酸ジメチルナトリウム52.5g、ビスフェノキシエタノールフルオレン(東京化成工業社製)75.0g、エチレングリコール50.4g、チタンテトラブトキシド51mg、酢酸ナトリウム436mgを仕込み、常圧、窒素雰囲気下、マントルヒータで1時間45分かけて、外温190℃から260℃まで昇温し、そのまま6.5時間加熱撹拌してエステル交換反応を行った。20分かけて外温260から290℃まで昇温し、同時に常圧から3.5kPaまで減圧した後、1.5時間かけて外温290℃から300℃まで昇温し、同時に3.5kPaから520Paまで減圧しながら撹拌して重縮合を行い、白黄色固体(室温)のポリエステル化合物20を得た。なお、ポリエステル化合物20中のジオールユニットの組成については、プロトンNMRからは各成分ピークが重なったため分析することができなかった。
〔性能評価方法〕
[中性水への溶解性]
コーヒーミル(大阪ケミカル株式会社製 Mini Blender)にて粉砕(粉砕時間は120秒)したポリマー粉末0.25gを表3、表4、及び表5に示す所定の温度のイオン交換水5gに分散させ、10分間超音波照射を行った。溶け残ったポリマーを減圧濾過により濾別(アドバンテック社製、濾紙No.5C/70mm)し、少量のイオン交換水で洗浄した後、乾燥した。溶け残ったポリマーの乾燥質量を測定し、下記式により溶解率を算出した。ただし、70℃での溶解性試験では、ポリマー粉末の量を0.5g、イオン交換水の量を10gとして分散させ、超音波照射は行わず、その温度で静置した。
溶解率(%)=(溶解前のポリマー質量―溶け残ったポリマー質量)/溶解前のポリマー質量×100
イオン交換水の代わりにエチレングリコールモノターシャリーブチルエーテル(東京化成工業)の10質量%水溶液を使用し、上記と同様にして溶解率を算出した。
上記と同様の方法で粉砕したポリマー粉末約2gを80℃で3時間、真空乾燥した後、シャーレに精秤し、25℃、98RH%の恒湿槽に放置した。24時間後、質量測定を行い、下記式により、吸湿率を算出した。
吸湿率(%)=(放置後のポリマー質量-放置前ポリマー質量)/放置前のポリマー質量×100
合成例15で得られたポリエステル化合物15を41.7g、クラリティLA4285(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) 8.3gについて溶融混練機(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、白色混合物である組成物1を得た。
合成例16で得られたポリエステル化合物16 12kg、及びクラリティLA2250(株式会社クラレ製: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) 2.4kgを減圧下60℃で乾燥後、これらをヘンシェルミキサーにて予備混合した後、二軸混練機(株式会社池貝製:PCM-30、スクリュー径29mm、L/D=36.5)を用いてシリンダー温度180℃、シリンダー回転数200rpm、吐出速度3kg/hにて溶融混練し、白色混合物である組成物2を得た。
合成例16で得られたポリエステル化合物16 12kg、クラリティLA2250(株式会社クラレ製: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)2.4kg及び相溶化剤としてボンドファスト7B(住友化学株式会社製:エチレン-酢酸ビニル-メタクリル酸グリシジル共重合体)0.6kgを減圧下60℃で乾燥後、これらをヘンシェルミキサーにて予備混合した後、組成物2の調製で用いた二軸混練機により、シリンダー温度190℃、シリンダー回転数300rpm、吐出速度3kg/hの条件にて溶融混練し、白色混合物である組成物3を得た。
組成物2の延伸フィラメントを作成するために、押し出し機、冷却水槽、巻き取り装置及び熱風槽を備え付けたモノフィラメント製造装置(株式会社中部マシン製:モノフィラメント製造装置)を使用した。5mmのノズル径を有する押し出し機(ギヤポンプ=1.2cc/回転、スクリュー径30mm、L/D=28)のホッパーに組成物2を仕込み、シリンダー温度195℃、回転数36rpmにして押し出した。押し出した組成物は水で冷却した後、10.0m/minの速度でフィラメントをロールに巻き取り、さらに200℃の熱風により加熱(フィラメント温度実測値:100℃)して18.0m/minの速度でロールに巻き取りながら延伸(総延伸倍率8.7~11倍)を行い、直径約1.5~1.7mmのフィラメントを得た。この組成物2の延伸フィラメントは実施例16と同じようにキャピログラフから作成された同じ組成の低延伸倍率(1.8倍)のフィラメントと比べ明らかに靱性が高くなっていることがわかった。
組成物3の延伸フィラメントを作成するために、押し出し機、冷却水槽、巻き取り装置及び熱風槽を備え付けたモノフィラメント製造装置(株式会社中部マシン製:モノフィラメント製造装置)を使用した。5mmのノズル径を有する押し出し機(ギヤポンプ=1.2cc/回転、スクリュー径30mm、L/D=28)のホッパーに組成物3を仕込み、シリンダー温度210℃、回転数37rpmにして押し出した。押し出した組成物は水で冷却した後、8.0m/minの速度でフィラメントをロールに巻き取り、さらに195℃の熱風により加熱(フィラメント温度実測値:100℃)して20.5m/minの速度でロールに巻き取りながら延伸(総延伸倍率8.7~9.8倍)を行い、直径約1.6~1.7mmのフィラメントを得た。この組成物3の延伸フィラメントは実施例16と同じようにキャピログラフから作成された同じ組成の低延伸倍率(1.8倍)のフィラメントと比べ明らかに靱性が高くなっていることがわかった。
