CN108178994B - 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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- CN108178994B CN108178994B CN201810187632.1A CN201810187632A CN108178994B CN 108178994 B CN108178994 B CN 108178994B CN 201810187632 A CN201810187632 A CN 201810187632A CN 108178994 B CN108178994 B CN 108178994B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
A kind of 3D printing platform spray formulation is prepared: anion film forming polymer, the acrylate of hydrophobically modified or its salt, the block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block, organic solvent, liquefied low boiling point organic compound gas, polysiloxanes by the raw material components comprising following weight percent；Each component has synergistic effect in preparation, make the spray formulation sprayed that 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 technique
3D printing (also known as increases material manufacturing technology) 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 construct the technology of object by the way that successively accumulation is cumulative.
The 3D printing technique of mainstream mainly includes four kinds: Stereolithography (SLA), three-dimensional powder bonding (3DP), selectivity
Laser sintered (SLS), fusion sediment are read as type (FDM) fastly.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
Degree and the high advantage of complexity, 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 especially directly contacted with platform,
Molding on relatively cold platform to there are problems that easy warpage in the process, the three-dimensional model after generation warpage can not be certainly
So it is pasted on print platform.
Currently, the method for solving warpage mainly has:
One, by overlaying binder on platform, as Airwolf company of the U.S. sell respectively for ABS, PETG,
TPE, TPU, PC/ABS, PLA, nylon, polyester binder, then the material printed is formed on binder, by viscous
The model of formation is bonded on platform by the bonding characteristic of knot agent, to reduce the probability of warpage appearance.However, in practical application
In, to the resin materials such as ABS, PA, nylon adhesion strength with higher, the model for forming printing is bonded in above-mentioned binder
It is easy to cause model bottom to damage when being not easy to remove on platform, or removing.Also, binder is easy to generate residual on platform,
It needs to carry out platform to clear up just to can be carried out and continues to print, influence printing effect.In addition, there is also not for binder used at present
The shortcomings that easily smoothing out, influences the formed precision of model.
Two, platform temperature is improved, is adapted it with the material printed, by the temperature difference for reducing platform and printed material
To avoid the generation of warpage.However, the resins such as this method ABS lower for melting temperature can be applicable in, for melting temperature
Higher resin, since 3D printing platform temperature cannot be excessively high, applicability is poor.
Three, bed patch, such as CN205553228U are laid with.Bed patch is divided into several layers, in use, tearing bottom, bed is attached to
On print platform, printed material is then printed upon bed patch surface.Bed patch material is identical as the material of printing, thus makes to print material
Material well stick in bed by fusion.However, being difficult to separate with bed patch using there are the materials of printing when this method, model essence is influenced
The problem of spending.
Four, texture is formed in platform surface or be 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 generates texture, influences surface smoothness, and equally exists the problem of influencing model accuracy.
Summary of the invention
It is easy to produce warpage for the resin material printed in FDM technology, and the method used at present for avoiding warpage is deposited
Adhesion strength it is excessively high, there are problems that pollution on platform, influence formed precision, it is spraying that the present invention provides a kind of 3D printing platform
Preparation and preparation method thereof.
The present invention adopts the following technical scheme:
A kind of 3D printing platform spray formulation, it is characterised in that: 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 acid polymer, octyl 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, trichlorofluoromethane, 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, comprising:
(1) acrylic acid of the anion film forming polymer, the hydrophobically modified is weighed respectively by predetermined quality percentage
Rouge or its salt, the block polymer being made of at least one polyethylene glycol block and at least one polyethylene glycol block, institute
Organic solvent, the polysiloxanes and the deionized water are stated, it is spare；
(2) deionized water is added in reaction vessel, airtight heating is to 30-50 DEG C；Described in being opened after the completion of heating
Reaction vessel, and the anion film forming polymer, the acrylate of the hydrophobically modified or its salt and described is successively added
Organic solvent, closed holding heat 60-350 DEG C, time 1-1.5 hour；
(3) reaction system after reaction, is cooled to 50 DEG C hereinafter, open the reaction vessel, institute is added by step (2)
State the block polymer and the poly- silicon oxygen being made of at least one polyethylene glycol block and at least one polyethylene glycol block
Alkane, closed holding heat 70-300 DEG C, time 0.5-1 hour；
(4) temperature of reaction system after reaction, is down to 50-60 DEG C by step (3), is opened the reaction vessel, is existed side by side
Cooling reaction product is taken out, is transferred them in salable, pressurization automiser spray；
(5) liquefaction is filled with into salable, pressurization the automiser spray of the reaction product equipped with the cooling
Low boiling point organic compound gas, then seal automiser spray.
