CN108178994A - A kind of 3D printing platform spray formulation and preparation method thereof - Google Patents
A kind of 3D printing platform spray formulation and preparation method thereof Download PDFInfo
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- CN108178994A CN108178994A CN201810187632.1A CN201810187632A CN108178994A CN 108178994 A CN108178994 A CN 108178994A CN 201810187632 A CN201810187632 A CN 201810187632A CN 108178994 A CN108178994 A CN 108178994A
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- printing platform
- spray formulation
- acrylate
- polyethylene glycol
- polymer
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- 239000007921 spray Substances 0.000 title claims abstract description 117
- 238000010146 3D printing Methods 0.000 title claims abstract description 93
- 238000009472 formulation Methods 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 46
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- -1 polysiloxanes Polymers 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 43
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229920006037 cross link polymer Polymers 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- 229920000570 polyether Polymers 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 17
- 238000007639 printing Methods 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000686 essence Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 244000028178 Marasmius oreades Species 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
A kind of 3D printing platform spray formulation is prepared by the raw material components comprising following weight percent：Anion film forming polymer, the acrylate of hydrophobically modified or its salt, block polymer, organic solvent, liquefied low boiling point organic compound gas, the polysiloxanes being made of at least one polyethylene glycol block and at least one polyethylene glycol block；Each component has synergistic effect in preparation, make the spray formulation of ejection there is suitable viscosity, adhesion strength, shear thinning behavior and setting rate jointly, and then it can uniformly be coated on 3D printing platform surface, and there is suitable intensity after solidification, it is ensured that formed precision and the generation for effectively avoiding warpage.
Description
Technical field
The present invention relates to 3D printing fields, and in particular to a kind of 3D printing platform spray formulation.
Background technology
3D printing（Also known as increases material manufacturing technology）It is one kind of rapid shaping technique, is to set CAD data by molding
The adhesive materials such as received shipment powdery metal or plastic are by successively accumulating the cumulative technology and constructed object.
The 3D printing technique of mainstream mainly includes four kinds：Stereolithography（SLA）, three-dimensional powder bonding（3DP）, selectivity
It is laser sintered（SLS）, fusion sediment is read as type soon（FDM）.Wherein, the 3D printer based on FDM technology is to utilize ABS, PA, Buddhist nun
The heating for dissolving characteristic of the resins such as dragon, successively squeezes out on print platform and forms three-dimensional model, fast with manufacturing speed, essence
The advantages of degree and complexity are high, it is possible to produce conventional method does not manufacture product come, extremely complex.However, by
In resin with characteristic of significantly expanding with heat and contract with cold, the relatively hot material printed, the material layer being particularly in direct contact with platform,
On relatively cold platform it is molding during there are problems that easy warpage, generate the three-dimensional model after warpage not can from
So it is pasted onto on print platform.
At present, the method for solving warpage mainly has：
First, by overlaying binding agent on platform, as Airwolf companies of the U.S. sell respectively for ABS, PETG, TPE,
TPU, PC/ABS, PLA, nylon, polyester binding agent, then the material printed is molded on binding agent, by binding agent
Bonding characteristic the model of formation is bonded on platform, with reduce warpage appearance probability.However, in practical applications, on
State binding agent has higher adhesion strength to resin materials such as ABS, PA, nylon, and the model that printing is formed is made to be bonded in platform
On be not easy to remove or be easy to cause when removing model bottom damage.Also, binding agent easily generates residual on platform, needs
Platform, which is cleared up, could carry out continuing to print, and influence printing effect.It is not easy to smear in addition, the binding agent used at present also exists
The shortcomings that flat, influences the formed precision of model.
2nd, platform temperature is improved, it is made to be adapted with the material printed, by the temperature difference for reducing platform and printed material
To avoid the generation of warpage.However, this method can be applicable in the resins such as the relatively low ABS of melting temperature, for melting temperature
Higher resin, since 3D printing platform temperature cannot be excessively high, applicability is poor.
3rd, bed patch, such as CN205553228U are laid with.If bed patch is divided into dried layer, in use, tearing bottom, bed is attached to
On print platform, printed material is then printed upon bed patch surface.Bed patch material and the material identical of printing, thus make printing material
Material well in bed stick by fusion.However, being difficult to detach with bed patch there are the material of printing using during this method, model essence is influenced
The problem of spending.
4th, it forms texture in platform surface or is laid with textured structure, such as CN107521087A, by printing material
Material avoids the generation of warpage with the Anchoring Effect with textured platform surface.However, this method can be in the model bottom table of formation
Face generation texture, the problem of influencing surface smoothness, and equally exist influence model accuracy.
