CN115141322B - Three-dimensional printing material, three-dimensional object and three-dimensional object printing method - Google Patents
Three-dimensional printing material, three-dimensional object and three-dimensional object printing method Download PDFInfo
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- CN115141322B CN115141322B CN202210752335.3A CN202210752335A CN115141322B CN 115141322 B CN115141322 B CN 115141322B CN 202210752335 A CN202210752335 A CN 202210752335A CN 115141322 B CN115141322 B CN 115141322B
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- 239000000463 material Substances 0.000 title claims abstract description 155
- 238000010146 3D printing Methods 0.000 title claims abstract description 101
- 238000007639 printing Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 238000000016 photochemical curing Methods 0.000 claims description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 4
- 102100037651 AP-2 complex subunit sigma Human genes 0.000 claims description 3
- 101000806914 Homo sapiens AP-2 complex subunit sigma Proteins 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims 1
- 230000006353 environmental stress Effects 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 8
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- 238000005516 engineering process Methods 0.000 description 16
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- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001875 Ebonite Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
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- AZXGXVQWEUFULR-UHFFFAOYSA-N 2',4',5',7'-tetrabromofluorescein Chemical compound OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 AZXGXVQWEUFULR-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- LFZDEAVRTJKYAF-UHFFFAOYSA-L barium(2+) 2-[(2-hydroxynaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21.C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 LFZDEAVRTJKYAF-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229940104573 pigment red 5 Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The application provides a three-dimensional printing material, a three-dimensional object and a three-dimensional object printing method, wherein the three-dimensional printing material comprises the following components in percentage by mass: 40-80% of a first light-cured component, 5-50% of a second light-cured component, 5-15% of a compatibility promoter and 0.5-10% of a photoinitiator; wherein the first light-curable component comprises a first prepolymer and a reactive monomer, the second curable component comprises a second prepolymer, the number average molecular weight of the first prepolymer is smaller than the number average molecular weight of the second prepolymer, and the surface tension of the first prepolymer is different from the surface tension of the second prepolymer. The three-dimensional printing material and the three-dimensional object can ensure the discharge stability of the three-dimensional printing material, and the three-dimensional object formed by using the three-dimensional printing material can be compatible with hardness and toughness, and has stronger environmental stress cracking resistance and temperature resistance.
Description
Technical Field
The application relates to the technical field of three-dimensional printing, in particular to a three-dimensional printing material, a three-dimensional object and a three-dimensional object printing method.
Background
The printing device prints layer by layer and stacks the three-dimensional object according to the slice layer printing data.
The three-dimensional object printing technology mainly comprises a three-dimensional light curing technology (SLA technology for short), a digital light processing technology (DLP technology for short), a continuous liquid level manufacturing technology (CLIP technology for short), a three-dimensional ink-jet printing technology and the like, and the three-dimensional object printing technology is based on the principle that a liquid photosensitive material is subjected to crosslinking reaction under ultraviolet irradiation to form a three-dimensional object.
In the three-dimensional printing technology, the three-dimensional printing material is critical to the properties of a three-dimensional object, taking the three-dimensional ink-jet printing technology as an example, the three-dimensional object obtained by printing by the existing photo-curing three-dimensional ink-jet printing material has the problems of poor toughness, easy environmental stress cracking, poor weather resistance and the like, when toughening particles are added into the photo-curing three-dimensional ink-jet printing material to improve the toughness of the three-dimensional object, the strength of the three-dimensional object is easy to reduce, and the viscosity of the three-dimensional printing material containing the toughening particles is higher, and if the three-dimensional ink-jet printing material is used for three-dimensional ink-jet printing, the blockage of a printing head can be caused, so that the three-dimensional ink-jet printing material with the requirements of hardness and toughness is particularly critical.
Disclosure of Invention
According to the three-dimensional printing material, the three-dimensional object and the three-dimensional object printing method, components of the three-dimensional printing material are improved and adjusted, so that when the three-dimensional printing material is adopted, the discharge stability of the three-dimensional printing material can be ensured, and the three-dimensional object formed by using the three-dimensional printing material can be considered in terms of hardness and toughness, and has strong environmental stress cracking resistance and temperature resistance.
In a first aspect, the present application provides a three-dimensional printing material, where the three-dimensional printing material includes, in mass percent:
40-80% of a first light-cured component, 5-50% of a second light-cured component, 5-15% of a compatibility promoter and 0.5-10% of a photoinitiator; wherein the first light-curable component comprises a first prepolymer and a reactive monomer, the second curable component comprises a second prepolymer, the number average molecular weight of the first prepolymer is smaller than the number average molecular weight of the second prepolymer, and the surface tension of the first prepolymer is different from the surface tension of the second prepolymer.
In some alternative embodiments, the first prepolymer, the second prepolymer are independently selected from at least one of polyester acrylate, polyether acrylate, polyurethane acrylate, and neat acrylic resin.
In some alternative embodiments, the reactive monomer is selected from at least one of (meth) acrylate monomers, (meth) acrylate derivatives, N-acryloylmorpholine, N-vinylpyrrolidone, vinyl ethers, vinyl ether derivatives, acrylamides, and acrylamide derivatives.