A method of above-mentioned 3D printing platform spray formulation is applied to 3D printing platform, comprising:
(1) it is sprayed using the automiser spray equipped with the 3D printing platform spray formulation in 3D printing platform, by 3D
The uniform spraying of print platform spray formulation is on the 3D printing platform；
(2) spraying is scraped using scraper plate in the spray formulation on 3D printing platform, makes viscosity 5000-
The spray formulation dilutionization of 50000mPa.s and the print area for being uniformly layed in the 3D printing platform；
(3) it in dilutionization and is uniformly layed 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 performance of the type of each raw material component and its content to spray formulation in 3D printing platform spray formulation of the 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 lower than 1.0% than content, the consistency of spray formulation is too low, and viscosity is small, cannot 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 and 3D printing platform of cooled and solidified and
Adhesion strength is excessively high between the model of formation, it is difficult to it is easy that the faying face of model is made to generate breakage when separating, and separating, and
Residual is easy to produce 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 effectivelying prevent warpage 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 lower 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, cannot be 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, when separation, are easy to generate the faying face of model damaged, and residual are easy to produce on 3D printing platform.
The conjunction of the 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%.It is spraying when its weight percent content is lower than 0.06%
Preparation still has high viscosity after scraping, it is difficult to be 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 lower than 0.1%, the setting time of spray formulation is too long, causes spray formulation cannot be after model bottom is formed i.e.
It is effectively bonded, the effect for avoiding warpage from occurring is poor；When its weight percent content is higher than 0.35%, spray formulation is solidifying
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.
Spray formulation of the 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 constituted have
Synergistic effect, influences each other, and the spray formulation sprayed is made to have suitable viscosity, shear thinning behavior and setting rate jointly,
And then it can be uniformly coated on 3D printing platform surface, and there is suitable intensity after solidification, it is ensured that formed precision
And effectively avoid the generation of warpage.
The utility model has the advantages that 3D printing platform spray formulation of the invention be it is transparent, with clear gel form presence, and
And there is special rheological behavior, that is, there is 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 be based on preferable shear thinning
Property, it is ensured that the flatness of print platform.The spray formulation has suitable adhesion strength, makes to print 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 for being easy that residue glue is had no from the removing 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 lower, need to only apply small power
Can be effectively separated by the two, it not will lead to model and spray formulation faying face be damaged.
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 to these embodiments.