Invention content
Warpage is easily generated for the resin material printed in FDM technology, and the method for avoiding warpage used at present is deposited
Adhesion strength it is excessively high, there are problems that pollution on platform, influence formed precision, the present invention provides a kind of spraying of 3D printing platform
Preparation and preparation method thereof.
The present invention adopts the following technical scheme that：
A kind of 3D printing platform spray formulation, it is characterised in that：It is prepared by the raw material components comprising following weight percent：
A. anion film forming polymer 1.0%-2.8%；
B. the acrylate of hydrophobically modified or its salt 1.0%-2.5%；
C. the block polymer 0.06%- being made of at least one polyethylene glycol block and at least one polyethylene glycol block
0.8%；
D. organic solvent 0.05%-0.2%；
E. liquefied low boiling point organic compound gas 0.01%-0.3%；
F. polysiloxanes 0.1%-0.35%；
And the deionized water of surplus.
Preferably, the anion film forming polymer is selected from 2- acrylamide-2-methylpro panesulfonic acids polymer, octyl group third
Acrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylamide-dimethyl diallyl ammonium chloride-propylene
At least one of butyl acrylate copolymer.
Preferably, the acrylate of the hydrophobically modified or its salt are selected from acrylate/20 methyl of octadecyl ethyoxyl
Acrylate copolymer, -20 Methacrylate Crosspolymer of acrylate/stereth, acrylate/octadecyl
50 acrylate copolymer of ethyoxyl, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer, acrylate/octadecyl
At least one of 20 itaconate copolymeric of ethyoxyl.
Preferably, the block polymerization being made of at least one polyethylene glycol block and at least one polyethylene glycol block
Object is selected from least one of polyethylene glycol propylene glycol copolymers, polypropylene glycol-polyethylene glycol propylene glycol copolymers.
Preferably, the organic solvent is selected from least one of ethyl alcohol, propyl alcohol, acetone.
Preferably, the low boiling point organic compound gas is selected from dimethyl ether, Arcton 11, dichlorotetra-fluoroethane, two
At least one of dichlorodifluoromethane.
Preferably, the polysiloxanes is selected from ring five dimethyl silicone polymer, hexamethyldisiloxane, three ethoxy of mercapto propyl
At least one of base silane, methyl vinyl silicone.
Preferably, the 3D printing platform spray formulation exists with clear gel form, viscosity 5000-
50000mPa.s。
Preferably, 3D printing platform spray formulation of the invention includes essence, preservative, antioxidant, stabilizer, complexing
Agent, filtering agent.
The preparation method of above-mentioned 3D printing platform spray formulation, including：
（1）By predetermined quality percentage weigh respectively the anion film forming polymer, the hydrophobically modified acrylate or
Its salt, described has the block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block
Solvent, the polysiloxanes and the deionized water, it is spare；
（2）The deionized water is added in reaction vessel, airtight heating is to 30-50 DEG C；The reaction is opened after the completion of heating
Container, and successively add in the anion film forming polymer, the acrylate of the hydrophobically modified or its salt and described organic
Solvent, it is closed to be kept for 60-350 DEG C of heating, time 1-1.5 hour；
（3）Step（2）After reaction, reaction system is cooled to 50 DEG C hereinafter, open the reaction vessel, add in it is described by
The block polymer and the polysiloxanes that at least one polyethylene glycol block and at least one polyethylene glycol block are formed, it is close
Close 70-300 DEG C of holding heating, time 0.5-1 hour；
（4）Step（3）After reaction, temperature of reaction system is down to 50-60 DEG C, opens the reaction vessel, and take immediately
Go out the reaction product of cooling, transfer them in salable, pressurization automiser spray；
（5）It is filled with into salable, pressurization the automiser spray of the reaction product equipped with the cooling described liquefied low
Boiling organic compounds gas, then seals automiser spray.
A kind of method that above-mentioned 3D printing platform spray formulation is applied to 3D printing platform, including：
（1）It is sprayed using the automiser spray equipped with the 3D printing platform spray formulation in 3D printing platform, by 3D printing
The uniform spraying of platform spray formulation is on the 3D printing platform；
（2）Spraying is scraped in the spray formulation on 3D printing platform using scraper plate, it is 5000-50000mPa.s to make viscosity
Spray formulation dilutionization and be uniformly layed in the print area of the 3D printing platform；
（3）It is layed in dilutionization and uniformly on the spray formulation of the print area and carries out 3D printing.
A kind of automiser spray equipped with above-mentioned 3D printing platform spray formulation.
The type of each raw material components and its content are to the performance of spray formulation in the 3D printing platform spray formulation of the present invention
With great influence.