In some alternative embodiments, the three-dimensional printed material meets at least one of the following characteristics:
(1) The number average molecular weight of the first prepolymer is less than or equal to 500 and less than or equal to 3000;
(2) 3000 < the number average molecular weight of the second prepolymer is less than or equal to 15000;
(3) The surface tension sigma 1 of the first prepolymer is larger than the surface tension sigma 2 of the second prepolymer, and the surface tension sigma 1 of the first prepolymer is less than or equal to 10mN/m and less than or equal to 15mN/m (sigma 1-sigma 2).
In some alternative embodiments, the compatibility promoter is selected from at least one of (meth) acryloxysilane, cycloaliphatic (meth) acrylate monomers, and propoxylated (meth) acrylate monomers.
In some alternative embodiments, the first prepolymer is present in the first photocurable component in an amount of from 5% to 15% by weight and the reactive monomer is present in the first photocurable component in an amount of from 85% to 95% by weight.
In some alternative embodiments, the three-dimensional printed material meets at least one of the following characteristics:
(4) The surface tension of the first photo-curing component is 35 mN/m-45 mN/m;
(5) The surface tension of the active monomer is 32-45 mN/m;
(6) The surface tension of the second photo-curing component is 25 mN/m-30 mN/m;
(7) The surface tension of the compatibility promoter is 25 mN/m-32 mN/m.
In some alternative embodiments, the three-dimensional printing material further comprises, in mass percent: 0.05-8% of auxiliary agent, wherein the auxiliary agent comprises at least one of retarder, flatting agent, dispersing agent and coloring agent.
In some alternative embodiments, the three-dimensional printing material further comprises, in mass percent: 0.01 to 3 percent of retarder, 0.01 to 3 percent of flatting agent, 0 to 5 percent of dispersing agent and 0 to 5 percent of colorant.
In some alternative embodiments, the retarder is selected from at least one of an antioxidant, a polymerization inhibitor.
In some alternative embodiments, the photoinitiator is selected from at least one of alpha-hydroxy ketone initiators, acyl phosphorus oxide compounds, alpha-amino ketones, and thioxanthone initiators.
In a second aspect, the present application provides a three-dimensional object printed by a three-dimensional object additive manufacturing process using a three-dimensional printing material as described above.
In some alternative embodiments, the three-dimensional object includes a continuous phase formed from a first photocurable component in the three-dimensional printing material after a photocuring reaction, and a dispersed phase dispersed around the continuous phase formed from a second photocurable component in the three-dimensional printing material after a photocuring reaction.
In some alternative embodiments, the three-dimensional object meets at least one of the following characteristics:
(1) The glass transition temperature of the continuous phase is 50-150 ℃;
(2) The glass transition temperature of the disperse phase is-40 to-10 ℃.
In a third aspect, the present application provides a three-dimensional object printing method, the method comprising:
forming a material layer by using the three-dimensional printing material according to the layer printing data;
providing energy to cure at least a portion of the material layer to form a sliced layer, wherein a first photocurable component in the three-dimensional printing material cures to form a continuous phase and a second photocurable component in the three-dimensional printing material cures to form a dispersed phase;
and repeatedly executing the steps from the material layer to the slicing layer to form the three-dimensional object.
The technical scheme of the application has the following beneficial effects:
the application provides a three-dimensional printing material and a three-dimensional object, wherein two photo-curing components with poor compatibility are blended to form a uniform and stable system by adding a compatibility promoter, so that the discharge stability of the three-dimensional printing material is ensured; after the photo-curing reaction, the phase separation is caused by the poor structural compatibility of the two photo-curing components, the second photo-curing component with large number average molecular weight can form a disperse phase, the first photo-curing component with small number average molecular weight can form a continuous phase, the disperse phase plays a role in toughening the continuous phase, the glass transition temperature of the continuous phase cannot be obviously reduced, and the photo-curing composition has stronger environmental stress cracking resistance and temperature resistance and can also take strength and toughness into consideration.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings to be used in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort to a person of ordinary skill in the art.
Fig. 1 is a schematic flow chart of a three-dimensional printing method according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a three-dimensional printing device according to an embodiment of the present application.
Reference numerals illustrate:
1-a material container; 2-an ink supply tube; 3-an inkjet printhead; 4-three-dimensional printing material; 5-leveling means; 6-energy supply means; 7, a guide rail; 8-supporting a platform; 9-a lifting mechanism; 10-a controller; 11-a forming chamber; 12-three-dimensional object.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
Detailed Description
For a better understanding of the technical solutions of the present application, embodiments of the present application are described in detail below with reference to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which would be apparent to one of ordinary skill in the art without making any inventive effort, are intended to be within the scope of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
The application provides a three-dimensional printing material, which comprises the following components in percentage by mass: 40-80% of a first light-cured component, 5-50% of a second light-cured component, 5-15% of a compatibility promoter and 0.5-10% of a photoinitiator; wherein the first light-curable component comprises a first prepolymer and a reactive monomer, the second curable component comprises a second prepolymer, the number average molecular weight of the first prepolymer is smaller than the number average molecular weight of the second prepolymer, and the surface tension of the first prepolymer is different from the surface tension of the second prepolymer.
