WO2016037555A1 - 3d printer and preparation method of workbench film layer thereof, and 3d printer workbench coating and preparation method thereof - Google Patents

3d printer and preparation method of workbench film layer thereof, and 3d printer workbench coating and preparation method thereof Download PDF

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Publication number
WO2016037555A1
WO2016037555A1 PCT/CN2015/089097 CN2015089097W WO2016037555A1 WO 2016037555 A1 WO2016037555 A1 WO 2016037555A1 CN 2015089097 W CN2015089097 W CN 2015089097W WO 2016037555 A1 WO2016037555 A1 WO 2016037555A1
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mass
parts
solution
acrylic resin
printer
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PCT/CN2015/089097
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French (fr)
Chinese (zh)
Inventor
余嘉
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珠海天威飞马打印耗材有限公司
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Publication of WO2016037555A1 publication Critical patent/WO2016037555A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12Homopolymers or copolymers of methyl methacrylate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a coating, and more particularly to a coating applied to a 3D printer table, a method of preparing the coating, a 3D printer coated with the coating, and a coating of the coating on a 3D printer.
  • Membrane method The present application is based on a Chinese patent application filed on Sep. 10, 2014, the entire disclosure of which is incorporated herein by reference.
  • 3D printing technology is a kind of rapid prototyping technology.
  • the common printing process is: firstly modeling by computer modeling software, and then “partitioning” the built 3D model into layer-by-layer sections, ie slices, to guide the printer layer by layer. print.
  • melt layer forming technology FDM
  • 3DP three-dimensional printing technology
  • SLA stereolithography
  • SLS selective laser sintering
  • DLP laser forming technology
  • UV ultraviolet light UV ultraviolet light.
  • FDM melt extrusion stacking technology
  • ABS acrylonitrile-butadiene-styrene terpolymer
  • PLA polylactic acid
  • PA nylon
  • PC polycarbonate
  • molten material of about 220 ° C, such as ABS or PLA
  • the molten material begins to transform into a solid state, at which point the interface between the table and the molten material generates a transient.
  • Adhesion adhesion must be large enough to ensure smooth printing process, if the adhesion is too small, the molding process cannot be completed.
  • the adhesion will decrease correspondingly during the temperature drop of the printing object. When the temperature of the printing object reaches room temperature, the adhesion must be small enough to ensure that the printing object is easily removed from the table.
  • the 3D printer is usually provided with a layer of stickers on the workbench.
  • the printed material such as polylactic acid directly penetrates into the interior of the sticker after being melted at a high temperature, and adheres to the sticker.
  • the printed object is cooled to room temperature, it is printed. Objects stick to the sticker and are therefore difficult to remove.
  • the sticker of the workbench needs to be replaced, and the sticker is replaced in actual work. The process is cumbersome and the cost is significantly improved.
  • the present invention is directed to the above problems, and mainly provides a coating applied to a 3D printer table and a method of preparing the coating.
  • the present invention provides a method of preparing a film layer attached to a 3D printer stage and a 3D printer formed thereby.
  • the coating provided on the 3D printer table provided by the present invention is prepared from the following parts by mass:
  • Fumed silica of 0.2 to 0.8 parts by mass
  • the diluent is 25 to 65 parts by mass.
  • the acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl acrylate, methacrylic acid, methyl Hydroxypropyl acrylate, glycidyl tert-carbonate.
  • the invention also provides a coating preparation method coated on a 3D printer workbench, the method comprising the following steps: (1) preparing a mixed liquid, the mass fraction of the mixed liquid is: the acrylic resin copolymer is 10 to 25 mass Parts; fumed silica is 0.2 to 0.8 parts by mass; diluent is 25 to 65 parts by mass; (2) 0.2 to 0.6 parts by mass of a silane coupling agent is added to the mixed liquid of the step (1), and uniformly mixed to obtain a coating. .
  • the method for preparing the mixed liquid of the step (1) comprises the steps of: (a) dissolving 0.2 to 0.8 parts by mass of fumed silica in 15 to 35 parts by mass of a diluent, and completely dissolving to form a solution A; b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of a diluent. Solution B is formed after complete dissolution; (c) Solution A is mixed with Solution B to obtain a mixed solution.
  • the present invention also provides a 3D printer comprising a table and a film layer coated on the table, wherein the film layer coated on the table is prepared from the following parts by mass: acrylic copolymer is 10 To 25 parts by mass; fumed silica is 0.2 to 0.8 parts by mass; and silane coupling is 0.2 to 0.6 parts by mass.
  • the invention also provides a method for preparing a film layer coated on a 3D printer workbench, comprising the following steps: (1) preparing a mixed liquid, the mass fraction of the mixed liquid is: the acrylic resin copolymer is 10 to 25 mass Parts; fumed silica is 0.2 to 0.8 parts by mass; diluent is 25 to 65 parts by mass; (2) 0.2 to 0.6 parts by mass of a silane coupling agent is added to the mixed liquid of the step (1), and uniformly mixed to obtain a coating. . (3) Spray the coating of step (2) on a workbench and bake at 150 ° C to 180 ° C for 60 to 90 minutes.
  • the method for preparing the mixed liquid of the step (1) comprises the steps of: (a) dissolving 0.2 to 0.8 parts by mass of fumed silica in 15 to 35 parts by mass of a diluent, and completely dissolving to form a solution A; b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of a diluent. Solution B is formed after complete dissolution; (c) Solution A is mixed with Solution B to obtain a mixed solution.
  • the coating preparation method provided by the invention in the 3D printer table has the advantages of fewer steps, easy operation, short time and the like, and can realize large-scale industrial production.
  • the coating obtained by the above preparation method is safe, environmentally friendly, and inexpensive.
  • the process of preparing the mixed liquid prepared by the step (1) in the method of the invention is simple and easy to operate, and it is found that the preparation method is adopted during the experiment, the dissolution process of the solute is rapid, the dispersion is uniform, and the preparation time of the mixed liquid is shortened. Moreover, the dispersion effect of the solute in the mixed solution is superior to other preparation methods.
  • the 3D printer provided by the invention has a film layer on the workbench, the surface of the film layer is a porous silicon structure, and the lower part is a dense high temperature resistant acrylic resin copolymer film.
  • the film has the following two characteristics: on the one hand, when the high-temperature molten material contacts the film layer, the temperature begins to decrease and a strong instantaneous adhesion is generated, thereby smoothly completing the printing process of the object, when the printing process is finished, When the object is cooled to room temperature, the adhesion between the printed object and the film layer becomes smaller, and the object can be removed directly by hand; on the other hand, after the film layer on the worktable is formed by one spray, the service life is long and the frequent avoidance is avoided.
  • the operation of replacing the film on the workbench improves the printing efficiency and reduces the cost.
  • Figure 1 is a flow diagram of an embodiment of a method of making a film layer on a 3D printer stage of the present invention.
  • FIG. 2 is a schematic diagram of an embodiment of a 3D printer of the present invention.
  • Figure 3 is a cross-sectional view of the stage in the embodiment of the 3D printer of the present invention.
  • the coating of the present invention is applied to a workbench of a 3D printer, and the 3D printer coated with such a paint can conveniently remove the printed object from the workbench after printing the finished object.
  • the coating, the preparation method of the coating, and the 3D printer coated with the coating will be described in detail below.
