CN104263150B - The preparation method of a kind of 3D printer and its workbench film layer, coating coated in 3D printer workbench and preparation method thereof - Google Patents
The preparation method of a kind of 3D printer and its workbench film layer, coating coated in 3D printer workbench and preparation method thereof Download PDFInfo
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- CN104263150B CN104263150B CN201410459324.1A CN201410459324A CN104263150B CN 104263150 B CN104263150 B CN 104263150B CN 201410459324 A CN201410459324 A CN 201410459324A CN 104263150 B CN104263150 B CN 104263150B
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The present invention provides a kind of coating and preparation method applied to 3D printer workbench, and the coating is prepared by the component of following mass parts：Acrylic resin copolymer is 10 to 25 mass parts, and aerosil is 0.2 to 0.8 mass parts, and silane coupler is 0.2 to 0.6 mass parts, and diluent is 25 to 65 mass parts.The preparation method of above-mentioned coating, this method prepare mixed liquor first, and above-mentioned mixed liquor component is：Acrylic resin copolymer is 10 to 25 mass parts, and aerosil is 0.2 to 0.8 mass parts, and diluent is 25 to 65 mass parts, then adds the silane coupler of 0.2 to 0.6 mass parts in above-mentioned mixed liquor, uniformly obtains coating after mixing.Preparation method provided by the invention applied to 3D printer workbench paint has the advantages that process is few, easy to operate, the time is short, can realize scale industrial production.In addition, the coating obtained by above-mentioned preparation method is safe to use, environment-friendly, cheap.
Description
Technical field
The present invention relates to a kind of coating, and in particular to a kind of coating coated in 3D printer workbench and this coating
Preparation method, the 3D printer coated with this coating and the side that film made of this coating is coated on 3D printer
Method.
Background technology
3D printing technique is one kind of rapid shaping technique, and its common print procedure is:It is soft to first pass through microcomputer modelling
Part is modeled, then the threedimensional model built up " subregion " is cut into slices, so as to instruct printer successively to print into section successively.
Rapid shaping technique in the market is broadly divided into melt-laminated molding technology（FDM), three dimensional printing technology
（3DP）, stereolithography techniques（SLA）, precinct laser sintering（SLS）, laser forming technology（DLP）It is molded with UV ultraviolets
Technology etc..Melted extrusion modeling forming technique（FDM）It is a kind of technical matters commonly used in 3D printing techniques, principle is to utilize
Thermoplastic, polymeric materials in the molten state, squeeze out at shower nozzle, and solidification forms the thin layer of contour shape, another layer one
The superposition of layer ground ultimately forms product.The more common polymeric material of melted extrusion modeling forming technique is propylene in the market
Nitrile-butadiene-styrene terpolymer（ABS）, PLA（PLA）, nylon（PA）And makrolon（PC）.
In the 3D printer course of work, when about 220 DEG C of melted materials such as ABS or PLA are expressed to work from shower nozzle
After making on platform, melted material starts to be converted into solid-state, and now the contact surface of workbench and melted material can produce one instantaneously
Adhesive force, adhesive force sufficiently large must can ensure being smoothed out for print procedure, can not be completed if adhesive force is less than normal
Forming process.And after printing objects formation, during printing objects temperature is gradually reduced, under adhesive force meeting is corresponding
Drop, when printing objects temperature to room temperature, adhesive force must be sufficiently small, can so ensure that printing objects are easy to take from workbench
Under.
During 3D printing, if directly by melted material printing on the table, the molecule of the object printed will
Interpenetrated with the molecule of workbench, the object and workbench for causing printing are consumingly bonded together, it is difficult to remove and printed
Into object.In the prior art, a layered paper would generally be posted on the workbench of 3D printer, however, printed material such as poly- breast
Acid can directly penetrate into the inside of paster after high-temperature fusion, and paster adhesion, after printing objects are cooled to room temperature, due to printing
Object is sticked together with paster, therefore is not easy to remove.Need to be separated object with paster with scuppit in real work, it is such
Operation certainly will be easily destroyed object and paster, and just need to enter the paster of workbench after often completing one or pieces printed matter Products
Row is changed, and the technique that paster is changed in real work is cumbersome, and cost significantly improves.