In the scheme, the three-dimensional printing material comprises the first light-cured component and the second light-cured component which are poor in structural compatibility, and the first light-cured component and the second light-cured component are blended through the compatibility promoter to form a uniform and stable system, so that the discharge stability of the three-dimensional printing material is ensured, and the three-dimensional printing material can be effectively prevented from blocking a printing head; after the curing reaction, the first light curing component containing the first prepolymer with small number average molecular weight is cured to form a continuous phase of the three-dimensional object, and the second light curing component containing the second prepolymer with large number average molecular weight is cured to form a disperse phase of the three-dimensional object, so that the three-dimensional object can have both high strength brought by the continuous phase and high toughness brought by the disperse phase, and thus, the high strength and the high toughness of the three-dimensional object can be considered, and the three-dimensional object has stronger environmental stress cracking resistance and temperature resistance.
The continuous phase is a substance in which other substances are dispersed in the system, and mainly bears the mechanical properties of the system, and has high stability, and can improve the strength of the three-dimensional object.
The dispersed phase is a substance in the form of fine particles in a dispersion system, and forms a 'sea-island structure' with the continuous phase, wherein the dispersed phase acts as islands in the 'sea-island structure', and can enhance the strength and toughness of the three-dimensional object.
By a compatibilizing agent is meant that the two polymers that are incompatible are brought together by intermolecular bonding forces, thereby obtaining a stable blend. The first prepolymer and the second prepolymer have poor compatibility due to different number average molecular weights and surface tension, and are blended to obtain a uniform and stable system through the action of the compatibility promoter, so that the discharge stability of the three-dimensional printing material is ensured, and the blockage of the printing head by the three-dimensional printing material can be effectively avoided.
The use of different compounds for each component, or different proportions of the individual components, has an impact on the properties of the three-dimensional printing material. In the present application, by adjusting the specific selection of the respective components, and adjusting the ratio between the respective components, a low-viscosity material for three-dimensional inkjet printing or a high-viscosity printing material for SLA technology or DLP technology can be obtained.
Compared with the SLA technology and the DLP technology, the three-dimensional ink-jet printing technology has higher requirements on the viscosity and fluency of the three-dimensional printing material, such as the viscosity of the three-dimensional printing material needs to be reduced to the viscosity suitable for normal spraying within the normal working temperature range of the printing head, such as 8-15 cp, and especially when the normal working temperature of the printing head is lower than 80 ℃, the viscosity of the three-dimensional printing material needs to be reduced to the viscosity suitable for normal spraying instantaneously, which requires the three-dimensional printing material to have lower viscosity at the room temperature of 25 ℃, such as lower than 50cp.
The three-dimensional printing material provided in some examples of the present application has a viscosity of 10cp to 60cp at 25 ℃ and a surface tension of 20mN/m to 35mN/m; the viscosity is 8 cp-15 cp at the working temperature of 30-70 ℃ and the surface tension is 20 mN/m-35 mN/m. Therefore, the printing material has viscosity and surface tension suitable for the printing head to spray, is favorable for smooth three-dimensional printing, saves energy consumption and effectively prolongs the service life of the printing head.
In the above-mentioned scheme, by controlling the proportion of each component in the above-mentioned range, the three-dimensional object obtained by printing can be basically made to have excellent mechanical properties and temperature resistance, and particularly excellent strength, toughness and environmental stress cracking resistance.
In some embodiments, the first light-curable component includes a first prepolymer and an active monomer, the first prepolymer being present in the first light-curable component in an amount of 5% to 15% by mass, based on 100% by mass of the first light-curable component, and the active monomer being present in the first light-curable component in an amount of 85% to 95% by mass.
The first prepolymer is at least one selected from polyester acrylate, polyether acrylate, polyurethane acrylate and pure acrylic resin. In particular, the first prepolymer is preferably a polyether acrylate or polyurethane acrylate, such as BR-372 from Bomar, CN981NS from Shadoma, N3D-I2939, genome 2235 from RAHN, and the like. The mass percentage of the first prepolymer in the first photo-curing component may be specifically 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14% or 15%, etc., and is not limited herein.
The reactive monomer can be used to improve the rheology of the first prepolymer, and under the action of the photoinitiator, the reactive monomer and the first prepolymer together undergo a photo-curing reaction, thereby improving the curing speed while achieving higher strength. The first photocurable component comprising the first prepolymer and the reactive monomer can ensure fluidity and curing efficiency of the first photocurable component.
In some embodiments, the reactive monomer is selected from at least one of (meth) acrylate monomers, (meth) acrylate derivatives, N-Acryloylmorpholine (ACMO), N-vinylpyrrolidone, vinyl ether derivatives, acrylamide, and acrylamide derivatives. For example, the (meth) acrylate monomer may be SR833NS of the company sand gama, SR531, EM214 of the company Changxing, or the like. The mass percentage of the reactive monomer in the first photo-curing component may be 85%, 86%, 87%, 88%, 89%, 90%, 92%, 94% or 95%, etc., and is not limited herein.
The surface tension of the first photocurable component is 35 to 45mN/m, specifically, 35, 36, 38, 40, 41, 42, 43, 45 or the like, and is not limited thereto.
The surface tension of the reactive monomer is 32mN/m to 45mN/m, specifically, 32mN/m, 33mN/m, 34mN/m, 35mN/m, 36mN/m, 38mN/m, 40mN/m, 43mN/m, 45mN/m, or the like, and is not limited thereto.
The second photocurable component includes a second prepolymer, and in some embodiments, the second photocurable component is a second prepolymer. Wherein the second prepolymer is at least one selected from polyester acrylate, polyether acrylate, polyurethane acrylate and pure acrylic resin. The second prepolymer is preferably a polyester acrylate or polyurethane acrylate, such as CN8899NS, CN8891NS, co-mingling UFC052, etc. from the company sandomax.