  • step S1 when preparing the coating applied to the 3D printer table, step S1 is first performed, Synthetic acrylic resin copolymer.
  • a solvent is added to a four-necked flask equipped with a stirrer, a condenser, a thermometer, and a constant pressure dropping funnel, the active intermediate glycidyl carbonate is mixed, the acrylic monomer is mixed, and the acrylic monomer can be selected from methacrylic acid.
  • MMA methyl ester
  • BA butyl acrylate
  • MAA methacrylic acid
  • HPMA hydroxypropyl acrylate
  • the solvent in the flask was heated to 90 ° C, and then the acrylic mixed monomer was added dropwise, and the dropwise addition was completed in about 2.5 hours.
  • the temperature was kept constant, and the reaction was continued for about 3 hours to obtain a slightly viscous, viscous liquid.
  • the temperature was lowered to about 60 ° C, a quantitative amount of the amine neutralizing agent was added to 10 to 20 parts, stirring was continued for 0.5 hours, and water was added dropwise to the system to obtain an acrylic resin copolymer.
  • an isocyanate curing agent may be added to the reaction system to enhance the performance of the acrylic monomer. More preferably, the isocyanate curing agent is preferably added in an amount of 0.8% by mass of the total reaction system, and isocyanate is added in this proportion, and acrylic acid is excellent in adhesion and high temperature resistance.
  • the acrylic resin copolymer is provided by Dongguan Xintiandi Technology Co., Ltd., and the product model is WZ510.
  • the use of the acrylic resin copolymer provided by the company meets the special requirements of the present invention for the acrylic resin copolymer, and shortens the time for preparing the coating.
  • step S2 is performed, and the acrylic resin copolymer obtained in step S1 is dissolved in a diluent to prepare a solution A.
  • the diluent used in the present embodiment may be selected from one of the following solvents or a mixed solvent of two or more solvents: ethyl acetate, amyl acetate, and butyl acetate.
  • the step S3 is performed, and the fumed silica is dissolved in the diluent to prepare the solution B.
  • step S4 is performed, and the solution A obtained in step S2 is mixed with the solution B obtained in step S3 to obtain a mixed solution C, and the mixing process may drop the solution A into the solution B or the solution B.
  • step S5 is performed, and the mixed liquid C obtained in step S4 is mixed with a silane coupling agent to obtain a mixed liquid D.
  • a silane coupling agent is added dropwise to the mixture D.
  • the silane coupling agent is one or a mixture of two or more of the following reagents: ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane , ⁇ -aminopropyltriethoxysilane.
  • step S6 the mixed solution D obtained in the step S5 is sufficiently dissolved and dispersed to obtain a coating material.
  • the mixed liquid D is dispersed by a high-speed disperser for a dispersion time of 1 to 2 hours.
  • Step 1 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90. After ° C, the mixed solution was started to be added dropwise, and the composition of the mixed solution was: 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), and 0.4 parts by mass of methacrylic acid (MAA).
  • DEMA N-methyldiethanolamine
  • TSA triethylamine
  • E10 glycidyl tert-carbonate
  • Step 2 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of ethyl acetate, and completely dissolved to form a solution A.
  • Step 3 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixture C, and then 0.4 part by mass of a coupling agent was added to obtain a mixed solution D.
  • Step 5 The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
  • Step 1 10 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 10 parts by mass of amyl acetate, and completely dissolved to form a solution A.
  • Step 2 0.4 part of fumed silica was dissolved in 15 parts by mass of amyl acetate, and completely dissolved to form a solution B.
  • Step 3 Solution A was added to Solution B to obtain a mixture C, and 0.4 parts by mass of ⁇ -glycidyl ether propyltrimethoxysilane was further added to obtain a mixed solution D.
  • Step 4 The mixture D was dispersed under a high speed disperser for 1.5 hours to obtain a coating.
  • Step 1 10 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 10 parts by mass of butyl acetate, and completely dissolved to form a solution A.
  • Step 2 0.2 part of fumed silica was dissolved in 25 parts by mass of butyl acetate, and completely dissolved to form a solution B.
  • Step 3 Solution B was added to Solution A to obtain a mixture C, and 0.2 part by mass of ⁇ -aminopropyltriethoxysilane was further added to obtain a mixed solution D.
  • Step 4 The mixture D was dispersed under a high speed disperser for 2 hours to obtain a coating.
  • Step 1 In a four-necked flask equipped with a stirrer, a condenser, a thermometer, and a constant pressure dropping funnel, 100 parts by mass of N-methyldiethanolamine (DEMA), 2 parts by mass of glycidyl tert-carbonate, and then 100 parts by mass of acrylic monomer may be mixed, and the acrylic monomer may be one selected from methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and hydroxypropyl acrylate (HPMA). A plurality of parts by mass of a benzoyl peroxide (BPO) initiator are dissolved in the mixed acrylic monomer.
  • DEMA N-methyldiethanolamine
  • BA butyl acrylate
  • MAA methacrylic acid
  • HPMA hydroxypropyl acrylate
  • BPO benzoyl peroxide
  • the solvent in the flask was heated to 90 ° C, and the acrylic monomer was added dropwise, and the addition was completed in about 2.5 hours.
  • the temperature was kept constant, and the reaction was continued for about 3 hours to obtain a slightly viscous, viscous liquid. Then, the temperature was lowered to about 60 ° C, 20 parts of triethanolamine was added, stirring was continued for 0.5 hour, and 20 parts of water was added dropwise to the system to obtain an acrylic resin copolymer.
  • Step 2 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 20 parts by mass of butyl acetate, and completely dissolved to form a solution A.
  • Step 3 0.5 part of fumed silica was dissolved in 25 parts by mass of ethyl acetate to completely dissolve to form solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixture C, and 0.6 parts by mass of ⁇ -aminopropyltriethoxysilane was further added to obtain a mixed solution D.
  • Step 5 The mixture D was dispersed under a high speed disperser for 1.2 hours to obtain a coating.
  • Step 1 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90.
  • DEMA N-methyldiethanolamine
  • TAA triethylamine
  • E10 glycidyl tert-carbonate
  • Step 2 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 20 parts by mass of amyl acetate, and completely dissolved to form a solution A.
  • Step 3 0.5 part of fumed silica was dissolved in 25 parts by mass of amyl acetate, and completely dissolved to form a solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixture C, and 0.4 parts by mass of ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane was further added to obtain a mixed solution D.
  • Step 5 The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
  • Step 1 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask to give a mass of 27 Methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), 9 parts by mass of hydroxypropyl methacrylate (HPMA) and 0.4 mass A portion of benzoyl peroxide (BPO) was used as an initiator, and 0.1 part by mass of an initiator adjuvant BYK was mixed for use.
  • DEMA N-methyldiethanolamine
  • TSA triethylamine
  • E10 glycidyl tert-carbonate
  • the solvent in the flask was heated to 90 ° C, and the mixed solution was added dropwise thereto, and the dropwise addition was completed in about 2.5 hours.
  • the reaction temperature is 90 ° C, the reaction is continued for about 3 hours, and a slightly pale yellow transparent viscous liquid is obtained, and the temperature is lowered to about 60 ° C. 20 parts by mass of triethanolamine is added, stirring is continued for 0.5 hours, and 18 masses are added dropwise. A portion of water was added to the system to prepare an acrylic resin copolymer.