Embodiment one
A kind of 3D printing platform spray formulation is prepared: a. octyl propylene by the raw material components comprising following weight percent
Amide/acrylate/butylaminoethyl methacrylate copolymer 2.1%；B. -20 methyl-prop of acrylate/stereth
Olefin(e) acid ester 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
Are as follows: (1) octyl acrylamide/acrylate/butylaminoethyl methacrylate is weighed respectively by predetermined quality percentage be copolymerized
Object, -20 Methacrylate Crosspolymer of acrylate/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,
Airtight heating is to 30 DEG C；Reaction vessel is opened after the completion of heating, and octyl acrylamide/acrylate/methyl-prop is successively added
Olefin(e) acid fourth amino ethyl ester copolymer, -20 Methacrylate Crosspolymer of acrylate/stereth and ethyl alcohol, it is close
Close 60 DEG C, the time 1.5 hours of holding heating；(3) reaction system after reaction, is cooled to 40 DEG C, opens reaction by step (2)
Polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer are added in container, and closed holding heats 70 DEG C, and the time 1 is small
When；(4) temperature of reaction system after reaction, is down to 50 DEG C, and take out cooling reaction product immediately, by it by step (3)
It is transferred in salable, pressurization automiser spray；(5) to salable, pressurization the automiser spray equipped with cooling reaction product
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) being 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 is scraped using scraper plate in the spray formulation on 3D printing platform, makes the spray of viscosity
Mist preparation diluentization is simultaneously uniformly layed in print area；(3) on the spray formulation in dilutionization and being uniformly layed in 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
Whether the but adhesion strength after solidification with the adhesion strength of 3D printing platform and model, model occur warpage, and removing rear platform is
The no residual for having glue, whether model faying face has breakage after removing, is as a result listed in table 1.
Embodiment two
A kind of 3D printing platform spray formulation is prepared: a. octyl propylene by the raw material components comprising following weight percent
Amide/acrylate/butylaminoethyl methacrylate copolymer 1 .7%；B. -20 methyl-prop of acrylate/stereth
Olefin(e) acid ester 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
Are as follows: (1) octyl acrylamide/acrylate/butylaminoethyl methacrylate is weighed respectively by predetermined quality percentage be copolymerized
Object, -20 Methacrylate Crosspolymer of acrylate/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,
Airtight heating is to 50 DEG C；Reaction vessel is opened after the completion of heating, and octyl acrylamide/acrylate/methyl-prop is successively added
Olefin(e) acid fourth amino ethyl ester copolymer, -20 Methacrylate Crosspolymer of acrylate/stereth and ethyl alcohol, it is close
Close 350 DEG C, the time 1.5 hours of holding heating；(3) reaction system after reaction, is cooled to 50 DEG C by step (2), is opened anti-
Container is answered, polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer are added, closed holding heats 300 DEG C, the time 1
Hour；(4) temperature of reaction system after reaction, is down to 60 DEG C, and take out cooling reaction product immediately by step (3), will
It is transferred in salable, pressurization automiser spray；(5) to salable, pressurization the spraying appearance equipped with cooling reaction product
It is filled with liquefied dimethyl ether in device, then seals automiser spray.The spray formulation being prepared is applied to 3D printing platform, packet
It includes: (1) being 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 is scraped using scraper plate in the spray formulation on 3D printing platform, makes the spray of viscosity
Mist preparation diluentization is simultaneously uniformly layed in print area；(3) on the spray formulation in dilutionization and being uniformly layed in 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
Whether the but adhesion strength after solidification with the adhesion strength of 3D printing platform and model, model occur warpage, and removing rear platform is
The no residual for having glue, whether model faying face has breakage after removing, is as a result listed in table 1.