In some embodiments, the first prepolymer has a number average molecular weight M1 that is less than the number average molecular weight M2 of the second prepolymer, and the first prepolymer has a surface tension σ1 that is greater than the surface tension σ2 of the second prepolymer.
Wherein, the number average molecular weight M1 of the first prepolymer is 500 or less and 3000 or less, and the value of M1 can be specifically 500, 800, 1000, 1200, 1500, 1800, 2000, 2500, 2800 or 3000 or the like, without limitation. The number average molecular weight M2 of the second prepolymer is 3000 or less and 15000 or less, and the value of M1 may be 3000, 3050, 3200, 3500, 4000, 5000, 8000, 9000, 10000 or 15000 or the like, and is not limited herein.
Further, the surface tension sigma 1 of the first prepolymer is larger than the surface tension sigma 2 of the second prepolymer, and the value range of (sigma 1-sigma 2) is 10mN/m, 11mN/m, 12mN/m, 13mN/m, 14mN/m or 15mN/m, etc. which is less than or equal to 10mN/m and less than or equal to 15mN/m is satisfied, and the value range is not limited herein.
In some embodiments, the surface tension of the first photocurable component is from 35mN/m to 45mN/m, specifically, may be 35mN/m, 36mN/m, 38mN/m, 40mN/m, 42mN/m, 45mN/m, or the like, without limitation.
In some embodiments, the surface tension of the second photocurable component is 25 to 30mN/m, specifically 25, 26, 27, 28, 29, or 30mN/m, etc., without limitation herein.
In some embodiments, the first photocurable component has a glass transition temperature (Tg) of 50 ℃ to 150 ℃ after the photocuring reaction, and specifically may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 100 ℃, 120 ℃, 150 ℃, or the like. The glass transition temperature (Tg) of the second photo-curing component after photo-curing reaction is-40 ℃ to-10 ℃, and can be specifically-40 ℃, -35 ℃, -30 ℃, -25 ℃, -20 ℃, -15 ℃ or-10 ℃ and the like. By controlling the mass percentage content of the first light-cured component and the second light-cured component, the glass transition temperature of the first light-cured component after the light-cured reaction is not obviously reduced after the light-cured reaction occurs in the second light-cured component, so that the first light-cured component can enable the three-dimensional object to have higher thermal deformation temperature, and the second light-cured component can enable the three-dimensional object to have stronger environmental stress resistance and prevent the three-dimensional object from cracking.
The first prepolymer and the second prepolymer have poor structural compatibility due to the difference in number average molecular weight and surface tension. And further, because the compatibility of the first light-cured component and the second light-cured component is poor, after the light-cured reaction, the first light-cured component with small number average molecular weight forms a continuous phase of the three-dimensional object, the second light-cured component with large number average molecular weight forms a dispersed phase of the three-dimensional object, and the dispersed phase and the continuous phase form a sea-island structure, wherein the dispersed phase serves as islands in the sea-island structure, and the dispersed phase plays a toughening role relative to the continuous phase, so that the high strength and the high toughness of the three-dimensional object are ensured.
In some embodiments, the surface tension of the compatibility promoter is 25mN/m to 32mN/m for promoting the blending of the first and second photocurable components, and the compatibility promoter can be photocured together with the photoinitiator and the second prepolymer, so that the three-dimensional object can obtain high toughness while ensuring uniform stability of the three-dimensional printing material system.
Specifically, the compatibility accelerator is selected from at least one of (meth) acryloxysilane, alicyclic (meth) acrylate monomer, and propoxylated (meth) acrylate monomer. Exemplary are 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl methyl triisopropoxy silane, SR420NS, SR506EG of the company sand, and the like.
The photoinitiators of the present application are free radical photoinitiators. Specifically, the radical photoinitiator may be selected from at least one of an α -hydroxyketone initiator, an acylphosphorus oxide compound, an α -aminoketone, and a thioxanthone initiator. By way of example, it may be photoinitiator 1173, photoinitiator 183, photoinitiator TPO-L, photoinitiator 819, photoinitiator 369, photoinitiator 907, photoinitiator ITX, photoinitiator DETX, and the like.
Further, the three-dimensional printing material further comprises the following components in percentage by mass: 0.05 to 8 percent of auxiliary agent. Wherein the auxiliary agent is at least one selected from a retarder, a leveling agent, a dispersing agent and a colorant.
Optionally, the three-dimensional printing material further comprises the following components in percentage by mass: 0.01 to 3 percent of retarder, 0.01 to 3 percent of flatting agent, 0 to 5 percent of dispersing agent and 0 to 5 percent of colorant.
Specifically, the retarder is at least one selected from an antioxidant and a polymerization inhibitor. The antioxidant mainly has the function of delaying or inhibiting the oxidation of the polymer, and can be an antioxidant 1010, an antioxidant 168, an antioxidant 292 and the like. The polymerization inhibitor mainly prevents free radicals in the polymerization inhibitor from undergoing polymerization reaction, and improves the storage stability of the material. The polymerization inhibitor may be at least one selected from phenols, quinones or nitrite-based polymerization inhibitors, for example, at least one selected from hydroquinone, p-tert-butylcatechol, 2, 6-di-tert-butyl-p-methylphenol, etc.