  • Step 2 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of ethyl acetate, and completely dissolved to form a solution A.
  • Step 3 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixture C, and 0.5 part by mass of a coupling agent was further added to obtain a mixed solution D.
  • Step 5 The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
  • Step 1 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), 9 parts by mass of hydroxypropyl methacrylate (HPMA), and 0.4 parts by mass of benzoyl peroxide (BPO) was used as an initiator, and 0.1 part by mass of an initiator adjuvant BYK was mixed for use.
  • DEMA N-methyldiethanolamine
  • TSA triethylamine
  • E10 glycidyl tert-carbonate
  • the solvent in the flask was heated to 90 ° C, and the mixed solution was added dropwise. After about 2.5 hours, the dropwise addition was completed, the temperature was maintained, and the reaction was continued for about 3 hours to obtain a transparent yellowish transparent viscous liquid, and the temperature was lowered to about 60 ° C.
  • the amine neutralizer was further stirred for 0.5 hours, and a predetermined amount of water was added dropwise to the system to obtain an acrylic resin copolymer.
  • Step 2 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 15 parts by mass of a diluent, and completely dissolved to form a solution A.
  • Step 3 0.6 part of fumed silica was dissolved in 45 parts by mass of ethyl acetate to completely dissolve to form solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixture C, and then 0.4 part by mass of a coupling agent was added to obtain a mixed solution D.
  • Step 5 The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
  • a method of preparing a film coated on a 3D printer table using the above-described paint is described below, and a 3D printer having such a film layer will be described.
  • the 3D printer of the present invention comprises a housing structure 1, a print head 2, and a table 3.
  • the print head 2 can be moved laterally or longitudinally in the plane in which the table 3 is located, and the table 3 can be moved in the direction of the plumb line by the action of the lifting mechanism.
  • the 3D printer adopts a layer-by-layer printing method to continuously adjust the positions of the print head 2 and the table 3, and the molten material extruded by the print head 2 such as ABS or PLA can form a three-dimensional object on the table 3.
  • the paint is obtained after performing steps S1 to S6 as shown in FIG. 1, and then step S7 is performed, and the paint obtained in step S6 is sprayed on the table 3 of the 3D printer.
  • the table 3 is usually a heat-conductive glass or aluminum plate, and the spraying process can be performed using an existing instrument dedicated to spraying or manually.
  • step S8 is subsequently performed to bake the paint sprayed on the table 3 to finally form a film layer 31 which can be applied to the 3D printer.
  • the thickness of the film layer 31 on the table 3 is any value. A preferred embodiment is that the film layer thickness is preferably between 50 micrometers and 80 micrometers.
  • the worktable 3 can be directly placed in the dry box, and the heating method of electric heating, infrared, microwave, etc. is adopted, the baking temperature is set to 150 ° C to 180 ° C, and the baking time is 60 to 90 minutes.
  • the cross section of the table 3 sequentially includes a heating layer 33, an aluminum plate layer 32, and a film layer 31.
  • the table 3 is heated and maintained at a constant temperature by the heating layer 33.
  • the constant temperature may vary depending on the nature of the material for different printed materials. For example, when printing with ABS material, the temperature is usually set to 110 ° C, and if PLA material is applied, the temperature should be raised to 70 ° C. The effect of heating the table 3 is to prevent warpage or deformation of the printed object.
  • the temperature of the molten material having a temperature of 220 ° C begins to decrease and is converted into a solid state, and a strong instantaneous adhesion is generated, thereby smoothly completing the printing process of the object. Due to the addition of fumed silica during the preparation of the coating of the present invention, the layers coated on the table 3 are loosely arranged, and a large cavity structure is formed between the molecules. After the printing process, the object is cooled to room temperature. The molecules in contact with the film layer 31 enter the hole structure without being fused with the film molecules or generating an intermolecular force, so the adhesion between the printed object and the film layer 31 becomes small, and the direct use is The object can be removed by hand.
  • Step 1 Use the product of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. as the acrylic resin copolymer.
  • Step 2 0.8 parts by mass of fumed silica was dissolved in 35 parts by mass of a diluent, and completely dissolved to form a solution A.
  • Step 3 25 parts by mass of the acrylic resin was dissolved in 30 parts by mass of a diluent, and completely dissolved to form a solution B.
  • Step 4 Solution A was added to Solution B, and 0.4 part by mass of a coupling agent was further added, and dispersed under a high speed disperser for 2 hours to obtain a coating.
  • Step 5 Spray the paint obtained in step 4 onto the workbench by spraying, and bake at 150 ° C for 90 minutes.
  • Step 1 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90. After ° C, 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), and 9 parts by mass of methacrylic acid were then added dropwise.
  • DEMA N-methyldiethanolamine
  • TSA triethylamine
  • E10 glycidyl tert-carbonate
  • a mixed solution of hydroxypropyl ester (HPMA) and 0.4 parts by mass of benzoyl peroxide (BPO) as an initiator and 0.1 part by mass of an initiator adjuvant BYK was added dropwise over about 2.5 hours. Maintain the temperature, continue to react for about 3 hours, and obtain a slightly pale yellow transparent viscous liquid, cool to about 60 ° C, add 17 parts by mass of triethanolamine, continue to stir for 0.5 hours, and add 15 parts by mass of water by dropping. Into the system, an acrylic resin copolymer was obtained.
  • Step 2 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of a diluent, and completely dissolved to form a solution A.
  • Step 3 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
  • Step 4 Solution A was added to Solution B to obtain a mixed solution C, and 0.4 part by mass of a coupling agent was further added thereto, and dispersed under a high speed dispersing machine for 1 hour to obtain a coating material.
  • Step 5 Spray the paint obtained in step 4 onto the workbench by spraying, and bake at 180 ° C for 60 minutes.
  • Step 1 25 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 20 parts by mass of butyl acetate, and completely dissolved to form a solution A.
  • Step 2 0.4 part of fumed silica was dissolved in 35 parts by mass of butyl acetate, and completely dissolved to form a solution B.
  • Step 3 Solution B was added to Solution A to obtain a mixed solution C, and 0.3 parts by mass of ⁇ -aminopropyltriethoxysilane was further added thereto, and dispersed under a high-speed dispersing machine for 2 hours to obtain a coating material.
  • Step 4 The coating obtained in the step: 3 is sprayed on a workbench by spraying, and baked at 170 ° C for 80 minutes.
  • the paint provided by the present invention can be used for coating on a workbench of a 3D printer, and the 3D printer coated with such paint can conveniently remove the printed object from the workbench after printing the finished object.
  • the present invention provides a method for preparing the above-mentioned coating material, which is simple in process and low in production cost by using the above method.

Abstract

A coating applied to a 3D printer workbench, prepared from the following constituents in parts by mass: 10-25 parts of an acrylic resin copolymer, 0.2-0.8 parts of a gas-phase silicon dioxide, 0.2-0.6 parts of a silane coupling agent and 25-65 parts of a diluent. The preparation method of the coating comprises: preparing a mixed solution of the acrylic resin copolymer, the gas-phase silicon dioxide and the diluent, adding the silane coupling agent to the mixed solution, and uniformly mixing the mixed solution to obtain the coating.