Embodiment three
A kind of 3D printing platform spray formulation is prepared: a.2- acryloyl by the raw material components comprising following weight percent
Amido -2- methyl propane sulfonic acid 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 cross-linked polymer 1.0%；C. polyethylene glycol propylene glycol copolymers 0.4%, polypropylene glycol-polyethylene glycol propylene glycol are total
Polymers 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
Specifically the preparation method comprises the following steps: (1) weighs 2- acrylamide-2-methylpro panesulfonic acid polymer, third by predetermined quality percentage respectively
Acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer, -20 methacrylic acid of acrylate/stereth
Ester cross-linked polymer, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer, polyethylene glycol propylene glycol copolymers, poly- third
Glycol-polyethylene glycol propylene glycol copolymers, ethyl alcohol, acetone, liquefied dimethyl ether, liquefied dichlorotetra-fluoroethane, ring five are poly-
Dimethyl siloxane, methyl vinyl silicone and deionized water, it is spare；(2) deionized water is added in reaction vessel, it is close
It closes and is heated to 40 DEG C；Reaction vessel is opened after the completion of heating, and the polymerization of 2- acrylamide-2-methylpro panesulfonic acid is successively added
Object, acrylamide-dimethyl diallyl ammonium chloride-butyl acrylate copolymer, -20 methyl of acrylate/stereth
Acrylate crosspolymers, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer and ethyl alcohol, acetone, closed holding
90 DEG C, the time 1 hour of heating；(3) reaction system after reaction, is cooled to 40 DEG C, opens reaction vessel, add by step (2)
Enter polyethylene glycol propylene glycol copolymers, polypropylene glycol-polyethylene glycol propylene glycol copolymers, five polydimethylsiloxanes of ring
Alkane, methyl vinyl silicone, closed holding heat 240 DEG C, the time 1 hour；(4) step (3) after reaction, by reactant
It is that temperature is down to 55 DEG C, and takes out cooling reaction product immediately, transfers them in salable, pressurization automiser spray；(5)
Liquefied dimethyl ether, liquefied dichloro-tetrafluoro are filled with into salable, pressurization the automiser spray equipped with cooling reaction product
Ethane then seals automiser spray.The spray formulation being prepared is applied to 3D printing platform, comprising: (1) using equipped with 3D
The automiser spray of print platform spray formulation is sprayed, by the uniform spraying of 3D printing platform spray formulation in 3D printing platform
On；(2) spraying is scraped using scraper plate in the spray formulation on 3D printing platform, makes the spray formulation dilutionization of viscosity simultaneously
Uniformly it is layed in print area；(3) 3D printing is carried out on the spray formulation in dilutionization and being uniformly layed in print area.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
Whether the but adhesion strength after solidification with the adhesion strength of 3D printing platform and model, model occur warpage, and removing rear platform is
The no residual for having glue, whether model faying face has breakage after removing, is as a result listed in table 1.
Example IV
A kind of 3D printing platform spray formulation is prepared: a.2- acryloyl by the raw material components comprising following weight percent
Amido -2- methyl propane sulfonic acid 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
20 methacrylate copolymer 0.2% of ethyoxyl, -20 Methacrylate Crosspolymer of acrylate/stereth
0.2%, 50 acrylate copolymer 0.4% of acrylate/octadecyl ethyoxyl, acrylate/C10-30Alkylol acrylamide acid esters is handed over
Linked polymer 0.3%, acrylate/20 itaconate copolymeric 0.5% of octadecyl ethyoxyl；C. polyethylene glycol propylene glycol
Copolymer 0.4%, 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 trichlorofluoromethane 0.03%, liquefied dichlorotetra-fluoroethane 0.04%, liquefaction
Dicholorodifluoromethane 0.04%；F. ring five dimethyl silicone polymer 0.06%, hexamethyldisiloxane 0.03%, three second of mercapto propyl
Oxysilane 0.07%, methyl vinyl silicone 0.1%；And the deionized water of surplus.The specific preparation of above-mentioned spray formulation
Method are as follows: (1) weigh 2- acrylamide-2-methylpro panesulfonic acid polymer, octyl acryloyl respectively by predetermined quality percentage
Amine/acrylate/butylaminoethyl methacrylate copolymer, acrylamide-dimethyl diallyl ammonium chloride-acrylic acid fourth
Ester copolymer, propernoic acid ester/20 methacrylate copolymer of octadecyl ethyoxyl, acrylate/stereth -20
Methacrylate Crosspolymer, acrylate/50 acrylate copolymer of octadecyl ethyoxyl, acrylate/C10-30