The retarder is 0.01% -3% by mass of the three-dimensional printing material, for example, 0.01%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1.5%, 1.8%, 2%, 2.5% or 3% by mass based on 100% by mass of the three-dimensional printing material. Of course, the mass percentage of the material can be proportioned according to actual use conditions, and the material is not limited.
The leveling agent is mainly used for improving the fluidity of the liquid three-dimensional printing material, and simultaneously adjusting the surface tension of the material to enable the material to print normally. The choice of the leveling agent is not particularly limited as long as the leveling agent satisfies the above performance requirements. The products currently available on the market are BYK333, BYK377, BYK-UV3530, BYK-UV3575, BYK-UV3535, etc. of the Pick company, TEGO wet 500, TEGO wet 270, TEGO Glide 450, TEGO RAD 2010, TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200, etc.
The leveling agent may be 0.01% -3% by mass, for example, 0.01%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1.5%, 1.8%, 2%, 2.5% or 3% by mass based on 100% by mass of the three-dimensional printing material. Of course, the mass percentage of the material can be proportioned according to actual use conditions, and the material is not limited.
The main function of the dispersing agent is to improve the dispersion stability of the particles in the material. The choice of dispersant is not particularly limited as long as the dispersant satisfies the above performance requirements. The products currently sold in the market are more, and can be BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, and Di high Dispers 655, dispers675, dispers710, dispers630, dispers 670 and the like.
The dispersant may be 0% to 5% by mass, for example, 0%, 1%, 2%, 2.5%, 3%, 3.5%, 4% or 5% by mass based on 100% by mass of the three-dimensional printing material. Of course, the mass percentage of the material can be proportioned according to actual use conditions, and the material is not limited.
When the material does not contain a colorant, the material is transparent, and the printed product has high transparency, and the transparency can reach 90%, 80%, 70%, 60%, 50% and the like, and is not limited herein.
When included, the colorant may be a pigment or dye, in which case the colorant is preferably a pigment, and the pigment may specifically be selected from C.I.pigment White 6, C.I.pigment Red3, C.I.pigment Red 5, C.I.pigment Red 7, C.I.pigment Red9, C.I.pigment Red 12, C.I.pigment Red 13, C.I.pigment Red 21, C.I.pigment Red31, C.I.pigment Red49:1, C.I.pigment Red 58:1, C.I.pigment Red 175; c.i. pigment Yellow 63, c.i. pigment Yellow 3, c.i. pigment Yellow 12, c.i. pigment Yellow 16, c.i. pigment Yellow 83; one or more of C.I.pigment Blue 1, C.I.pigment Blue 10, C.I.pigment Blue B, phthalocyanine Blue BX, phthalocyanine Blue BS, C.I.pigment Blue61:1, etc.
The colorant may be present in the three-dimensional printing material in an amount of 0 to 5% by mass, based on 100% by mass of the total three-dimensional printing material, for example, 0%, 1%, 2%, 2.5%, 3%, 3.5%, 4% or 5%. Of course, the mass percentage of the material can be proportioned according to actual use conditions, and the material is not limited.
The three-dimensional printing material can stably exist under the light-shading condition, so that the three-dimensional printing material is high in stability, long-time transportation and storage can be realized, the viscosity of the three-dimensional printing material is low, and the phenomenon of blocking a spray hole of a printing head can not occur. In the specific application process, the phase separation is caused by poor structural compatibility of the two photocuring components after the photocuring reaction, the second photocuring component with large number average molecular weight forms a disperse phase, the first photocuring component with small number average molecular weight forms a continuous phase, and the disperse phase plays a role in toughening the continuous phase, and the glass transition temperature of the continuous phase cannot be obviously reduced, so that the three-dimensional object formed by printing has stronger environmental stress resistance and temperature resistance, is not easy to crack, and can be compatible with strength and toughness.
The compositions provided in examples 1-4 are shown in Table 1, and the compositions provided in comparative examples 1-4 are shown in Table 2.
TABLE 1
The number average molecular weight of the first prepolymer and the second prepolymer is tested by adopting a gel chromatographic column method, the number average molecular weight of the first prepolymer N3D-I2939 is about 1500, the number average molecular weight of genome 2235 is about 500, and the number average molecular weight of BR-372 is about 3000; the second prepolymer CN8899NS has a number average molecular weight of about 15000, a number average molecular weight of about 10000 of UFC052, and a number average molecular weight of about 3000 of CN8891 NS.
TABLE 2
Wherein the number average molecular weight of the first prepolymer MIRAMER PU210 is less than 3000 and the number average molecular weight of the second prepolymer MIRAMER PU340 is less than 3000 as tested by gel chromatography.
A second aspect of the present application provides a three-dimensional printing method using the three-dimensional printing material of the first aspect, and fig. 2 is a flowchart of the three-dimensional printing method according to the present invention, including the following steps:
s1: forming a material layer using the three-dimensional printing material according to the first aspect, based on the layer printing data;
s2: providing energy to cure at least a portion of the material layer to form a sliced layer, wherein a first photocurable component in the three-dimensional printing material cures to form a continuous phase and a second photocurable component cures to form a dispersed phase;
s3: and repeatedly executing the steps from the material layer to the slicing layer to form the three-dimensional object.
The execution subject of the printing method may be a printing apparatus that realizes the above steps S1 to S3 by controlling the dispensing of the three-dimensional printing material and the curing process, and finally produces the three-dimensional object.