The content of the invention
The present invention provides a kind of coating coated in 3D printer workbench and this coating for problem above
Preparation method;In addition prepare what is be attached to the method for 3D printer workbench film layer and be consequently formed present invention also offers a kind of
3D printer.
A kind of coating coated in 3D printer workbench, it is characterised in that prepared by the component of following mass parts：
The mass parts of acrylic resin copolymer 10 to 25；
The mass parts of aerosil 0.2 to 0.8；
The mass parts of silane coupler 0.2 to 0.6；
The mass parts of diluent 25 to 65.
It is further characterized in that：Acrylic resin copolymer comprises at least one kind in following monomer：Acrylic acid, propylene
Acid butyl ester, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, methacrylic acid hydroxypropyl
Ester, tertiary carbonic acid glycidyl ester.
Present invention also offers a kind of preparation method for coating coated in 3D printer workbench, it is characterised in that including with
Lower step：（1）Mixed liquor is prepared, the component of the mass parts of mixed liquor is：Acrylic resin copolymer is 10 to 25 mass parts；Gas
Aerosil is 0.2 to 0.8 mass parts；Diluent is 25 to 65 mass parts；（2）By the silane coupled of 0.2 to 0.6 mass parts
Agent adds step（1）In mixed liquor, uniformly coating is obtained after mixing.
It is provided by the invention to have that process is few, easy to operate, the time is short coated in 3D printer workbench paint preparation method
The advantages that, scale industrial production can be realized.In addition, the coating obtained by above-mentioned preparation method is safe to use, environment is friendly
It is good, cheap.
It is further characterized in that：Acrylic resin copolymer comprises at least one kind in following monomer：Acrylic acid, propylene
Acid butyl ester, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, methacrylic acid hydroxypropyl
Ester, tertiary carbonic acid glycidyl ester.
It is yet further characterised in that step（1）The preparation method of mixed liquor comprise the following steps：（a）By 0.2 to 0.8
The aerosil of mass parts is dissolved in the diluent of 15 to 35 mass parts, and solution A is formed after being completely dissolved；（b）By acrylic acid
The mass parts of resin copolymer 10 to 25 are dissolved in the diluent of 10 to 30 mass parts.Solution B is formed after being completely dissolved；（c）By solution A
Mixed with solution B, obtain mixed liquor.
It is easy that the process of mixed liquor is made using above-mentioned steps, it is easily operated, and discovery uses this in experimentation
Kind compound method, solute course of dissolution is rapid, is uniformly dispersed, and shortens the preparation time of mixed liquor, and solute in mixed liquor
Dispersion effect be better than other compound methods.
Present invention also offers a kind of 3D printer, including workbench and coating film layer on the table, its feature exists
In the film layer coated on the table is prepared by the component of following mass parts：Acrylic resin copolymer is 10 to 25 matter
Measure part；Aerosil is 0.2 to 0.8 mass parts；Silane coupled is 0.2 to 0.6 mass parts.
3D printer provided by the invention, there is film layer on the table, the surface of film layer is Porous Silicon structures, and bottom is cause
Close high temperature resistant acrylic resin copolymer film.The film layer possesses following two features, when hot melt materials and film layer connect
Temperature begins to decline and can produce a very strong instantaneous adhesion after touch, so as to smoothly complete the print procedure of object, when beating
After print process terminates, object is cooled to room temperature, and the adhesive force between printing objects and film layer can diminish, and can directly be removed with hand
Object.Film layer on workbench service life length, avoids the behaviour for frequently changing film on workbench after once spraying formation
Make, printing effect lifting, cost reduces.
It is further characterized in that：Acrylic resin copolymer comprises at least one kind in following monomer：Acrylic acid, propylene
Acid butyl ester, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, methacrylic acid hydroxypropyl
Ester, tertiary carbonic acid glycidyl ester.
The method coated in film layer on 3D printer workbench is prepared present invention also offers a kind of, it is characterised in that including
Following steps：(1）Mixed liquor is prepared, the component of the mass parts of mixed liquor is：Acrylic resin copolymer is 10 to 25 mass parts；
Aerosil is 0.2 to 0.8 mass parts；Diluent is 25 to 65 mass parts；（2）The silane of 0.2 to 0.6 mass parts is even
Join agent and add step（1）In mixed liquor, uniformly coating is obtained after mixing.（3）By step（2）Coating be sprayed at workbench, 150
DEG C to 180 DEG C toast 60 to 90 minutes.