Alkylol acrylamide acid esters cross-linked polymer, acrylate/20 itaconate copolymeric of octadecyl ethyoxyl, polyethylene glycol third
Diol copolymer, polypropylene glycol-polyethylene glycol propylene glycol copolymers, ethyl alcohol, propyl alcohol, acetone, liquefied dimethyl ether, liquefaction
Trichlorofluoromethane, liquefied dichlorotetra-fluoroethane, liquefied dicholorodifluoromethane, ring five dimethyl silicone polymer, hexamethyl
Disiloxane, mercaptopropyltriethoxysilane, methyl vinyl silicone and deionized water, it is spare；(2) deionized water is added
Enter in reaction vessel, airtight heating is to 55 DEG C；Reaction vessel is opened after the completion of heating, and 2- acrylamido -2- is successively added
Methyl propane sulfonic acid polymer, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylamide-two
Methyl diallyl ammonium chloride-butyl acrylate copolymer, propernoic acid ester/20 methacrylate of octadecyl ethyoxyl are total
Polymers, -20 Methacrylate Crosspolymer of acrylate/stereth, acrylate/octadecyl ethyoxyl 50
Acrylate copolymer, acrylate/C10-30Alkylol acrylamide acid esters cross-linked polymer, acrylate/octadecyl ethyoxyl 20
Itaconate copolymeric and ethyl alcohol, propyl alcohol, acetone, closed holding heat 200 DEG C, the time 1 hour；(3) step (2) reaction knot
Reaction system is cooled to 30 DEG C, opens reaction vessel, polyethylene glycol propylene glycol copolymers, polypropylene glycol-are added by Shu Hou
Polyethylene glycol propylene glycol copolymers, ring five dimethyl silicone polymer, two silicon oxygen of hexamethyl, mercapto propyl-triethoxysilicane, methyl
Vinylsiloxane, closed holding heat 180 DEG C, the time 1 hour；(4) step (3) after reaction, by temperature of reaction system
55 DEG C are down to, and takes out cooling reaction product immediately, is transferred them in salable, pressurization automiser spray；(5) to being equipped with
Liquefied dimethyl ether, liquefied trichlorofluoromethane, liquefaction are filled in salable, pressurization the automiser spray of cooling reaction product
Dichlorotetra-fluoroethane, liquefied dicholorodifluoromethane, then seal automiser spray.The spray formulation being prepared is applied to
3D printing platform, comprising: (1) be sprayed using the automiser spray equipped with 3D printing platform spray formulation, by 3D printing platform
The uniform spraying of spray formulation is on 3D printing platform；(2) spraying is carried out in the spray formulation on 3D printing platform using scraper plate
It scrapes, make the spray formulation dilutionization of viscosity and is uniformly layed in print area；(3) in dilutionization and uniformly it is layed in print zone
3D printing is carried out on the spray formulation in domain.
Test the rest viscosity of spray formulation, if there is shear thinning behavior, 3D printing platform can be spread evenly across, it is cold
Whether the but adhesion strength after solidification with the adhesion strength of 3D printing platform and model, model occur warpage, and removing rear platform is
The no residual for having glue, whether model faying face has breakage after removing, is as a result listed in table 1.
Comparative example one
The raw material that uses, preparation method, application method, test method are the same as example 1, only will be in embodiment one
Octyl 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 the same as example 1, only will be in embodiment one
Octyl 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 the same as example 1, only will be in embodiment one
- 20 Methacrylate Crosspolymer content of acrylate/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 the same as example 1, only will be in embodiment one
- 20 Methacrylate Crosspolymer content of acrylate/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 the same as example 1, only will be in embodiment one
Polyethylene glycol propylene 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 the same as example 1, only will be in embodiment one
Polyethylene glycol propylene 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 the same as example 1, only will be in embodiment one
Polysiloxane level 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 the same as example 1, only will be in embodiment one
Polysiloxane level 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
Embodiment 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, tests are not added
Method is the same as example 1, and is as a result 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,
Raw material that he uses, preparation method, application method, test method are the same as example 1, and are as a result listed in table 1.
Comparative example 12
Do not add polysiloxanes, other raw material used, preparation method, application method, test methods with embodiment one
It is identical, as a result it is listed in table 1.