Fig. 2 is a schematic structural diagram of a three-dimensional object printing apparatus provided in the present application, and as shown in fig. 2, an embodiment of the present application further provides a three-dimensional object forming apparatus, configured to implement the printing method of a three-dimensional object, where the apparatus includes:
an inkjet printhead 3 for providing a three-dimensional printing material 4 to form a material layer;
a support platform 8 for carrying the layer of material;
an energy supply means 6 for supplying energy to cure at least part of said material layer.
In one embodiment, the inkjet printhead 3 may be a single-channel printhead or a multi-channel printhead, or a combination of a single-channel printhead and a multi-channel printhead. The number of inkjet printheads 3 is at least 1, the number of inkjet printheads 3 being dependent on the amount of three-dimensional printing material used that needs to be applied. In other embodiments, the number of inkjet printheads 3 may also be dependent on the type of three-dimensional printing material used and the amount that needs to be applied, for example, when the three-dimensional printing material in the liquid phase comprises functional materials of different colors, the three-dimensional printing material of different colors is ejected through different inkjet printheads or different channels of the same inkjet printhead. For example, when the volume of a single ink droplet, which is larger in the amount of the three-dimensional printing material to be applied, is insufficient to satisfy the demand, in order to improve the printing efficiency, inkjet printing may be performed using a plurality of inkjet printheads or a plurality of channel ejections at the same time.
The energy provided by the energy supply device 6 may be radiant energy or thermal energy, and in this embodiment, the energy provided by the energy supply device 6 is radiant energy, and the energy supply device 6 is an ultraviolet LED lamp, a mercury lamp, a metal halogen lamp, an electrodeless lamp, a xenon lamp, or the like.
It will be appreciated that the device may also include a material container 1 and an ink supply tube 2, the material container 1 being adapted to store three-dimensional printing material and being capable of delivering the three-dimensional printing material stored therein to a printhead via the ink supply tube 2.
Further, the three-dimensional object printing device of the present application may further include a lifting mechanism 9, where the lifting mechanism 9 is connected to the supporting platform 8, and drives the supporting platform 8 to lift or descend along a vertical direction, so as to change a relative distance between the supporting platform 8 and the inkjet printhead 3 in a Z direction, thereby continuously forming a slice layer and forming the three-dimensional object 12 by stacking layer by layer.
Further, the three-dimensional object printing apparatus of the present application may further include a leveling member 5, the leveling member 5 being located between the inkjet printhead 3 and the energy supply device 6 for leveling the material layer. In particular, the levelling member 5 may be a levelling rod, with the dispensed surplus three-dimensional printing material being carried away by the action of the rotation of the levelling rod.
The inkjet printhead 3, leveling component 5 and energy supply device 6 in this embodiment are all mounted on a carriage (not shown in fig. 2) that reciprocates on a guide rail 7. The material container 1, the ink supply tube 2, the inkjet printhead 3, the three-dimensional printing material 4, the leveling component 5, the energy supply device 6, the guide rail 7, the support platform 8, and the lifting mechanism 9 are all disposed within a forming chamber 11, and the forming chamber 11 may be a sealed chamber.
Further, the three-dimensional object printing apparatus of the present application may further include a controller 10, the controller 10 being configured to control the operation of at least one of the inkjet printhead 3, the energy supply device 6, the elevating mechanism 9, and the leveling member 5. Illustratively, the controller 10 may control the inkjet printhead 3 to dispense the three-dimensional printing material 4 according to the layer printing data, the controller 10 may control the radiation intensity and the radiation time of the energy supply device 6 to the material layer, the controller 10 may control the relative distance between the support platform 8 and the inkjet printhead 3 in the Z-direction, and the like.
The specific process of implementing three-dimensional printing by using the three-dimensional object forming device can be as follows:
before S1, the three-dimensional printing material may be subjected to a preheating treatment as needed.
In S1, the inkjet printhead 3 forms a material layer on the support platform 8 using the three-dimensional printing material according to the layer printing data.
Specifically, the layer print data is data representing a cross section of the three-dimensional object, the method for obtaining the layer print data is not limited, any method for obtaining the layer print data in the three-dimensional object printing process in the field can be adopted, for example, before the three-dimensional object is printed, model data of the three-dimensional object needs to be obtained, data format conversion is carried out on the model data, such as conversion into a STL format, PLY format, WRL format and the like, which can be identified by slicing software, slicing and layering processing is carried out on the model by using the slicing software, and data representing a cross section layer of the object is also called layer print data; the layer print data includes information representing the shape of the object, and/or information representing the color of the object.
In S2, the energy supply device 6 irradiates the material layer to cure at least part of the material layer, thereby forming a sliced layer. The first light-cured component in the three-dimensional printing material is cured to form a continuous phase, and the second light-cured component in the three-dimensional printing material is cured to form a disperse phase.
After each slice layer is formed, the controller 10 controls the lifting mechanism 9 to drive the supporting platform 8 to move downwards by a certain distance (such as a layer thickness distance) in the height direction (i.e. the Z direction), so that enough space is provided to accommodate a new slice layer; and then, after forming a slice layer according to the steps S1-S2, repeating the steps S1-S2, namely, continuously forming a material layer on the surface of the previous slice layer, and curing the material layer to form a new slice layer. When the slice layers are stacked layer by layer in the height direction, a three-dimensional object 12 is formed.