Description

一种3D打印机及其工作台膜层的制备方法、涂覆在3D打印机工作台的涂料及其制备方法  Method for preparing 3D printer and its worktable film layer, coating applied on 3D printer workbench and preparation method thereof 技术领域Technical field
本发明涉及一种涂料,具体涉及一种涂覆在3D打印机工作台的涂料以及这种涂料的制备方法、涂覆有这种涂料的3D打印机以及在3D打印机上涂覆这种涂料制成的膜的方法。本申请是基于申请日为2014年9月10日,申请号为201410459324.1的中国发明专利申请,该申请的内容引入本文作为参考。 The present invention relates to a coating, and more particularly to a coating applied to a 3D printer table, a method of preparing the coating, a 3D printer coated with the coating, and a coating of the coating on a 3D printer. Membrane method. The present application is based on a Chinese patent application filed on Sep. 10, 2014, the entire disclosure of which is incorporated herein by reference.
背景技术Background technique
3D打印技术为快速成型技术的一种,其常见的打印过程为:先通过计算机建模软件建模,再将建成的三维模型“分区”成逐层的截面,即切片,从而指导打印机逐层打印。3D printing technology is a kind of rapid prototyping technology. The common printing process is: firstly modeling by computer modeling software, and then “partitioning” the built 3D model into layer-by-layer sections, ie slices, to guide the printer layer by layer. print.
目前市场上的快速成型技术主要分为熔融层积成型技术(FDM)、三维印刷技术(3DP)、立体平版印刷技术(SLA)、选区激光烧结(SLS)、激光成型技术(DLP)和UV紫外线成型技术等。熔融挤压堆积成型技术(FDM)是 3D 打印技术中常用的一种技术工艺,原理是利用热塑性聚合物材料在熔融状态下,从喷头处挤压出来,凝固形成轮廓形状的薄层,再一层一层地叠加最终形成产品。目前市场上熔融挤压堆积成型技术较常用的聚合物材料是丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)、聚乳酸(PLA)、尼龙(PA)和聚碳酸酯(PC)。The rapid prototyping technologies currently on the market are mainly divided into melt layer forming technology (FDM), three-dimensional printing technology (3DP), stereolithography (SLA), selective laser sintering (SLS), laser forming technology (DLP) and UV ultraviolet light. Molding technology, etc. Melt extrusion stacking technology (FDM) is 3D A technical process commonly used in printing technology, the principle is that the thermoplastic polymer material is extruded from the nozzle in a molten state, solidified to form a thin layer of contour shape, and then layered to form a final product. The most commonly used polymer materials for melt extrusion coating technology on the market are acrylonitrile-butadiene-styrene terpolymer (ABS), polylactic acid (PLA), nylon (PA) and polycarbonate (PC). .
在3D打印机工作过程中,当约为220℃的熔融材料,如ABS或者PLA从喷头挤压到工作台上之后,熔融材料开始转化为固态,此时工作台与熔融材料的接触面会产生一个瞬时附着力,附着力必须足够大才能够保证打印过程的顺利进行,如果附着力偏小则不能完成成型过程。而在打印物体形成之后,在打印物体温度逐渐下降的过程中,附着力会相应下降,当打印物体温度至室温,附着力必须足够小,这样才能够保证打印物体易于从工作台取下。During the operation of the 3D printer, when a molten material of about 220 ° C, such as ABS or PLA, is extruded from the nozzle onto the table, the molten material begins to transform into a solid state, at which point the interface between the table and the molten material generates a transient. Adhesion, adhesion must be large enough to ensure smooth printing process, if the adhesion is too small, the molding process cannot be completed. After the printing object is formed, the adhesion will decrease correspondingly during the temperature drop of the printing object. When the temperature of the printing object reaches room temperature, the adhesion must be small enough to ensure that the printing object is easily removed from the table.
然而,3D打印过程中,如果直接将熔融材料打印在工作台上,打印出来的物体的分子将与工作台的分子互相渗透,导致打印的物体和工作台强烈地粘合在一起,难以取下打印完成的物体。现有技术中,3D打印机的工作台上通常会贴有一层贴纸,然而,打印材料如聚乳酸在高温熔融后会直接渗入贴纸的内部,与贴纸粘连,当打印物体冷却至室温后,由于打印物体与贴纸粘连在一起,因此不易取下。实际工作中需要用小铲将物体与贴纸分离,这样的操作势必容易破坏物体和贴纸,而每完成一件或数件打印物品后就需要对工作台的贴纸进行更换,而实际工作中更换贴纸的工艺繁琐,成本显著提高。However, in the 3D printing process, if the molten material is directly printed on the workbench, the molecules of the printed object will penetrate with the molecules of the workbench, causing the printed object and the workbench to be strongly bonded together, which is difficult to remove. Print the finished object. In the prior art, a 3D printer is usually provided with a layer of stickers on the workbench. However, the printed material such as polylactic acid directly penetrates into the interior of the sticker after being melted at a high temperature, and adheres to the sticker. When the printed object is cooled to room temperature, it is printed. Objects stick to the sticker and are therefore difficult to remove. In actual work, it is necessary to use a spatula to separate the object from the sticker. Such an operation is likely to damage the object and the sticker. After completing one or several pieces of printed items, the sticker of the workbench needs to be replaced, and the sticker is replaced in actual work. The process is cumbersome and the cost is significantly improved.
技术问题technical problem
本发明针对以上问题,主要提供一种涂覆在3D打印机工作台的涂料以及这种涂料的制备方法。The present invention is directed to the above problems, and mainly provides a coating applied to a 3D printer table and a method of preparing the coating.
此外,本发明还提供一种制备贴在3D打印机工作台膜层的方法以及由此形成的3D打印机。Further, the present invention provides a method of preparing a film layer attached to a 3D printer stage and a 3D printer formed thereby.
技术解决方案Technical solution
为了实现上述的主要目的,本发明提供的涂覆在3D打印机工作台的涂料由以下质量份的组分制备获得:In order to achieve the above main object, the coating provided on the 3D printer table provided by the present invention is prepared from the following parts by mass:
丙烯酸树脂共聚物 10至25质量份;Acrylic resin copolymer 10 to 25 parts by mass;
气相二氧化硅 0.2至0.8质量份;Fumed silica of 0.2 to 0.8 parts by mass;
硅烷偶联剂 0.2至0.6质量份;a silane coupling agent of 0.2 to 0.6 parts by mass;
稀释剂 25至65质量份。The diluent is 25 to 65 parts by mass.
一个优选的方案是,丙烯酸树脂共聚物至少包括以下单体中的一种:丙烯酸、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯、叔碳酸缩水甘油酯。In a preferred embodiment, the acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl acrylate, methacrylic acid, methyl Hydroxypropyl acrylate, glycidyl tert-carbonate.
本发明还提供一种涂覆在3D打印机工作台的涂料制备方法,该方法包括以下步骤:(1)制备混合液,混合液的质量份的组分为:丙烯酸树脂共聚物为10至25质量份;气相二氧化硅为0.2至0.8质量份;稀释剂为25至65质量份;(2)将0.2至0.6质量份的硅烷偶联剂加入步骤(1)混合液中,均匀混合后得到涂料。The invention also provides a coating preparation method coated on a 3D printer workbench, the method comprising the following steps: (1) preparing a mixed liquid, the mass fraction of the mixed liquid is: the acrylic resin copolymer is 10 to 25 mass Parts; fumed silica is 0.2 to 0.8 parts by mass; diluent is 25 to 65 parts by mass; (2) 0.2 to 0.6 parts by mass of a silane coupling agent is added to the mixed liquid of the step (1), and uniformly mixed to obtain a coating. .