The appropriate level of the anion film forming polymer is 1.0%-2.8%, preferably 1.3%-2.0%.When its weight percent
When being less than 1.0% than content, the consistency of spray formulation is too low, and viscosity is small, it is impossible to be uniformly distributed, cause on 3D printing platform
Adhesion strength is low, can not avoid the generation of warpage well.Also, the smooth degree of faying face is low, influences the precision of model.When
Its weight percent content be higher than 2.8% when, printing complete when, between the spray formulation of cooled and solidified and 3D printing platform and
Adhesion strength is excessively high between the model of formation, it is difficult to easily make when detaching, and detaching model faying face generate it is damaged and
Residual is easily generated on 3D printing platform.When its weight percent content is 1.3%-2.0%, spray formulation adhesion strength is most
To be moderate, spray formulation after cooling and model delamination, faying face light can be enable while warpage is effectively prevent to occur
It is sliding, and avoid generating colloid residual on print platform.
The acrylate of the hydrophobically modified or the suitable weight percentage content of its salt are 1.0%-2.5%, preferably 1.2%-
1.8%.When its weight percent content is less than 1.0%, spray formulation adhesion strength is low, can not avoid the hair of warpage well
It is raw；When its weight percent content is higher than 2.5%, spray formulation viscosity is excessive, it is impossible to it is uniformly distributed on 3D printing platform,
And printing is completed and adhesion strength is excessively high between 3D printing platform and the model of formation after spray formulation cooled and solidified, it is difficult to
Separation, it is damaged that when separation, easily generates the faying face of model, and residual is easily generated on 3D printing platform.
The conjunction of block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block
Suitable weight percent content is 0.06%-0.8%, preferably 0.3%-0.6%.When its weight percent content is less than 0.06%, spraying
Preparation still has high viscosity after scraping, it is difficult to is uniformly distributed on 3D printing platform, influence the precision of model；When its weight
Degree be higher than 0.8% when, spray formulation cannot be stabilized with gel form, make its be not suitable for 3D printing platform into
Row 3D printing forms model.
The suitable weight percentage content of the polysiloxanes is 0.1%-0.35%, preferably 0.2%-0.3%.When its weight hundred
When dividing than content less than 0.1%, the setting time of spray formulation is long, causes spray formulation cannot be after model bottom is formed i.e.
It is effectively bonded, avoids the effect that warpage occurs poor；When its weight percent content is higher than 0.35%, spray formulation coagulates
Gu the time pass it is shorter, the model bottom of 3D printing not complete printing shaping when spray formulation solidified, can not effectively avoid sticking up
Bent generation.
The spray formulation of the present invention is prepared in raw material, anion film forming polymer, hydrophobically modified acrylate or its
The block polymer and polysiloxanes that salt, at least one polyethylene glycol block and at least one polyethylene glycol block are formed have
Synergistic effect, influences each other, and makes the spray formulation of ejection have suitable viscosity, shear thinning behavior and setting rate jointly,
And then 3D printing platform surface can be uniformly coated on, and there is suitable intensity after solidification, it is ensured that formed precision
And effectively avoid the generation of warpage.
Advantageous effect：The 3D printing platform spray formulation of the present invention is transparent, is existed with clear gel form, and
And with special rheological behavior, i.e., with high rest viscosity and shear thinning behavior.The rheological behavior prevent product from
It is flowed out from pipe alone, and becomes the stable gel with high rest viscosity upon discharge, and based on preferable shear thinning
Property, it is ensured that the flatness of print platform.The spray formulation has suitable adhesion strength, makes printing formed thereon
Model, which can consolidate, is pasted on 3D printing platform, effectively prevent the generation of warpage.Printing is completed, the spray formulation after cooled and solidified
Adhesion strength is greatly reduced, and makes it have the effect that residue glue is easily had no from the stripping of 3D printing platform.And it is surprising that
The faying face of spray formulation and the model of printing formation after solidification is relatively smooth, and adhesion strength is relatively low, only need to apply small power
Can be effectively separated by the two, model will not be caused damaged with spray formulation faying face.
Specific embodiment
Some embodiments of the present invention presented below, to help the present invention, but protection scope of the present invention is further understood
It is not limited in these embodiments.