The application uses an energy supply device to provide energy to the material layer, so that the three-dimensional printing material is subjected to a photo-curing reaction to be in a solidification or semi-solidification state, and the specific energy can be UV light. After the photo-curing reaction, the phase separation is caused by poor structural compatibility of the two photo-curing components, the second photo-curing component with large number average molecular weight forms a disperse phase of the three-dimensional object, the first photo-curing component with small number average molecular weight forms a continuous phase of the three-dimensional object, and the three-dimensional object with a phase separation structure can be formed, wherein the disperse phase is the continuous phase and plays a toughening role, the glass transition temperature of the continuous phase cannot be obviously reduced, the environmental stress cracking resistance and the temperature resistance are relatively strong, and the three-dimensional object can have both high strength and high toughness.
The present application was carried out according to the three-dimensional printing materials provided by examples 1 to 4 and comparative examples 1 to 4, and three-dimensional objects were obtained by printing with a three-dimensional printing apparatus and a three-dimensional printing method, and the three-dimensional objects were subjected to the following performance tests, and the specific results are shown in tables 3, 4.
1. Viscosity detection
And testing the viscosity of the three-dimensional printing material by using a DV-I digital display viscometer.
2. Surface tension test
And testing the surface tension of each component of the three-dimensional printing material by adopting a platinum plate surface tensiometer.
3. Fluency testing
And a 3D photo-curing ink-jet printer of the Saina J501 is adopted to continuously print three-dimensional printing materials, the printing is continued for 4 hours, the ink outlet condition of the spray heads before and after printing is tested, the number of broken lines before and after printing is not more than 10, namely the printing fluency ok is tested.
4. Shore hardness of
The three-dimensional printing material is applied to a 3D photo-curing ink-jet printer of the Sauna J501, and the tested material with the required size specification in GB/T2411-2008 (Shore hardness) is printed by using a durometer to measure plastics and hard rubber, and the Shore hardness is tested according to the standard.
5. Tensile Strength
The three-dimensional printing material is applied to a 3D photo-curing ink-jet printer of the Saina J501, a tested material with the size and specification required by GB/T528-2009 "determination of tensile stress and strain properties of vulcanized rubber or thermoplastic rubber" is printed, and the 1 st part of the determination of the tensile properties of plastics "is according to GB/T1040-2006: general rules test the tensile strength of three-dimensional printed materials.
6. Flexural Strength
The three-dimensional printing material is applied to a Sauna J501D photo-curing ink-jet printer, and the tested material with the size specification required in GB/T9341-2008 'determination of Plastic bending Property' is printed and the bending strength is tested according to the standard.
7. Impact Strength
The three-dimensional printing material is applied to a Saina J501D photo-curing ink-jet printer, and the tested material with the size specification required by GB/T1843-2008 'determination of impact Strength of Plastic cantilever beam' is printed and the impact strength is tested according to the standard.
8. Glass transition temperature
The three-dimensional printing material is applied to a Sauna J501 3D photo-curing ink-jet printer, and GB/T19466.2-2004 Plastic differential scanning calorimetry part 2: determination of glass transition temperature the glass transition temperature is measured on test materials of the required dimensions according to this standard.
9. Heat distortion temperature
The three-dimensional printing material is applied to a Sauna J501 3D photo-curing ink-jet printer, and the part 2 of the specification of the plastic load deformation temperature of GB/T1634.2-2004 is printed: the heat distortion temperature (0.45 MPa) was measured according to the standard for test materials of the required dimensional specifications for plastics, hard rubber and long-fiber reinforced composites.
The measured results of the performance tests of the three-dimensional printed materials provided in examples 1 to 4 and comparative examples 1 to 4 are shown in Table 3, and the measured results of the performance tests of the three-dimensional objects made of the three-dimensional printed materials provided in examples 1 to 4 and comparative examples 1 to 4 are shown in Table 4.
TABLE 3 Table 3
TABLE 4 Table 4
Conclusion: from the test results provided in tables 3-4, the three-dimensional printing materials provided by the present invention are suitable for inkjet printing; in addition, the three-dimensional objects (examples 1-4) obtained by printing with the three-dimensional printing material have high mechanical properties, specifically, the tensile strength, the bending strength, the impact strength and the Shore hardness of the three-dimensional objects are excellent, and the three-dimensional objects have high heat distortion temperature, namely, the three-dimensional objects have high temperature resistance.
In example 3, since the second prepolymer content is higher, the tensile strength and the flexural strength are slightly weaker, but the impact strength is the greatest because the second photocurable component forms more dispersed phases, and more dispersed phases can further improve the toughness of the three-dimensional object, i.e., the impact strength increases.
The three-dimensional object formed without the second photo-curing component in comparative example 1 was inferior in toughness (impact strength).
The first photocurable component and the second photocurable component of comparative example 2 are compatible, and it is difficult to form a continuous phase and a dispersed phase, resulting in a three-dimensional object having poor toughness (impact strength).
In comparative example 3, the first and second photocurable components failed to form a uniform system without using a compatibility accelerator, and the inkjet printing was extremely poor in smoothness and unsuitable for inkjet printing.
Comparative example 4 using the second prepolymer having a smaller number average molecular weight, it was difficult to form a continuous phase and a dispersed phase, and the formed three-dimensional object was inferior in mechanical properties (tensile strength, flexural strength, impact strength).