优选地,步骤(1)的混合液的制备方法包括以下步骤:(a)将0.2至0.8质量份的气相二氧化硅溶于15至35质量份的稀释剂,完全溶解后形成溶液A;(b)将丙烯酸树脂共聚物10至25质量份溶于10至30质量份的稀释剂。完全溶解后形成溶液B;(c)将溶液A与溶液B混合,得到混合液。Preferably, the method for preparing the mixed liquid of the step (1) comprises the steps of: (a) dissolving 0.2 to 0.8 parts by mass of fumed silica in 15 to 35 parts by mass of a diluent, and completely dissolving to form a solution A; b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of a diluent. Solution B is formed after complete dissolution; (c) Solution A is mixed with Solution B to obtain a mixed solution.
本发明还提供一种3D打印机,包括工作台和涂覆在工作台上的膜层,其中,涂覆在工作台上的膜层由以下质量份的组分制备获得:丙烯酸树脂共聚物为10至25质量份;气相二氧化硅为0.2至0.8质量份;硅烷偶联为0.2至0.6质量份。The present invention also provides a 3D printer comprising a table and a film layer coated on the table, wherein the film layer coated on the table is prepared from the following parts by mass: acrylic copolymer is 10 To 25 parts by mass; fumed silica is 0.2 to 0.8 parts by mass; and silane coupling is 0.2 to 0.6 parts by mass.
本发明还提供一种制备涂覆在3D打印机工作台上膜层的方法,包括以下步骤:(1)制备混合液,混合液的质量份的组分为:丙烯酸树脂共聚物为10至25质量份;气相二氧化硅为0.2至0.8质量份;稀释剂为25至65质量份;(2)将0.2至0.6质量份的硅烷偶联剂加入步骤(1)混合液中,均匀混合后得到涂料。(3)将步骤(2)的涂料喷涂于工作台,150℃至180℃烘烤60至90分钟。The invention also provides a method for preparing a film layer coated on a 3D printer workbench, comprising the following steps: (1) preparing a mixed liquid, the mass fraction of the mixed liquid is: the acrylic resin copolymer is 10 to 25 mass Parts; fumed silica is 0.2 to 0.8 parts by mass; diluent is 25 to 65 parts by mass; (2) 0.2 to 0.6 parts by mass of a silane coupling agent is added to the mixed liquid of the step (1), and uniformly mixed to obtain a coating. . (3) Spray the coating of step (2) on a workbench and bake at 150 ° C to 180 ° C for 60 to 90 minutes.
优选地,步骤(1)的混合液的制备方法包括以下步骤:(a)将0.2至0.8质量份的气相二氧化硅溶于15至35质量份的稀释剂,完全溶解后形成溶液A;(b)将丙烯酸树脂共聚物10至25质量份溶于10至30质量份的稀释剂。完全溶解后形成溶液B;(c)将溶液A与溶液B混合,得到混合液。Preferably, the method for preparing the mixed liquid of the step (1) comprises the steps of: (a) dissolving 0.2 to 0.8 parts by mass of fumed silica in 15 to 35 parts by mass of a diluent, and completely dissolving to form a solution A; b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of a diluent. Solution B is formed after complete dissolution; (c) Solution A is mixed with Solution B to obtain a mixed solution.
有益效果Beneficial effect
本发明提供的涂覆在3D打印机工作台涂料制备方法具有步骤少、易操作、时间短等优点,能够实现规模化工业生产。此外,通过上述制备方法得到的涂料使用安全、环境友好、价格低廉。The coating preparation method provided by the invention in the 3D printer table has the advantages of fewer steps, easy operation, short time and the like, and can realize large-scale industrial production. In addition, the coating obtained by the above preparation method is safe, environmentally friendly, and inexpensive.
采用本发明的方法中步骤(1)所制得混合液的过程简便,易于操作,并且在实验过程中发现采用这种配制方法,溶质溶解过程迅速、分散均匀,缩短了混合液的配制时间,并且混合液中溶质的分散效果优于其它配制方法。The process of preparing the mixed liquid prepared by the step (1) in the method of the invention is simple and easy to operate, and it is found that the preparation method is adopted during the experiment, the dissolution process of the solute is rapid, the dispersion is uniform, and the preparation time of the mixed liquid is shortened. Moreover, the dispersion effect of the solute in the mixed solution is superior to other preparation methods.
本发明提供的3D打印机在工作台上有膜层,膜层的表面为多孔硅结构,下部为致密的耐高温丙烯酸树脂共聚物膜。该膜层具备了以下两个特点:一方面,当高温熔融材料与膜层接触后温度开始下降并会产生一个很强的瞬时附着力,从而顺利完成物体的打印过程,当打印过程结束后,物体冷却至室温,打印物体与膜层之间的附着力会变小,直接用手便可取下物体;另一方面,工作台上的膜层经过一次喷涂形成后,使用寿命长,避免了频繁更换工作台上膜的操作,打印效率提升,成本降低。The 3D printer provided by the invention has a film layer on the workbench, the surface of the film layer is a porous silicon structure, and the lower part is a dense high temperature resistant acrylic resin copolymer film. The film has the following two characteristics: on the one hand, when the high-temperature molten material contacts the film layer, the temperature begins to decrease and a strong instantaneous adhesion is generated, thereby smoothly completing the printing process of the object, when the printing process is finished, When the object is cooled to room temperature, the adhesion between the printed object and the film layer becomes smaller, and the object can be removed directly by hand; on the other hand, after the film layer on the worktable is formed by one spray, the service life is long and the frequent avoidance is avoided. The operation of replacing the film on the workbench improves the printing efficiency and reduces the cost.
附图说明DRAWINGS
图1是本发明制备3D打印机工作台上膜层的方法实施例的流程图。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram of an embodiment of a method of making a film layer on a 3D printer stage of the present invention.
图2是本发明3D打印机实施例的示意图。2 is a schematic diagram of an embodiment of a 3D printer of the present invention.
图3是本发明3D打印机实施例中工作台的剖视图。Figure 3 is a cross-sectional view of the stage in the embodiment of the 3D printer of the present invention.
本发明的实施方式Embodiments of the invention
本发明的涂料用于涂覆在3D打印机的工作台上,涂覆有这种涂料的3D打印机在打印完成物体后,可以方便地将打印完成的物体从工作台上取下。下面将详细介绍这种涂料、涂料的制备方法以及涂覆有这种涂料的3D打印机。The coating of the present invention is applied to a workbench of a 3D printer, and the 3D printer coated with such a paint can conveniently remove the printed object from the workbench after printing the finished object. The coating, the preparation method of the coating, and the 3D printer coated with the coating will be described in detail below.