Table 1:
| Rest viscosity/mPa.s | Shear thinning | Even spread | Setting time/min | With platform adhesion strength | With model adhesion strength | Warpage occurs | There is glue residua | Model accuracy | |
| 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, ◎ indicate affirmative as a result, zero indicate negative as a result ,-indicate 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 component 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 constituted
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.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of 3D printing platform spray formulation, it is characterised in that: prepared by plurality of raw materials, the plurality of raw materials includes following heavy
Measure the component of percentage:
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 acid 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, it is characterised in that: the propylene of the hydrophobically modified
It is poly- that acid esters or its salt are selected from acrylate/20 methacrylate copolymer of octadecyl ethyoxyl, acrylate/stearyl alcohol
- 20 Methacrylate Crosspolymer of ether, acrylate/50 acrylate copolymer of octadecyl ethyoxyl, acrylic acid
Ester/C10-30In alkylol acrylamide acid esters cross-linked polymer, acrylate/20 itaconate copolymeric of octadecyl ethyoxyl extremely
Few one kind.
4. a kind of 3D printing platform spray formulation according to claim 1, it is characterised in that: described by least one poly- second
The block polymer that diol block and at least one polyethylene glycol block are constituted is selected from polyethylene glycol propylene glycol copolymers, gathers
At least one of propylene glycol-polyethylene glycol propylene glycol copolymers.
5. a kind of 3D printing platform spray formulation according to claim 1, it is characterised in that: the organic solvent is selected from second
At least one of alcohol, propyl alcohol, acetone.
6. a kind of 3D printing platform spray formulation according to claim 1, it is characterised in that: the low boiling point organic compound
Object gas is selected from least one of dimethyl ether, trichlorofluoromethane, dichlorotetra-fluoroethane, dicholorodifluoromethane.
7. a kind of 3D printing platform spray formulation according to claim 1-6, it is characterised in that: the poly- silicon oxygen
Alkane is ring five dimethyl silicone polymer.
8. a kind of preparation method of 3D printing platform spray formulation according to claim 1-7, it is characterised in that:
Including following preparation step:
(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) 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 the anion film forming polymer, the acrylate of the hydrophobically modified or its salt and described organic is successively added
Solvent, closed holding heat 60-350 DEG C, time 1-1.5 hour；
(3) reaction system after reaction, is cooled to 50 DEG C hereinafter, open the reaction vessel by step (2), be added 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 constituted, it is close
Close 70-300 DEG C of holding heating, time 0.5-1 hour；
(4) temperature of reaction system after reaction, is down to 50-60 DEG C by step (3), opens the reaction vessel, and take immediately
Cooling reaction product out transfers 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 described in any item 3D printing platform spray formulations of claim 1-7 are applied to the method for 3D printing platform,
Include:
(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 using scraper plate in the spray formulation on 3D printing platform, makes viscosity 5000-50000mPa.s
Spray formulation dilutionization and be uniformly layed in the print area of the 3D printing platform；
(3) it in dilutionization and is uniformly layed on the spray formulation of the print area and carries out 3D printing.
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| CN111454458B (en) * | 2020-04-23 | 2022-03-11 | 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 |
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| CN105885735A (en) * | 2016-04-25 | 2016-08-24 | 厦门螺壳电子科技有限公司 | Adhesive for 3D printing platform and preparation method of adhesive |
| CN107521087A (en) * | 2017-02-28 | 2017-12-29 | 中国科学院宁波材料技术与工程研究所 | The method for preventing warpage during 3D printing |
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Denomination of invention: Spray preparation for 3D printing platform and preparation method thereof Effective date of registration: 20201014 Granted publication date: 20190222 Pledgee: Shenzhen hi tech investment small loan Co.,Ltd. Pledgor: SHENZHEN ANYCUBIC TECHNOLOGY Co.,Ltd. Registration number: Y2020980006766 |