It is further characterized in that：Acrylic resin copolymer comprises at least one kind in following monomer：Acrylic acid, propylene
Acid butyl ester, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, methacrylic acid hydroxypropyl
Ester, tertiary carbonic acid glycidyl ester.
It is yet further characterised in that step（1）The preparation method of mixed liquor comprise the following steps：（a）By 0.2 to 0.8
The aerosil of mass parts is dissolved in the diluent of 15 to 35 mass parts, and solution A is formed after being completely dissolved；（b）By acrylic acid
The mass parts of resin copolymer 10 to 25 are dissolved in the diluent of 10 to 30 mass parts.Solution B is formed after being completely dissolved；（c）By solution A
Mixed with solution B, obtain mixed liquor.
Brief description of the drawings
Fig. 1 is the flow chart that the present invention prepares the embodiment of the method for film layer on 3D printer workbench.
Fig. 2 is the schematic diagram of 3D printer embodiment of the present invention.
Fig. 3 is the sectional view of workbench in 3D printer embodiment of the present invention.
Embodiment
The coating of the present invention is used for the workbench coated in 3D printer, and the 3D printer coated with this coating is being beaten
After print completes object, easily the object for printing completion can be removed from workbench.
Preparation method coated in 3D printer workbench paint：
As shown in figure 1, when preparing the coating coated in 3D printer workbench, step S1, acrylic acid synthesizing is first carried out
Resin copolymer.Solvent is added in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel, activity
Intermediate tertiary carbonic acid glycidyl ester, by acrylic monomers mixing for standby use, acrylic monomers can choose methyl methacrylate
（MMA）, butyl acrylate（BA）, methacrylic acid（MAA）, base hydroxypropyl acrylate（HPMA）In one or more, monomer
The initiator of polymerization is dissolved in the acrylic monomers of mixing.It is single that acrylic acid mixing is added dropwise after solvent in flask is warming up into 90 DEG C
Body, it is added dropwise within about 2.5 hours.Keeping temperature is constant, continues reaction 3 hours or so, is made slightly lurid transparent sticky
Liquid.Then, 60 DEG C or so are cooled to, adds 10 to 20 parts of quantitative amine neutralizer, continues stirring 0.5 hour, with dropwise addition
Mode is added water in system, and acrylic resin copolymer is made.The scheme further optimized can be added in reaction system
Enter isocyanate curing agent（GH）, to lift the performance of acrylic monomers.The scheme further optimized is cured with isocyanates
The optimal addn of agent is the 0.8% of overall reaction system quality, and isocyanates, the cementability of acrylic acid and resistance to are added in this ratio
High-temperature behavior is excellent.
As another preferable scheme, acrylic resin copolymer is carried by dongguan new world technology co., ltd
For product type is WZ510 product.The acrylic resin copolymer provided using the said firm meets the present invention for acrylic acid
The particular/special requirement of resin copolymer, shorten the time for preparing coating.
Then, step S2 is performed, the obtained acrylic resin copolymers of step S1 are dissolved in wiring solution-forming in diluent
A.Diluent used in the present embodiment can select the mixed solvent of one or two kinds of above solvent in following solvent：
Ethyl acetate, amyl acetate, butyl acetate.While performing step S1 and step S2, step S3 is performed, by aerosil
It is dissolved in wiring solution-forming B in diluent.
After performing step S1, S2 and step S3, step S4 is performed, what the solution A that step S2 is obtained obtained with step S3
Solution B is mixed to get mixed liquor C, and its mixed process can instill solution A solution B, or solution B instills solution A.Then,
Perform step S5, the mixed liquor C obtained in step S4 and silane coupler be mixed to get mixed liquor D, preferable scheme be by
Silane coupler is added dropwise in mixed liquor D.Silane coupler chooses one or two kinds of above reagent in following reagent
Mixture：β-（3,4- epoxycyclohexyls）Ethyl triethoxysilane, γ-glycidol ether propyl trimethoxy silicane, γ-
Aminopropyl triethoxysilane.Finally, step S6 is performed, the mixed liquor D that step S5 is obtained fully is dissolved, disperses to be applied
Material.As preferable technical scheme, mixed liquor D is disperseed using high speed dispersor, jitter time is 1 to 2 hour.