涂覆在3D打印机工作台涂料的制备方法:Preparation method for coating on 3D printer table:
如图1所示,制备涂覆在3D打印机工作台的涂料时,首先执行步骤S1, 合成丙烯酸树脂共聚物。首先,在装有搅拌器、冷凝器、温度计和恒压滴液漏斗的四口烧瓶中加入溶剂,活性中间体叔碳酸缩水甘油酯,将丙烯酸单体混合备用,丙烯酸单体可以选取甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸(MAA)、基丙烯酸羟丙酯(HPMA)中的一种或多种,单体聚合的引发剂溶解在混合的丙烯酸单体中。然后,将烧瓶中溶剂升温至90℃后滴加丙烯酸混合单体,约2.5小时滴加完毕。保持温度恒定,继续反应3小时左右,制得略带浅黄色的透明黏稠液体。接着,降温至60℃左右,加入定量的胺中和剂10到20份,继续搅拌0.5小时,以滴加的方式将水加入体系中,制得丙烯酸树脂共聚物。As shown in FIG. 1, when preparing the coating applied to the 3D printer table, step S1 is first performed, Synthetic acrylic resin copolymer. First, a solvent is added to a four-necked flask equipped with a stirrer, a condenser, a thermometer, and a constant pressure dropping funnel, the active intermediate glycidyl carbonate is mixed, the acrylic monomer is mixed, and the acrylic monomer can be selected from methacrylic acid. One or more of methyl ester (MMA), butyl acrylate (BA), methacrylic acid (MAA), hydroxypropyl acrylate (HPMA), monomer polymerization initiator dissolved in mixed acrylic monomer . Then, the solvent in the flask was heated to 90 ° C, and then the acrylic mixed monomer was added dropwise, and the dropwise addition was completed in about 2.5 hours. The temperature was kept constant, and the reaction was continued for about 3 hours to obtain a slightly viscous, viscous liquid. Next, the temperature was lowered to about 60 ° C, a quantitative amount of the amine neutralizing agent was added to 10 to 20 parts, stirring was continued for 0.5 hours, and water was added dropwise to the system to obtain an acrylic resin copolymer.
优选地,在反应体系中可以加入异氰酸酯固化剂(GH),以提升丙烯酸单体的性能。更优选地,异氰酸酯固化剂的最佳加入量为总反应体系质量的0.8%,按此比例加入异氰酸酯,丙烯酸的粘接性和耐高温性能优异。Preferably, an isocyanate curing agent (GH) may be added to the reaction system to enhance the performance of the acrylic monomer. More preferably, the isocyanate curing agent is preferably added in an amount of 0.8% by mass of the total reaction system, and isocyanate is added in this proportion, and acrylic acid is excellent in adhesion and high temperature resistance.
可选地,丙烯酸树脂共聚物由东莞市新天地科技有限公司提供,产品型号为WZ510的产品。采用该公司提供的丙烯酸树脂共聚物符合本发明对于丙烯酸树脂共聚物的特殊要求,缩短了制备涂料的时间。Optionally, the acrylic resin copolymer is provided by Dongguan Xintiandi Technology Co., Ltd., and the product model is WZ510. The use of the acrylic resin copolymer provided by the company meets the special requirements of the present invention for the acrylic resin copolymer, and shortens the time for preparing the coating.
接着,执行步骤S2,将步骤S1得到的丙烯酸树脂共聚物溶解在稀释剂中配成溶液A。本实施例中所使用的稀释剂可以选择以下溶剂中的一种或者两种以上溶剂的混合溶剂:醋酸乙酯、醋酸戊酯、醋酸丁酯。执行步骤S1与步骤S2的同时,执行步骤S3,将气相二氧化硅溶解在稀释剂中配成溶液B。Next, step S2 is performed, and the acrylic resin copolymer obtained in step S1 is dissolved in a diluent to prepare a solution A. The diluent used in the present embodiment may be selected from one of the following solvents or a mixed solvent of two or more solvents: ethyl acetate, amyl acetate, and butyl acetate. Simultaneously with the execution of the step S1 and the step S2, the step S3 is performed, and the fumed silica is dissolved in the diluent to prepare the solution B.
执行步骤S1、S2与步骤S3后,执行步骤S4,将步骤S2得到的溶液A与步骤S3得到的溶液B混合得到混合液C,其混合过程可以将溶液A滴入溶液B,或者溶液B滴入溶液A。然后,执行步骤S5,将步骤S4中得到的混合液C与硅烷偶联剂混合得到混合液D。优选地,将硅烷偶联剂逐滴加入到混合液D中。硅烷偶联剂选取以下试剂中的一种或者两种以上试剂的混合物:β-(3,4-环氧环己基)乙基三乙氧基硅烷、γ-缩水甘油醚丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷。最后,执行步骤S6,将步骤S5得到的混合液D充分溶解、分散得到涂料。作为优选的技术方案,采用高速分散机对混合液D进行分散,分散时间为1至2小时。After performing steps S1, S2 and step S3, step S4 is performed, and the solution A obtained in step S2 is mixed with the solution B obtained in step S3 to obtain a mixed solution C, and the mixing process may drop the solution A into the solution B or the solution B. Into solution A. Then, step S5 is performed, and the mixed liquid C obtained in step S4 is mixed with a silane coupling agent to obtain a mixed liquid D. Preferably, a silane coupling agent is added dropwise to the mixture D. The silane coupling agent is one or a mixture of two or more of the following reagents: β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane , γ-aminopropyltriethoxysilane. Finally, in step S6, the mixed solution D obtained in the step S5 is sufficiently dissolved and dispersed to obtain a coating material. As a preferred technical solution, the mixed liquid D is dispersed by a high-speed disperser for a dispersion time of 1 to 2 hours.
下面通过多个实施例介绍涂覆在3D打印机工作台涂料的具体制备方法。The specific preparation method of the coating applied to the 3D printer table will be described below by way of various embodiments.
实施例1:Example 1:
步骤1:将40质量份的N-甲基二乙醇胺(DEMA)、10质量份的三乙胺(TEA)、7.1质量份的叔碳酸缩水甘油酯(E10)加入四口烧瓶中,升温至90℃后,开始滴加混合溶液,该混合溶液成份为:27质量份的甲基丙烯酸甲酯(MMA)、6质量份的丙烯酸丁酯(BA)、0.4份质量份的甲基丙烯酸(MAA)、9质量份的甲基丙烯酸羟丙酯(HPMA)和0.4质量份的过氧化苯甲酰(BPO)引发剂、0.1质量份的引发剂助剂BYK,使用2.5 小时的时间滴加混合单体。保持温度恒定,继续反应持续3 小时,制得略带浅黄色的透明黏稠液体,降温至60℃左右,加入10质量份的三乙醇胺,继续搅拌0.5小时,以滴加的方式将10质量份的水加入体系中,制得丙烯酸树脂共聚物。Step 1: 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90. After ° C, the mixed solution was started to be added dropwise, and the composition of the mixed solution was: 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), and 0.4 parts by mass of methacrylic acid (MAA). 9 parts by mass of hydroxypropyl methacrylate (HPMA) and 0.4 parts by mass of benzoyl peroxide (BPO) initiator, 0.1 parts by mass of initiator additive BYK, used 2.5 The mixed monomer was added dropwise over an hour. Keep the temperature constant and continue the reaction for 3 In an hour, a slightly light yellow transparent viscous liquid was prepared, and the temperature was lowered to about 60 ° C. 10 parts by mass of triethanolamine was added, stirring was continued for 0.5 hours, and 10 parts by mass of water was added dropwise to the system to obtain acrylic acid. Resin copolymer.