Embodiment one
A kind of 3D printing platform spray formulation is prepared by the raw material components comprising following weight percent：A. octyl acrylamide/
Acrylate/butylaminoethyl methacrylate copolymer 2.1%；B. -20 methacrylate of acrylate/stereth
Cross-linked polymer 2.3%；C. polyethylene glycol propylene glycol copolymers 0.3%；D. ethyl alcohol 0.08%；E. liquefied dimethyl ether 0.2%；
F. ring five dimethyl silicone polymer 0.25%；And the deionized water of surplus.The specific preparation method of above-mentioned spray formulation is：（1）
Octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer, propylene are weighed respectively by predetermined quality percentage
It is -20 Methacrylate Crosspolymer of acid esters/stereth, polyethylene glycol propylene glycol copolymers, ethyl alcohol, liquefied
Dimethyl ether, ring five dimethyl silicone polymer and deionized water, it is spare；（2）Deionized water is added in reaction vessel, it is closed to add
Heat is to 30 DEG C；Reaction vessel is opened after the completion of heating, and successively adds in octyl acrylamide/acrylate/methacrylic acid fourth
Amino ethyl ester copolymer, -20 Methacrylate Crosspolymer of acrylate/stereth and ethyl alcohol, closed holding
60 DEG C of heating, 1.5 hours time；（3）Step（2）After reaction, reaction system is cooled to 40 DEG C, opens reaction vessel,
Polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer are added in, it is closed to be kept for 70 DEG C of heating, 1 hour time；（4）
Step（3）After reaction, temperature of reaction system is down to 50 DEG C, and takes out the reaction product of cooling immediately, transferred them to
In salable, pressurization automiser spray；（5）It is filled with into salable, pressurization the automiser spray of the reaction product equipped with cooling
Liquefied dimethyl ether, then seals automiser spray.The spray formulation being prepared is applied to 3D printing platform, including：（1）Make
It is sprayed with the automiser spray equipped with 3D printing platform spray formulation, the uniform spraying of 3D printing platform spray formulation is beaten in 3D
It prints on platform；（2）Spraying is scraped in the spray formulation on 3D printing platform using scraper plate, the spray formulation for making viscosity is dilute
Releasing simultaneously uniformly is layed in print area；（3）Progress 3D on the spray formulation of print area is layed in dilutionization and uniformly to beat
Print.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
But warpage whether occurs with the adhesion strength of 3D printing platform, the adhesion strength with model, model after solidifying, stripping rear platform is
The no residual for having glue, whether model faying face has breakage after stripping, is as a result listed in table 1.
Embodiment two
A kind of 3D printing platform spray formulation is prepared by the raw material components comprising following weight percent：A. octyl acrylamide/
Acrylate/butylaminoethyl methacrylate copolymer 1 .7%；B. -20 methacrylate of acrylate/stereth
Cross-linked polymer 1.3%；C. polyethylene glycol propylene glycol copolymers 0.4%；D. ethyl alcohol 0.1%；E. liquefied dimethyl ether 0.16%；
F. ring five dimethyl silicone polymer 0.22%；And the deionized water of surplus.The specific preparation method of above-mentioned spray formulation is：（1）
Octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer, third are weighed respectively by predetermined quality percentage
Olefin(e) acid ester/- 20 Methacrylate Crosspolymer of stereth, polyethylene glycol propylene glycol copolymers, ethyl alcohol, liquefaction
Dimethyl ether, ring five dimethyl silicone polymer and deionized water, it is spare；（2）Deionized water is added in reaction vessel, it is closed
It is heated to 50 DEG C；Reaction vessel is opened after the completion of heating, and successively adds in octyl acrylamide/acrylate/methacrylic acid
Fourth amino ethyl ester copolymer, -20 Methacrylate Crosspolymer of acrylate/stereth and ethyl alcohol, closed guarantor
Hold 350 DEG C of heating, 1.5 hours time；（3）Step（2）After reaction, reaction system is cooled to 50 DEG C, opens reaction and hold
Device adds in polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer, and closed to keep 300 DEG C of heating, the time 1 is small
When；（4）Step（3）After reaction, temperature of reaction system is down to 60 DEG C, and takes out the reaction product of cooling immediately, by it
It is transferred in salable, pressurization automiser spray；（5）To salable, pressurization the automiser spray of the reaction product equipped with cooling
In be filled with liquefied dimethyl ether, then seal automiser spray.The spray formulation being prepared is applied to 3D printing platform, packet
It includes：（1）It is sprayed using the automiser spray equipped with 3D printing platform spray formulation, 3D printing platform spray formulation is uniformly sprayed
It is distributed on 3D printing platform；（2）Spraying in the spray formulation on 3D printing platform is scraped using scraper plate, makes the spray of viscosity
Mist preparation diluentization is simultaneously uniformly layed in print area；（3）In dilutionization and uniformly it is layed on the spray formulation of print area
Carry out 3D printing.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
But warpage whether occurs with the adhesion strength of 3D printing platform, the adhesion strength with model, model after solidifying, stripping rear platform is
The no residual for having glue, whether model faying face has breakage after stripping, is as a result listed in table 1.