The foregoing description of the preferred embodiment of the present invention is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The three-dimensional printing material is characterized by comprising the following components in percentage by mass:
40-80% of a first light-cured component, 5-50% of a second light-cured component, 5-15% of a compatibility promoter and 0.5-10% of a photoinitiator; the first light-curing component comprises a first prepolymer and an active monomer, wherein the mass percentage of the first prepolymer in the first light-curing component is 5-15%, and the mass percentage of the active monomer in the first light-curing component is 85-95%;
the second curing component comprises a second prepolymer, the number average molecular weight of the first prepolymer is smaller than that of the second prepolymer, the number average molecular weight of the first prepolymer is not smaller than 500 and not larger than 3000, and the number average molecular weight of the second prepolymer is not larger than 3000 and not larger than 15000; the surface tension sigma 1 of the first prepolymer is larger than the surface tension sigma 2 of the second prepolymer, and the surface tension sigma 1 of the first prepolymer is less than or equal to 10mN/m and less than or equal to 15mN/m (sigma 1-sigma 2);
wherein the first prepolymer is selected from at least one of polyester acrylate, polyether acrylate, polyurethane acrylate, pure acrylic resin and aliphatic epoxy acrylate genome 2235;
the second prepolymer is at least one of polyester acrylate, polyether acrylate, polyurethane acrylate and pure acrylic resin;
the reactive monomer is at least one selected from (methyl) acrylic ester monomer, (methyl) acrylic ester derivative, N-acryloylmorpholine, N-vinyl pyrrolidone, vinyl ether derivative, acrylamide and acrylamide derivative;
the compatibility promoter is selected from at least one of (meth) acryloxysilane, cycloaliphatic (meth) acrylate monomer, and propoxylated (meth) acrylate monomer.
2. The three-dimensional printed material according to claim 1, wherein the three-dimensional printed material satisfies the following characteristics
At least one of:
(1) The surface tension of the first photo-curing component is 35 mN/m-45 mN/m;
(2) The surface tension of the active monomer is 32-45 mN/m;
(3) The surface tension of the second photo-curing component is 25 mN/m-30 mN/m;
(4) The surface tension of the compatibility promoter is 25 mN/m-32 mN/m.
3. The three-dimensional printed material according to claim 1, further comprising, in mass percent: 0.05-8% of auxiliary agent, wherein the auxiliary agent comprises at least one of retarder, flatting agent, dispersing agent and coloring agent.
4. The three-dimensional printed material according to claim 3, further comprising, in mass percent: 0.01 to 3 percent of retarder, 0.01 to 3 percent of flatting agent, 0 to 5 percent of dispersing agent and 0 to 5 percent of colorant.
5. The three-dimensional printed material according to claim 3 or 4, wherein the retarder is at least one selected from an antioxidant and a polymerization inhibitor.
6. The three-dimensional printing material according to claim 1, 3 or 4, wherein the photoinitiator is selected from at least one of α -hydroxy ketone initiators, acylphosphorus oxide compounds, α -amino ketones and thioxanthone initiators.
7. A three-dimensional object, characterized in that the three-dimensional object is printed by a three-dimensional object additive manufacturing process using the three-dimensional printing material according to any one of claims 1 to 6.
8. The three-dimensional object of claim 7, comprising a continuous phase formed from a first photocurable component in the three-dimensional printed material after a photocuring reaction and a dispersed phase dispersed around the continuous phase formed from a second photocurable component in the three-dimensional printed material after a photocuring reaction.
9. The three-dimensional object of claim 8, wherein the three-dimensional object meets at least one of the following characteristics:
(1) The glass transition temperature of the continuous phase is 50-150 ℃;
(2) The glass transition temperature of the disperse phase is-40 to-10 ℃.
10. A method of printing a three-dimensional object, the method comprising:
forming a material layer using the three-dimensional printing material according to any one of claims 1 to 6, according to the layer printing data;
providing energy to cure at least a portion of the material layer to form a sliced layer, wherein a first photocurable component in the three-dimensional printing material cures to form a continuous phase and a second photocurable component in the three-dimensional printing material cures to form a dispersed phase;
and repeatedly executing the steps from the material layer to the slicing layer to form the three-dimensional object.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210752335.3A CN115141322B (en) | 2022-06-28 | 2022-06-28 | Three-dimensional printing material, three-dimensional object and three-dimensional object printing method |
| PCT/CN2023/095278 WO2024001603A1 (en) | 2022-06-28 | 2023-05-19 | Three-dimensional printing material, three-dimensional object, and method for printing three-dimensional object |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210752335.3A CN115141322B (en) | 2022-06-28 | 2022-06-28 | Three-dimensional printing material, three-dimensional object and three-dimensional object printing method |
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| CN202210752335.3A Active CN115141322B (en) | 2022-06-28 | 2022-06-28 | Three-dimensional printing material, three-dimensional object and three-dimensional object printing method |
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| WO (1) | WO2024001603A1 (en) |
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| CN115141322B (en) * | 2022-06-28 | 2024-02-27 | 珠海赛纳三维科技有限公司 | Three-dimensional printing material, three-dimensional object and three-dimensional object printing method |
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| CN115141322A (en) | 2022-10-04 |
| WO2024001603A1 (en) | 2024-01-04 |
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