The specific preparation method of 3D printer workbench paint is coated in below by multiple embodiment introductions.
Embodiment 1：
Step 1：By the N methyldiethanol amine of 40 mass parts（DEMA）, 10 mass parts triethylamine（TEA）, 7.1 mass
The tertiary carbonic acid glycidyl ester of part（E10）Add in four-hole boiling flask, after being warming up to 90 DEG C, start that mixed solution, the mixing is added dropwise
Solution compolision is：The methyl methacrylate of 27 mass parts（MMA）, 6 mass parts butyl acrylate（BA）, 0.4 part of mass parts
Methacrylic acid（MAA）, 9 mass parts hydroxy propyl methacrylate（HPMA）With the benzoyl peroxide of 0.4 mass parts
（BPO）The initiator aid BYK of initiator, 0.1 mass parts, mix monomer is added dropwise using the times of 2.5 hours.Keeping temperature
It is constant, continue reaction and continue 3 hours, slightly lurid transparent viscous liquid is made, be cooled to 60 DEG C or so, add 10 matter
The triethanolamine of part is measured, continues stirring 0.5 hour, by the water addition system of 10 mass parts in a manner of dropwise addition, propylene is made
Acid resin copolymer.
Step 2：The mass parts of acrylic resin copolymer made from step 1 10 are dissolved in the ethyl acetate of 10 mass parts, it is complete
Solution A is formed after fully dissolved.
Step 3：0.2 part of aerosil is dissolved in the ethyl acetate of 15 mass parts, solution is formed after being completely dissolved
B。
Step 4：Solution A addition solution B is obtained into mixed liquor C, the coupling agent of 0.4 mass parts is added, obtains mixed liquor
D。
Step 5：Mixed liquor D is disperseed to obtain coating in 1 hour under high speed dispersor.
Embodiment 2：
Step 1：Use the acrylic resin that the product type produced by dongguan new world technology co., ltd is WZ510
The mass parts of copolymer 10 are dissolved in the amyl acetate of 10 mass parts, and solution A is formed after being completely dissolved.
Step 2：0.4 part of aerosil is dissolved in the amyl acetate of 15 mass parts, solution is formed after being completely dissolved
B。
Step 3：Solution A addition solution B is obtained into mixed liquor C, adds γ-glycidol ether propyl group of 0.4 mass parts
Trimethoxy silane, obtain mixed liquor D.
Step 4：Mixed liquor D is disperseed to obtain coating in 1.5 hours under high speed dispersor.
Embodiment 3：
Step 1：Use the acrylic acid tree that the product type produced by dongguan new world technology co., ltd is WZ510
The mass parts of resin copolymer 10 are dissolved in the butyl acetate of 10 mass parts, and solution A is formed after being completely dissolved.
Step 2：0.2 part of aerosil is dissolved in the butyl acetate of 25 mass parts, solution is formed after being completely dissolved
B。
Step 3：Solution B addition solution A is obtained into mixed liquor C, adds the gamma-aminopropyl-triethoxy of 0.2 mass parts
Silane, obtain mixed liquor D.
Step 4：Mixed liquor D is disperseed to obtain coating in 2 hours under high speed dispersor.
Embodiment 4:
Step 1：100 mass are added in the four-hole boiling flask equipped with agitator, condenser, thermometer and constant pressure funnel
Part N methyldiethanol amine（DEMA）, the tertiary carbonic acid glycidyl ester of 2 mass parts, then the acrylic monomers of 100 mass parts is mixed
Close, acrylic monomers can choose methyl methacrylate（MMA）, butyl acrylate（BA）, methacrylic acid（MAA）, base third
Olefin(e) acid hydroxypropyl acrylate（HPMA）In one or more, the benzoyl peroxide of 1 mass parts（BPO）Initiator is dissolved in the third of mixing
In acrylic monomer.Acrylic acid mix monomer is added dropwise after solvent in flask is warming up into 90 DEG C, is added dropwise within about 2.5 hours.Keep
Temperature is constant, continues reaction 3 hours or so, and slightly lurid transparent viscous liquid is made.Then, 60 DEG C or so are cooled to,
20 parts of triethanolamine is added, continues stirring 0.5 hour, by 20 parts of water addition system in a manner of dropwise addition, acrylic acid is made
Resin copolymer.