Embodiment three
A kind of 3D printing platform spray formulation is prepared by the raw material components comprising following weight percent：A.2- acrylamido-
2- methyl propane sulfonic acids polymer 1.0%, acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer 1.0%；B.
- 20 Methacrylate Crosspolymer 1.2% of acrylate/stereth, acrylate/C10-30Alkylol acrylamide acid esters is handed over
Linked polymer 1.0%；C. polyethylene glycol propylene glycol copolymers 0.4%, polypropylene glycol-polyethylene glycol propylene glycol copolymers
0.3%；D. ethyl alcohol 0.05%, acetone 0.08%；E. liquefied dimethyl ether 0.15%, liquefied dichlorotetra-fluoroethane 0.1%；F. ring five
Dimethyl silicone polymer 0.2%, methyl vinyl silicone 0.1%；And the deionized water of surplus.Above-mentioned spray formulation it is specific
Preparation method is：（1）2- acrylamide-2-methylpro panesulfonic acids polymer, acryloyl are weighed respectively by predetermined quality percentage
Amine-dimethyl diallyl ammonium chloride-butyl acrylate copolymer, -20 methacrylate of acrylate/stereth are handed over
Linked polymer, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer, polyethylene glycol propylene glycol copolymers, poly- the third two
Alcohol-polyethylene glycol propylene glycol copolymers, ethyl alcohol, acetone, liquefied dimethyl ether, liquefied dichlorotetra-fluoroethane, ring five poly- two
Methylsiloxane, methyl vinyl silicone and deionized water, it is spare；（2）Deionized water is added in reaction vessel, it is closed
It is heated to 40 DEG C；Opening reaction vessel after the completion of heating, and priority addition 2- acrylamide-2-methylpro panesulfonic acids polymer,
Acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer, -20 metering system of acrylate/stereth
Acid esters cross-linked polymer, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer and ethyl alcohol, acetone, it is closed to keep heating
90 DEG C, 1 hour time；（3）Step（2）After reaction, reaction system is cooled to 40 DEG C, opens reaction vessel, added in poly-
Ethylene glycol-polypropylene glycol copolymers, polypropylene glycol-polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer, first
Base vinylsiloxane, it is closed to be kept for 240 DEG C of heating, 1 hour time；（4）Step（3）After reaction, by reaction system temperature
Degree is down to 55 DEG C, and take out the reaction product of cooling immediately, transfers them in salable, pressurization automiser spray；（5）To dress
Liquefied dimethyl ether, liquefied dichlorotetra-fluoroethane are filled in salable, pressurization the automiser spray for having the reaction product of cooling,
Then seal automiser spray.The spray formulation being prepared is applied to 3D printing platform, including：（1）Using equipped with 3D printing
The automiser spray of platform spray formulation is sprayed, by the uniform spraying of 3D printing platform spray formulation on 3D printing platform；（2）
Spraying in the spray formulation on 3D printing platform is scraped using scraper plate, make the spray formulation dilutionization of viscosity and is uniformly spread
Set on print area；（3）It is layed in dilutionization and uniformly on the spray formulation of print area and carries out 3D printing.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
But warpage whether occurs with the adhesion strength of 3D printing platform, the adhesion strength with model, model after solidifying, stripping rear platform is
The no residual for having glue, whether model faying face has breakage after stripping, is as a result listed in table 1.
Example IV
A kind of 3D printing platform spray formulation is prepared by the raw material components comprising following weight percent：A.2- acrylamido-
2- methyl propane sulfonic acids polymer 0.8%, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer 0.5%,
Acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer 1.0%；B. propernoic acid ester/octadecyl ethyoxyl
20 methacrylate copolymers 0.2%, -20 Methacrylate Crosspolymer 0.2%, third of acrylate/stereth
50 acrylate copolymer 0.4% of olefin(e) acid ester/octadecyl ethyoxyl, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymeric
Object 0.3%, acrylate/20 itaconate copolymeric 0.5% of octadecyl ethyoxyl；C. polyethylene glycol propylene glycol copolymers
0.4%th, polypropylene glycol-polyethylene glycol propylene glycol copolymers 0.3%；D. ethyl alcohol 0.06%, propyl alcohol 0.08%, acetone 0.02%；E.