步骤2:将步骤1制得的丙烯酸树脂共聚物10质量份溶于10质量份的醋酸乙酯,完全溶解后形成溶液A。Step 2: 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of ethyl acetate, and completely dissolved to form a solution A.
步骤3:将0.2份的气相二氧化硅溶于15质量份的醋酸乙酯,完全溶解后形成溶液B。Step 3: 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.4质量份的偶联剂,得到混合液D。Step 4: Solution A was added to Solution B to obtain a mixture C, and then 0.4 part by mass of a coupling agent was added to obtain a mixed solution D.
步骤5:将混合液D在高速分散机下分散1小时得到涂料。Step 5: The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
实施例2:Example 2:
步骤1:使用由东莞市新天地科技有限公司生产的产品型号为WZ510的丙烯酸树脂共聚物10质量份溶于10质量份的醋酸戊酯,完全溶解后形成溶液A。Step 1: 10 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 10 parts by mass of amyl acetate, and completely dissolved to form a solution A.
步骤2:将0.4份的气相二氧化硅溶于15质量份的醋酸戊酯,完全溶解后形成溶液B。Step 2: 0.4 part of fumed silica was dissolved in 15 parts by mass of amyl acetate, and completely dissolved to form a solution B.
步骤3:将溶液A加入溶液B得到混合液C,再加入0.4质量份的γ-缩水甘油醚丙基三甲氧基硅烷,得到混合液D。Step 3: Solution A was added to Solution B to obtain a mixture C, and 0.4 parts by mass of γ-glycidyl ether propyltrimethoxysilane was further added to obtain a mixed solution D.
步骤4:将混合液D在高速分散机下分散1.5小时得到涂料。Step 4: The mixture D was dispersed under a high speed disperser for 1.5 hours to obtain a coating.
实施例3:Example 3:
步骤1:使用由东莞市新天地科技有限公司生产的产品型号为WZ510的丙烯酸树脂共聚物10质量份溶于10质量份的醋酸丁酯,完全溶解后形成溶液A。Step 1: 10 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 10 parts by mass of butyl acetate, and completely dissolved to form a solution A.
步骤2:将0.2份的气相二氧化硅溶于25质量份的醋酸丁酯,完全溶解后形成溶液B。Step 2: 0.2 part of fumed silica was dissolved in 25 parts by mass of butyl acetate, and completely dissolved to form a solution B.
步骤3:将溶液B加入溶液A得到混合液C,再加入0.2质量份的γ-氨丙基三乙氧基硅烷,得到混合液D。Step 3: Solution B was added to Solution A to obtain a mixture C, and 0.2 part by mass of γ-aminopropyltriethoxysilane was further added to obtain a mixed solution D.
步骤4:将混合液D在高速分散机下分散2小时得到涂料。Step 4: The mixture D was dispersed under a high speed disperser for 2 hours to obtain a coating.
实施例4:Example 4:
步骤1:在装有搅拌器、冷凝器、温度计和恒压滴液漏斗的四口烧瓶中加入100质量份N-甲基二乙醇胺(DEMA),2质量份的叔碳酸缩水甘油酯,再将100质量份的丙烯酸单体混合,丙烯酸单体可以选取甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸(MAA)、基丙烯酸羟丙酯(HPMA)中的一种或多种,1质量份的过氧化苯甲酰(BPO)引发剂溶解在混合的丙烯酸单体中。将烧瓶中溶剂升温至90℃后滴加丙烯酸混合单体,约2.5小时滴加完毕。保持温度恒定,继续反应3小时左右,制得略带浅黄色的透明黏稠液体。然后,降温至60℃左右,加入三乙醇胺20份,继续搅拌0.5小时,以滴加的方式将20份的水加入体系中,制得丙烯酸树脂共聚物。Step 1: In a four-necked flask equipped with a stirrer, a condenser, a thermometer, and a constant pressure dropping funnel, 100 parts by mass of N-methyldiethanolamine (DEMA), 2 parts by mass of glycidyl tert-carbonate, and then 100 parts by mass of acrylic monomer may be mixed, and the acrylic monomer may be one selected from methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and hydroxypropyl acrylate (HPMA). A plurality of parts by mass of a benzoyl peroxide (BPO) initiator are dissolved in the mixed acrylic monomer. The solvent in the flask was heated to 90 ° C, and the acrylic monomer was added dropwise, and the addition was completed in about 2.5 hours. The temperature was kept constant, and the reaction was continued for about 3 hours to obtain a slightly viscous, viscous liquid. Then, the temperature was lowered to about 60 ° C, 20 parts of triethanolamine was added, stirring was continued for 0.5 hour, and 20 parts of water was added dropwise to the system to obtain an acrylic resin copolymer.
步骤2:将步骤1制得的丙烯酸树脂共聚物15质量份溶于20质量份的醋酸丁酯,完全溶解后形成溶液A。Step 2: 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 20 parts by mass of butyl acetate, and completely dissolved to form a solution A.
步骤3:将0.5份的气相二氧化硅溶于25质量份的醋酸乙酯,完全溶解后形成溶液B。Step 3: 0.5 part of fumed silica was dissolved in 25 parts by mass of ethyl acetate to completely dissolve to form solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.6质量份的γ-氨丙基三乙氧基硅烷,得到混合液D。Step 4: Solution A was added to Solution B to obtain a mixture C, and 0.6 parts by mass of γ-aminopropyltriethoxysilane was further added to obtain a mixed solution D.
步骤5:将混合液D在高速分散机下分散1.2小时得到涂料。Step 5: The mixture D was dispersed under a high speed disperser for 1.2 hours to obtain a coating.
实施例5:Example 5:
步骤1:将40质量份的N-甲基二乙醇胺(DEMA)、10质量份的三乙胺(TEA)、7.1质量份的叔碳酸缩水甘油酯(E10)加入四口烧瓶中,升温至90℃,然后滴加混合溶液,混合溶液包括27质量份的丙烯酸(AA)、6质量份的丙烯酸丁酯(BA)、3质量份的丙烯酸2-乙基己酯(2-EHA)、0.4质量份的过氧化苯甲酰(BPO)作为引发剂、0.1质量份的引发剂助剂BYK和0.7质量份的异氰酸酯固化剂(GH),约2.5小时滴加完毕。保持温度,继续反应3小时左右,制得略带浅黄色的透明黏稠液体,降温至60℃左右,加入15质量份的三乙醇胺,继续搅拌0.5小时,以滴加的方式将15质量份的水加入体系中,制得丙烯酸树脂共聚物。Step 1: 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90. °C, then dropwise adding a mixed solution comprising 27 parts by mass of acrylic acid (AA), 6 parts by mass of butyl acrylate (BA), 3 parts by mass of 2-ethylhexyl acrylate (2-EHA), 0.4 mass The benzoyl peroxide (BPO) was used as an initiator, 0.1 part by mass of the initiator adjuvant BYK, and 0.7 part by mass of the isocyanate curing agent (GH), and the addition was completed in about 2.5 hours. Maintain the temperature, continue to react for about 3 hours, and obtain a slightly pale yellow transparent viscous liquid, cool down to about 60 ° C, add 15 parts by mass of triethanolamine, continue stirring for 0.5 hours, and add 15 parts by mass of water by dropping. Into the system, an acrylic resin copolymer was obtained.