Step 2：The mass parts of acrylic resin copolymer made from step 1 15 are dissolved in the butyl acetate of 20 mass parts, it is complete
Solution A is formed after fully dissolved.
Step 3：0.5 part of aerosil is dissolved in the ethyl acetate of 25 mass parts, solution is formed after being completely dissolved
B。
Step 4：Solution A addition solution B is obtained into mixed liquor C, adds the gamma-aminopropyl-triethoxy of 0.6 mass parts
Silane, obtain mixed liquor D.
Step 5：Mixed liquor D is disperseed to obtain coating in 1.2 hours under high speed dispersor.
Embodiment 5：
Step 1：By the N methyldiethanol amine of 40 mass parts（DEMA）, 10 mass parts triethylamine（TEA）, 7.1 mass
The tertiary carbonic acid glycidyl ester of part（E10）Add in four-hole boiling flask, be warming up to 90 DEG C, mixed solution, mixed solution is then added dropwise
Include the acrylic acid of 27 mass parts（AA）, 6 mass parts butyl acrylate（BA）, 3 mass parts 2-EHA（2-
EHA）, 0.4 mass parts benzoyl peroxide（BPO）As initiator, the initiator aid BYK of 0.1 mass parts and 0.7 mass
The isocyanate curing agent of part（GH）, it is added dropwise within about 2.5 hours.Keeping temperature, continue reaction 3 hours or so, be made slightly
Lurid transparent viscous liquid, 60 DEG C or so are cooled to, add the triethanolamine of 15 mass parts, continue stirring 0.5 hour, with
Acrylic resin copolymer is made by the water addition system of 15 mass parts in the mode of dropwise addition.
Step 2：The mass parts of acrylic resin copolymer 15 that step 1 obtains are dissolved in the amyl acetate of 20 mass parts, it is complete
Solution A is formed after fully dissolved.
Step 3：0.5 part of aerosil is dissolved in the amyl acetate of 25 mass parts, solution is formed after being completely dissolved
B。
Step 4：Solution A addition solution B is obtained into mixed liquor C, add the β of 0.4 mass parts-（3,4- epoxycyclohexyls）
Ethyl triethoxysilane, obtain mixed liquor D.
Step 5：Mixed liquor D is disperseed to obtain coating in 1 hour under high speed dispersor.
Embodiment 6：
Step 1：By the N methyldiethanol amine of 40 mass parts（DEMA）, 10 mass parts triethylamine（TEA）, 7.1 mass
The tertiary carbonic acid glycidyl ester of part（E10）Add in four-hole boiling flask, by the methyl methacrylate of 27 mass parts（MMA）, 6 mass
The butyl acrylate of part（BA）, 0.4 part of mass parts methacrylic acid（MAA）, 9 mass parts hydroxy propyl methacrylate
（HPMA）With the benzoyl peroxide of 0.4 mass parts（BPO）Initiator aid BYK mixing as initiator, 0.1 mass parts is standby
With.Solvent in flask is warming up to after 90 DEG C mixed solution is added dropwise, be added dropwise within about 2.5 hours.Reaction temperature is 90 DEG C, is continued
Reaction 3 hours or so, slightly lurid transparent viscous liquid is made, is cooled to 60 DEG C or so, add three second of 20 mass parts
Hydramine, continue stirring 0.5 hour, acrylic resin copolymerization in the water addition system of 18 mass parts, will be made in a manner of dropwise addition
Thing.
Step 2：The mass parts of acrylic resin copolymer 10 that step 1 obtains are dissolved in the ethyl acetate of 10 mass parts, it is complete
Solution A is formed after fully dissolved.