Liquefied dimethyl ether 0.05%, liquefied Arcton 11 0.03%, liquefied dichlorotetra-fluoroethane 0.04%, liquefied dichloro two
Fluoromethane 0.04%；F. ring five dimethyl silicone polymer 0.06%, hexamethyldisiloxane 0.03%, mercaptopropyltriethoxysilane
0.07%, methyl vinyl silicone 0.1%；And the deionized water of surplus.The specific preparation method of above-mentioned spray formulation is：
（1）2- acrylamide-2-methylpro panesulfonic acids polymer, octyl acrylamide/propylene are weighed respectively by predetermined quality percentage
Acid esters/butylaminoethyl methacrylate copolymer, acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymerization
Object, propernoic acid ester/20 methacrylate copolymer of octadecyl ethyoxyl, -20 methyl-prop of acrylate/stereth
Olefin(e) acid ester cross-linked polymer, acrylate/50 acrylate copolymer of octadecyl ethyoxyl, acrylate/C10-30Alkanol third
Olefin(e) acid ester cross-linked polymer, acrylate/20 itaconate copolymeric of octadecyl ethyoxyl, polyethylene glycol propylene glycol are total to
Polymers, polypropylene glycol-polyethylene glycol propylene glycol copolymers, ethyl alcohol, propyl alcohol, acetone, liquefied dimethyl ether, liquefied trichlorine
Fluoromethane, liquefied dichlorotetra-fluoroethane, liquefied dicholorodifluoromethane, ring five dimethyl silicone polymer, two silica of hexamethyl
Alkane, mercaptopropyltriethoxysilane, methyl vinyl silicone and deionized water, it is spare；（2）Deionized water is added in and is reacted
In container, airtight heating is to 55 DEG C；Reaction vessel is opened after the completion of heating, and successively adds in 2- acrylamido -2- methyl-props
Sulfonic acid polymer, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylamide-dimethyl two
Allyl ammonium chloride-butyl acrylate copolymer, propernoic acid ester/20 methacrylate copolymer of octadecyl ethyoxyl, third
Olefin(e) acid ester/- 20 Methacrylate Crosspolymer of stereth, acrylate/50 acrylate of octadecyl ethyoxyl
Copolymer, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer, acrylate/20 itaconate of octadecyl ethyoxyl
Copolymer and ethyl alcohol, propyl alcohol, acetone, it is closed to be kept for 200 DEG C of heating, 1 hour time；（3）Step（2）After reaction, will
Reaction system is cooled to 30 DEG C, opens reaction vessel, adds in polyethylene glycol propylene glycol copolymers, polypropylene glycol-poly- second two
Alcohol-polypropylene glycol copolymers, ring five dimethyl silicone polymer, two silica of hexamethyl, mercapto propyl-triethoxysilicane, methyl ethylene
Siloxanes, it is closed to be kept for 180 DEG C of heating, 1 hour time；（4）Step（3）After reaction, temperature of reaction system is down to 55
DEG C, and the reaction product of cooling is taken out immediately, it transfers them in salable, pressurization automiser spray；（5）To equipped with cooling
Liquefied dimethyl ether, liquefied Arcton 11, liquefied dichloro are filled in salable, pressurization the automiser spray of reaction product
Tetrafluoroethane, liquefied dicholorodifluoromethane, then seal automiser spray.The spray formulation being prepared is applied to 3D printing
Platform, including：（1）It is sprayed using the automiser spray equipped with 3D printing platform spray formulation, 3D printing platform is sprayed and is made
The uniform spraying of agent is on 3D printing platform；（2）Spraying in the spray formulation on 3D printing platform is scraped using scraper plate, is made
The spray formulation dilutionization of viscosity is simultaneously uniformly layed in print area；（3）It is layed in dilutionization and uniformly the spray of print area
3D printing is carried out on mist preparation.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
But warpage whether occurs with the adhesion strength of 3D printing platform, the adhesion strength with model, model after solidifying, stripping rear platform is
The no residual for having glue, whether model faying face has breakage after stripping, is as a result listed in table 1.
Comparative example one
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by octyl group in embodiment one
Acrylamide/acrylate/butylaminoethyl methacrylate copolymer level is determined as 0.9%, is as a result listed in table 1.
Comparative example two
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by octyl group in embodiment one
Acrylamide/acrylate/butylaminoethyl methacrylate copolymer level is determined as 3.0%, is as a result listed in table 1.
Comparative example three
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by propylene in embodiment one
- 20 Methacrylate Crosspolymer content of acid esters/stereth is determined as 0.85%, is as a result listed in table 1.
Comparative example four
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by propylene in embodiment one
- 20 Methacrylate Crosspolymer content of acid esters/stereth is determined as 2.8%, is as a result listed in table 1.
Comparative example five
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by second poly- in embodiment one
Glycol-polypropylene glycol copolymers content is determined as 0.04%, is as a result listed in table 1.