前記合成例で得られたポリエステル化合物1~17、前記組成物1~3、並びに下記市販のサポート材1及びサポート材2について、上記方法で中性水への溶解性及び吸湿性を評価した。結果を表3、及び表4に示す。また、前記合成例で得られたポリエステル化合物18~20、並びに下記市販のサポート材1及びサポート材2について、水溶性有機溶媒を含有する中性水への溶解性、及び吸湿性を評価した。結果を表5に示す。なお、表3、表4、及び表5中の市販品1及び市販品2はそれぞれ下記のとおりである。
・市販品1:Natural PVA/1.75mmポリビニルアルコール(ケンビル社製、数平均分子量30000、ガラス転移温度:80℃)
・市販品2:Soluble Support Material P400SR(登録商標)、メタクリル酸/メタクリル酸メチル:55/45質量%の共重合体(Stratasys社製、組成はプロトンNMR(DMSO-d6)で解析、重量平均分子量:130000、ガラス転移温度:100℃、可塑剤:リン酸トリフェニル等含有)
前記ポリエステル化合物6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2mm、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1.5mmのフィラメントに加工した。その後、フィラメントをGenkei社製Atom 3D Printerに供給し、230℃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。
Claims (15)
- 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、
スルホン酸塩基を有する芳香族ジカルボン酸モノマーユニットA、スルホン酸塩基を有さないジカルボン酸モノマーユニットB、及びジオールモノマーユニットを有し、
全ジカルボン酸モノマーユニットの合計に対する、前記芳香族ジカルボン酸モノマーユニットAの割合が10~70mol%であるポリエステル樹脂を含む、三次元造形用可溶性材料。 - 前記芳香族ジカルボン酸モノマーユニットAを誘導するための芳香族ジカルボン酸Aが、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種以上である、請求項1に記載の三次元造形用可溶性材料。
- 前記スルホン酸塩基を構成するスルホン酸基の対イオンが、ナトリウムイオン、カリウムイオン、マグネシウムイオン、及びアンモニウムイオンからなる群より選ばれる少なくとも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。
- 前記ジカルボン酸モノマーユニットBを誘導するためのジカルボン酸Bが、芳香族ジカルボン酸、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種以上を含む、請求項1~3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中の前記スルホン酸塩基の含有量が0.5~3mmol/gである、請求項1~4いずれか1項に記載の三次元造形用可溶性材料。
- 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Cの炭素数が2~31である、請求項1~5いずれか1項に記載の三次元造形用可溶性材料。
- 前記ジオールモノマーユニットがジエチレングリコールユニットを含み、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当該ジエチレングリコールユニットの割合が5mol%以上60mol%以下である、請求項1~6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の分子量が3000~80000である、請求項1~7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1~8いずれか1項に記載の三次元造形用可溶性材料。
- フィラメントの直径が、0.5~3.0mmである、請求項9に記載の三次元造形用可溶性材料。
- 前記三次元造形用可溶性材料が、延伸加工された三次元造形用可溶性材料である、請求項9又は10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1~11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12に記載の三次元物体の製造方法。
- 前記中性水が、水溶性有機溶媒を含む、請求項12又は13に記載の三次元物体の製造方法。
- 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、
スルホン酸塩基を有する芳香族ジカルボン酸モノマーユニットA、スルホン酸塩基を有さないジカルボン酸モノマーユニットB、及びジオールモノマーユニットを有し、
全ジカルボン酸モノマーユニットの合計に対する、前記芳香族ジカルボン酸モノマーユニットAの割合が10~70mol%であるポリエステル樹脂を含む、サポート材。
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BR112017016098B1 (pt) | 2022-08-23 |
US10717227B2 (en) | 2020-07-21 |
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US20180009160A1 (en) | 2018-01-11 |
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CA2974719A1 (en) | 2016-08-11 |
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