Step 3：0.2 part of aerosil is dissolved in the ethyl acetate of 15 mass parts, solution is formed after being completely dissolved
B。
Step 4：Solution A addition solution B is obtained into mixed liquor C, the coupling agent of 0.5 mass parts is added, obtains mixed liquor
D。
Step 5：Mixed liquor D is disperseed to obtain coating in 1 hour under high speed dispersor.
Embodiment 7：
Step 1：By the N methyldiethanol amine of 40 mass parts（DEMA）, 10 mass parts triethylamine（TEA）, 7.1 mass
The tertiary carbonic acid glycidyl ester of part（E10）Add in four-hole boiling flask, by the methyl methacrylate of 27 mass parts（MMA）, 6 matter
Measure the butyl acrylate of part（BA）, 0.4 part of mass parts methacrylic acid（MAA）, 9 mass parts hydroxy propyl methacrylate
（HPMA）With the benzoyl peroxide of 0.4 mass parts（BPO）Initiator aid BYK mixing as initiator, 0.1 mass parts is standby
With.Solvent in flask is warming up to after 90 DEG C mixed solution is added dropwise, be added dropwise within about 2.5 hours, keeping temperature, continue reaction 3
Hour or so, slightly lurid transparent viscous liquid is made, is cooled to 60 DEG C or so, adds quantitative amine neutralizer, continues
Stirring 0.5 hour, by quantitative water addition system in a manner of dropwise addition, acrylic resin copolymer is made.
Step 2：The mass parts of acrylic resin copolymer made from step 1 15 are dissolved in the diluent of 15 mass parts.Completely
Solution A is formed after dissolving.
0.6 part of aerosil is dissolved in the ethyl acetate of 45 mass parts by step 3., and solution is formed after being completely dissolved
B。
Solution A addition solution B is obtained mixed liquor C by step 4., is added the coupling agent of 0.4 mass parts, is obtained mixed liquor
D。
Mixed liquor D is disperseed to obtain coating in 1 hour by step 5. under high speed dispersor.
It is described below using method of the above-mentioned coating preparation coated in film layer on 3D printer workbench, and introduction has
The 3D printer of this film layer.
As shown in Fig. 2 the 3D printer of the present invention includes shell mechanism 1, printhead 2, workbench 3.Printhead 2 can be
Transversely or longitudinally moved in plane where workbench 3, workbench 3 can be along plumb line direction in the presence of elevating mechanism
It is mobile.By the way of successively printing, the position of constantly regulate printhead 2 and workbench 3, printhead 2 squeezes out 3D printer
The melted material such as ABS or PLA come can be to form three-dimensional body on workbench 3.
When preparing the film layer coated in 3D printer workbench 3, applied after performing step S1 to S6 as shown in Figure 1
Material, step S7 is then performed, the obtained coating of step S6 is sprayed on the workbench 3 of 3D printer.Work in the prior art
Platform 3 is usually the glass or aluminium sheet of heat conduction, and spraying process can use the existing instrument for being exclusively used in spraying or be accomplished manually.
As shown in figures 1 and 3, after performing step S7, step S8 is then performed, the coating being sprayed on workbench 3 is entered
Row baking, ultimately form the film layer 31 that can be applied to 3D printer.The thickness of film layer 31 on workbench 3 is arbitrary value, preferably
Technical scheme be preferred 50um to the 80um of thicknesses of layers.Workbench 3 can be directly placed into drying box by baking process, be adopted
Mode of heating, the baking temperatures such as power taking heating, infrared, microwave are set as 150 DEG C to 180 DEG C, and baking time continues 60 to 90 points
Clock.
As shown in figure 3, the section of workbench 3 includes zone of heating 33, aluminum layer 32 and film layer 31 successively.In 3D printing process
In, workbench 3 can heat up in the presence of zone of heating 33 and be maintained at a steady temperature, for different printed materials, on
Stating steady temperature can be different according to the property of material.For example, when printing using ABS material, the temperature is normally set up
For 110 DEG C, and if using PLA material, then temperature should be risen to 70 DEG C.The effect heated to workbench 3 is to prevent
Only there is warpage or deformation in printing objects.After the melted material that temperature is 220 DEG C contacts with film layer 31, melted material temperature
Begin to decline and be converted into solid-state and a very strong instantaneous adhesion can be produced, so as to smoothly complete the print procedure of object.