Comparative example six
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by second poly- in embodiment one
Glycol-polypropylene glycol copolymers content is determined as 1.0%, is as a result listed in table 1.
Comparative example seven
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by silicon poly- in embodiment one
Oxygen alkane content is determined as 0.08%, is as a result listed in table 1.
Comparative example eight
The raw material that uses, preparation method, application method, test method are identical with embodiment one, only by silicon poly- in embodiment one
Oxygen alkane content is determined as 0.43%, is as a result listed in table 1.
Comparative example nine
Do not add anion film forming polymer, other raw material used, preparation method, application method, test methods with implementation
Example one is identical, is as a result listed in table 1.
Comparative example ten
The acrylate or its salt of hydrophobically modified, other raw material used, preparation method, application method, test methods are not added
It is identical with embodiment one, as a result it is listed in table 1.
Comparative example 11
The block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block is not added, other make
Raw material, preparation method, application method, test method are identical with embodiment one, are as a result listed in table 1.
Comparative example 12
Polysiloxanes is not added, other raw material used, preparation method, application method, test methods are identical with embodiment one,
As a result it is listed in table 1.
Table 1：
| Rest viscosity/ mPa.s | Shear thinning | Uniformly apply Cloth | Setting time/ min | It is bonded with platform strong Degree | It is bonded with model strong Degree | It sticks up It is bent | There is the glue residual It stays | Model Precision | |
| Embodiment one | 5100 | ◎ | ◎ | 10 | It is moderate | It is moderate | ○ | ○ | It is high |
| Embodiment two | 10800 | ◎ | ◎ | 12 | It is moderate | It is moderate | ○ | ○ | It is high |
| Embodiment three | 21000 | ◎ | ◎ | 9 | It is moderate | It is moderate | ○ | ○ | It is high |
| Example IV | 48000 | ◎ | ◎ | 10 | It is moderate | It is moderate | ○ | ○ | It is high |
| Comparative example one | 6500 | — | ○ | 15 | It is low | It is low | ◎ | ○ | It is low |
| Comparative example two | 28000 | ◎ | ○ | 12 | It is high | It is high | ○ | ◎ | It is low |
| Comparative example three | 9800 | ◎ | ○ | 15 | It is low | It is low | ◎ | ○ | It is low |
| Comparative example four | 19000 | ◎ | ○ | 13 | It is high | It is high | ◎ | ○ | It is low |
| Comparative example five | 12800 | ○ | ○ | 17 | It is moderate | It is moderate | ○ | ○ | It is low |
| Comparative example six | 3500 | — | ○ | 40 | — | — | — | — | — |
| Comparative example seven | 4800 | ◎ | ◎ | 63 | It is low | It is low | ◎ | ◎ | It is low |
| Comparative example eight | 6200 | ◎ | ◎ | 4 | It is moderate | It is low | ◎ | ○ | It is low |
| Comparative example nine | 1800 | — | ◎ | 13 | It is low | It is low | ◎ | ○ | It is low |
| Comparative example ten | 900 | — | ◎ | 16 | It is low | It is low | ◎ | ○ | It is low |
| Comparative example 11 | 1300 | — | ◎ | 12 | It is low | It is low | ◎ | ○ | It is low |
| Comparative example 12 | 2200 | — | ◎ | 47 | It is low | It is low | ◎ | ○ | It is low |
Wherein, ◎ represent affirmative as a result, zero represent negative as a result ,-represent can not evaluate.
The embodiment of the present invention and comparative example the result shows that, in 3D printing platform spray formulation the type of each raw material components and
Its content has great influence to the performance of spray formulation, and spray formulation is prepared in raw material, anion film forming polymer, hydrophobic
The block polymerization that modified acrylate or its salt, at least one polyethylene glycol block and at least one polyethylene glycol block are formed
Object and polysiloxanes have synergistic effect, influence each other, and the spray formulation to be formed is made to have suitable viscosity, bonding jointly
Intensity, shear thinning behavior and setting rate, and then can uniformly be coated on 3D printing platform surface, it is ensured that molding essence
Spend and effectively avoid the generation of warpage.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of 3D printing platform spray formulation, it is characterised in that：It is prepared by the raw material components comprising following weight percent：
A. anion film forming polymer 1.0%-2.8%；
B. the acrylate of hydrophobically modified or its salt 1.0%-2.5%；
C. the block polymer 0.06%- being made of at least one polyethylene glycol block and at least one polyethylene glycol block
0.8%；
D. organic solvent 0.05%-0.2%；
E. liquefied low boiling point organic compound gas 0.01%-0.3%；
F. polysiloxanes 0.1%-0.35%；
And the deionized water of surplus.