Due to adding aerosil in the dope preparing process of the present invention, arrange and dredge between the membrane layer molecules coated in workbench 3
Pine, intermolecular to form larger void structure, after print procedure terminates, object is cooled to room temperature, and object connects with film layer 31
Tactile molecule can be entered in void structure, without intermolecular force is merged or produced with membrane layer molecules, therefore
Adhesive force between printing objects and film layer 31 can diminish, and directly can remove object with hand.
The method that film layer is prepared on 3D printer is described below.
Embodiment 8：
Step 1：Third is used as using the product that the product type produced by dongguan new world technology co., ltd is WZ510
Olefin(e) acid resin copolymer.
Step 2：The aerosil of 0.8 mass parts is dissolved in the diluent of 35 mass parts, formed after being completely dissolved molten
Liquid A.
Step 3：The mass parts of acrylic resin 25 are dissolved in the diluent of 30 mass parts, solution B is formed after being completely dissolved.
Step 4：Solution A is added into solution B, adds the coupling agent of 0.4 mass parts, it is small that 2 are disperseed under high speed dispersor
When obtain coating.
Step 5：The coating that step 4 is obtained is sprayed on workbench by spraying method, and 150 DEG C are toasted 90 minutes.
Embodiment 9：
Step 1；By the N methyldiethanol amine of 40 mass parts（DEMA）, 10 mass parts triethylamine（TEA）, 7.1 mass
The tertiary carbonic acid glycidyl ester of part（E10）Add in four-hole boiling flask, after being warming up to 90 DEG C, be then added dropwise by the methyl of 27 mass parts
Methyl acrylate（MMA）, 6 mass parts butyl acrylate（BA）, 0.4 part of mass parts methacrylic acid（MAA）, 9 mass parts
Hydroxy propyl methacrylate（HPMA）With the benzoyl peroxide of 0.4 mass parts（BPO）As initiator, 0.1 mass parts
The mixed solution of initiator aid BYK compositions, is added dropwise for about 2.5 hours.Keeping temperature, continue reaction 3 hours or so, be made
Slightly lurid transparent viscous liquid, 60 DEG C or so are cooled to, add the triethanolamine of 17 mass parts, it is small to continue stirring 0.5
When, by the water addition system of 15 mass parts in a manner of dropwise addition, acrylic resin copolymer is made.
Step 2：The mass parts of acrylic resin copolymer 10 that step 1 obtains are dissolved in the diluent of 10 mass parts, completely
Solution A is formed after dissolving.
Step 3：0.2 part of aerosil is dissolved in the ethyl acetate of 15 mass parts, solution is formed after being completely dissolved
B。
Step 4：Solution A addition solution B is obtained into mixed liquor C, adds the coupling agent of 0.4 mass parts, high speed dispersor
Disperse to obtain coating in 1 hour down.
Step 5：The coating that step 4 is obtained is sprayed on workbench by spraying method, and 180 DEG C are toasted 60 minutes.
Embodiment 10：
Step 1：The product type produced using dongguan new world technology co., ltd is that WZ510 acrylic resin is total to
The mass parts of polymers 25 are dissolved in the butyl acetate of 20 mass parts, and solution A is formed after being completely dissolved.
Step 2：0.4 part of aerosil is dissolved in the butyl acetate of 35 mass parts, solution is formed after being completely dissolved
B。
Step 3：Solution B addition solution A is obtained into mixed liquor C, adds the gamma-aminopropyl-triethoxy of 0.3 mass parts
Silane, disperse to obtain coating in 2 hours under high speed dispersor.
Step 4：By step:3 obtained coating are sprayed on workbench by spraying method, and 170 DEG C are toasted 80 minutes.
Claims (5)
1. a kind of 3D printer, including workbench, film layer is coated with the workbench, it is characterised in that：The film layer by with
The component of lower mass parts prepares：
The mass parts of acrylic resin copolymer 10 to 25；
The mass parts of aerosil 0.2 to 0.8；
The mass parts of silane coupler 0.2 to 0.6；
The surface of film layer is Porous Silicon structures, and bottom is fine and close high temperature resistant acrylic resin copolymer film；The film layer possesses
Following two features, temperature begins to decline and can produce a very strong instantaneous attachment after hot melt materials contact with film layer
Power, so as to smoothly complete the print procedure of object, after print procedure terminates, object is cooled to room temperature, printing objects and film layer
Between adhesive force can diminish, directly can remove object with hand.
2. printer according to claim 1, it is characterised in that：The acrylic resin copolymer is comprised at least to place an order
One kind in body：Acrylic acid, butyl acrylate, 2-EHA, methyl methacrylate, methacrylic acid, methyl
Hydroxypropyl acrylate, tertiary carbonic acid glycidyl ester.
3. a kind of prepare the method coated in film on 3D printer workbench, it is characterised in that comprises the following steps：
(1）Mixed liquor is prepared, the component of the mass parts of the mixed liquor is：
The mass parts of acrylic resin copolymer 10 to 25；
The mass parts of aerosil 0.2 to 0.8；
The mass parts of diluent 25 to 65；
（2）The silane coupler of 0.2 to 0.6 mass parts is added into step（1）In the mixed liquor, uniformly applied after mixing
Material；
（3）By step（2）The coating be sprayed at workbench, toasted 60 to 90 minutes at a temperature of 150 DEG C to 180 DEG C；
The surface of film layer is Porous Silicon structures, and bottom is fine and close high temperature resistant acrylic resin copolymer film；The film layer possesses
Following two features, temperature begins to decline and can produce a very strong instantaneous attachment after hot melt materials contact with film layer
Power, so as to smoothly complete the print procedure of object, after print procedure terminates, object is cooled to room temperature, printing objects and film layer
Between adhesive force can diminish, directly can remove object with hand.
4. according to the method for claim 3, it is characterised in that：The acrylic resin copolymer comprises at least following monomer
In one kind：Acrylic acid, butyl acrylate, 2-EHA, methyl methacrylate, methacrylic acid, methyl-prop
Olefin(e) acid hydroxypropyl acrylate, tertiary carbonic acid glycidyl ester.
5. according to the method for claim 3, it is characterised in that the step（1）The preparation method of the mixed liquor include
Following steps：
（a）The aerosil of 0.2 to 0.8 mass parts is dissolved in the diluent of 15 to 35 mass parts, formed after being completely dissolved
Solution A；
（b）The mass parts of acrylic resin copolymer 10 to 25 are dissolved in the diluent of 10 to 30 mass parts, formed after being completely dissolved
Solution B；
（c）The solution A is mixed with the solution B, obtains the mixed liquor.
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| CN201610225654.3A CN105936130B (en) | 2014-09-10 | 2014-09-10 | The forming method of 3D objects, the workbench of 3D printer and 3D printer |
| CN201410459324.1A CN104263150B (en) | 2014-09-10 | 2014-09-10 | The preparation method of a kind of 3D printer and its workbench film layer, coating coated in 3D printer workbench and preparation method thereof |
| PCT/CN2015/089097 WO2016037555A1 (en) | 2014-09-10 | 2015-09-08 | 3d printer and preparation method of workbench film layer thereof, and 3d printer workbench coating and preparation method thereof |
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| CN108466422B (en) * | 2015-04-17 | 2020-06-19 | 珠海天威飞马打印耗材有限公司 | Working method of three-dimensional printer |
| 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 |
| EP3600832B1 (en) * | 2017-03-30 | 2022-03-16 | Dow Silicones Corporation | Method of preparing porous silicone article and use of the silicone article |
| CN109774143A (en) * | 2017-11-13 | 2019-05-21 | 三纬国际立体列印科技股份有限公司 | The platform structure and its lamination microscope carrier of 3D printer |
| CN113416459B (en) * | 2021-06-11 | 2022-04-19 | 安徽强邦新材料股份有限公司 | Printing plate protective coating and preparation method thereof |
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| EP2514775A1 (en) * | 2011-04-20 | 2012-10-24 | Evonik Röhm GmbH | Maleic anhydride copolymers as soluble support material for fused deposition modelling (FDM) printer |
| WO2013090939A1 (en) * | 2011-12-15 | 2013-06-20 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
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