2. a kind of 3D printing platform spray formulation according to claim 1, it is characterised in that：The anion film-forming polymer
Object is selected from 2- acrylamide-2-methylpro panesulfonic acids polymer, octyl acrylamide/acrylate/methacrylic acid fourth amino
At least one of methacrylate copolymers, acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer.
3. a kind of 3D printing platform spray formulation according to claim 1 or 2, it is characterised in that：The hydrophobically modified
Acrylate or its salt are selected from acrylate/20 methacrylate copolymer of octadecyl ethyoxyl, acrylate/tristearin
- 20 Methacrylate Crosspolymer of alcohol polyethers, acrylate/50 acrylate copolymer of octadecyl ethyoxyl, propylene
Acid esters/C10-30In alkylol acrylamide acid esters cross-linked polymer, acrylate/20 itaconate copolymeric of octadecyl ethyoxyl
It is at least one.
4. according to a kind of 3D printing platform spray formulation of claim 1-3 any one of them, it is characterised in that：It is described by least
The block polymer that one polyethylene glycol block and at least one polyethylene glycol block are formed is total to selected from polyethylene glycol propylene glycol
At least one of polymers, polypropylene glycol-polyethylene glycol propylene glycol copolymers.
5. according to a kind of 3D printing platform spray formulation of claim 1-4 any one of them, it is characterised in that：It is described organic molten
Agent is selected from least one of ethyl alcohol, propyl alcohol, acetone.
6. according to a kind of 3D printing platform spray formulation of claim 1-5 any one of them, it is characterised in that：The low boiling point
Organic compound gas is selected from least one of dimethyl ether, Arcton 11, dichlorotetra-fluoroethane, dicholorodifluoromethane.
7. according to a kind of 3D printing platform spray formulation of claim 1-6 any one of them, it is characterised in that：The poly- silica
Alkane is in ring five dimethyl silicone polymer, hexamethyldisiloxane, mercaptopropyltriethoxysilane, methyl vinyl silicone
At least one.
8. according to a kind of preparation method of 3D printing platform spray formulation of claim 1-7 any one of them, it is characterised in that：
Including following preparation process：
（1）By predetermined quality percentage weigh respectively the anion film forming polymer, the hydrophobically modified acrylate or
Its salt, described has the block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block
Solvent, the polysiloxanes and the deionized water, it is spare；
（2）The deionized water is added in reaction vessel, airtight heating is to 30-50 DEG C；The reaction is opened after the completion of heating
Container, and successively add in the anion film forming polymer, the acrylate of the hydrophobically modified or its salt and described organic
Solvent, it is closed to be kept for 60-350 DEG C of heating, time 1-1.5 hour；
（3）Step（2）After reaction, reaction system is cooled to 50 DEG C hereinafter, open the reaction vessel, add in it is described by
The block polymer and the polysiloxanes that at least one polyethylene glycol block and at least one polyethylene glycol block are formed, it is close
Close 70-300 DEG C of holding heating, time 0.5-1 hour；
（4）Step（3）After reaction, temperature of reaction system is down to 50-60 DEG C, opens the reaction vessel, and take immediately
Go out the reaction product of cooling, transfer them in salable, pressurization automiser spray；
（5）It is filled with into salable, pressurization the automiser spray of the reaction product equipped with the cooling described liquefied low
Boiling organic compounds gas, then seals automiser spray.
9. a kind of 3D printing platform spray formulation of claim 1-7 any one of them is applied to the method for 3D printing platform,
Including：
（1）It is sprayed using the automiser spray of the 3D printing platform spray formulation equipped with the easily peelable model in 3D printing platform
Mist, by the uniform spraying of 3D printing platform spray formulation on the 3D printing platform；
（2）Spraying is scraped in the spray formulation on 3D printing platform using scraper plate, it is 5000-50000mPa.s to make viscosity
Spray formulation dilutionization and be uniformly layed in the print area of the 3D printing platform；
（3）It is layed in dilutionization and uniformly on the spray formulation of the print area and carries out 3D printing.
10. a kind of automiser spray equipped with the 3D printing platform spray formulation as described in claim any one of 1-7.
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| CN109135627A (en) * | 2018-08-29 | 2019-01-04 | 付远 | A kind of preparation method for the dedicated adherency glue of nonmetallic materials 3D printing |
| CN111454458A (en) * | 2020-04-23 | 2020-07-28 | 万华化学集团股份有限公司 | Novel nylon material, preparation method and application of novel nylon material in 3D printing |
| WO2022141374A1 (en) * | 2020-12-31 | 2022-07-07 | Elkem Silicones Shanghai Co., Ltd. | Method for post-treatment of an additive manufactured object |
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