步骤2:将步骤1得到的丙烯酸树脂共聚物15质量份溶于20质量份的醋酸戊酯,完全溶解后形成溶液A。Step 2: 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 20 parts by mass of amyl acetate, and completely dissolved to form a solution A.
步骤3:将0.5份的气相二氧化硅溶于25质量份的醋酸戊酯,完全溶解后形成溶液B。Step 3: 0.5 part of fumed silica was dissolved in 25 parts by mass of amyl acetate, and completely dissolved to form a solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.4质量份的β-(3,4-环氧环己基)乙基三乙氧基硅烷,得到混合液D。Step 4: Solution A was added to Solution B to obtain a mixture C, and 0.4 parts by mass of β-(3,4-epoxycyclohexyl)ethyltriethoxysilane was further added to obtain a mixed solution D.
步骤5:将混合液D在高速分散机下分散1小时得到涂料。Step 5: The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
实施例6:Example 6
步骤1:将40质量份的N-甲基二乙醇胺(DEMA)、10质量份的三乙胺(TEA)、7.1质量份的叔碳酸缩水甘油酯(E10)加入四口烧瓶中,将27质量份的甲基丙烯酸甲酯(MMA)、6质量份的丙烯酸丁酯(BA)、0.4份质量份的甲基丙烯酸(MAA)、9质量份的甲基丙烯酸羟丙酯(HPMA)和0.4质量份的过氧化苯甲酰(BPO)作为引发剂、0.1质量份的引发剂助剂BYK混合备用。将烧瓶中溶剂升温至90℃后滴加混合溶液,约2.5小时滴加完毕。反应温度为90℃,继续反应3小时左右,制得略带浅黄色的透明黏稠液体,降温至60℃左右,加入20质量份的三乙醇胺,继续搅拌0.5小时,以滴加的方式将18质量份的水加入体系中,制得丙烯酸树脂共聚物。Step 1: 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask to give a mass of 27 Methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), 9 parts by mass of hydroxypropyl methacrylate (HPMA) and 0.4 mass A portion of benzoyl peroxide (BPO) was used as an initiator, and 0.1 part by mass of an initiator adjuvant BYK was mixed for use. The solvent in the flask was heated to 90 ° C, and the mixed solution was added dropwise thereto, and the dropwise addition was completed in about 2.5 hours. The reaction temperature is 90 ° C, the reaction is continued for about 3 hours, and a slightly pale yellow transparent viscous liquid is obtained, and the temperature is lowered to about 60 ° C. 20 parts by mass of triethanolamine is added, stirring is continued for 0.5 hours, and 18 masses are added dropwise. A portion of water was added to the system to prepare an acrylic resin copolymer.
步骤2:将步骤1得到的丙烯酸树脂共聚物10质量份溶于10质量份的醋酸乙酯,完全溶解后形成溶液A。Step 2: 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of ethyl acetate, and completely dissolved to form a solution A.
步骤3:将0.2份的气相二氧化硅溶于15质量份的醋酸乙酯,完全溶解后形成溶液B。Step 3: 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.5质量份的偶联剂,得到混合液D。Step 4: Solution A was added to Solution B to obtain a mixture C, and 0.5 part by mass of a coupling agent was further added to obtain a mixed solution D.
步骤5:将混合液D在高速分散机下分散1小时得到涂料。Step 5: The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
实施例7:Example 7
步骤1:将40质量份的N-甲基二乙醇胺(DEMA)、10质量份的三乙胺(TEA)、7.1质量份的叔碳酸缩水甘油酯(E10)加入四口烧瓶中,将 27质量份的甲基丙烯酸甲酯(MMA)、6质量份的丙烯酸丁酯(BA)、0.4份质量份的甲基丙烯酸(MAA)、9质量份的甲基丙烯酸羟丙酯(HPMA)和0.4质量份的过氧化苯甲酰(BPO)作为引发剂、0.1质量份的引发剂助剂BYK混合备用。将烧瓶中溶剂升温至90℃后滴加混合溶液,约2.5小时滴加完毕,保持温度,继续反应3小时左右,制得略带浅黄色的透明黏稠液体,降温至60℃左右,加入定量的胺中和剂,继续搅拌0.5小时,以滴加的方式将定量的水加入体系中,制得丙烯酸树脂共聚物。Step 1: 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), 9 parts by mass of hydroxypropyl methacrylate (HPMA), and 0.4 parts by mass of benzoyl peroxide (BPO) was used as an initiator, and 0.1 part by mass of an initiator adjuvant BYK was mixed for use. The solvent in the flask was heated to 90 ° C, and the mixed solution was added dropwise. After about 2.5 hours, the dropwise addition was completed, the temperature was maintained, and the reaction was continued for about 3 hours to obtain a transparent yellowish transparent viscous liquid, and the temperature was lowered to about 60 ° C. The amine neutralizer was further stirred for 0.5 hours, and a predetermined amount of water was added dropwise to the system to obtain an acrylic resin copolymer.
步骤2:将步骤1制得的丙烯酸树脂共聚物15质量份溶于15质量份的稀释剂,完全溶解后形成溶液A。Step 2: 15 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 15 parts by mass of a diluent, and completely dissolved to form a solution A.
步骤3:将0.6份的气相二氧化硅溶于45质量份的醋酸乙酯,完全溶解后形成溶液B。Step 3: 0.6 part of fumed silica was dissolved in 45 parts by mass of ethyl acetate to completely dissolve to form solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.4质量份的偶联剂,得到混合液D。Step 4: Solution A was added to Solution B to obtain a mixture C, and then 0.4 part by mass of a coupling agent was added to obtain a mixed solution D.
步骤5:将混合液D在高速分散机下分散1小时得到涂料。Step 5: The mixture D was dispersed under a high speed disperser for 1 hour to obtain a coating.
下面介绍应用上述的涂料制备涂覆在3D打印机工作台上膜层的方法,并介绍具有这种膜层的3D打印机。A method of preparing a film coated on a 3D printer table using the above-described paint is described below, and a 3D printer having such a film layer will be described.
如图2所示,本发明的3D打印机包括外壳结构1、打印头2、工作台3。打印头2可以在工作台3所在的平面内横向或者纵向移动,在升降机构的作用下工作台3可以沿铅垂线方向移动。3D打印机采用逐层打印的方式,不断调节打印头2与工作台3的位置,打印头2挤压出来的熔融材料如ABS或者PLA便可以在工作台3上形成三维物体。As shown in FIG. 2, the 3D printer of the present invention comprises a housing structure 1, a print head 2, and a table 3. The print head 2 can be moved laterally or longitudinally in the plane in which the table 3 is located, and the table 3 can be moved in the direction of the plumb line by the action of the lifting mechanism. The 3D printer adopts a layer-by-layer printing method to continuously adjust the positions of the print head 2 and the table 3, and the molten material extruded by the print head 2 such as ABS or PLA can form a three-dimensional object on the table 3.
制备涂覆在3D打印机工作台3的膜层时,执行如图1所示的步骤S1至S6后获得涂料,然后执行步骤S7,将步骤S6得到的涂料喷涂在3D打印机的工作台3上。现有技术中工作台3通常为导热的玻璃或铝板,喷涂过程可以使用现有的专用于喷涂的仪器或者人工完成。When the film layer coated on the 3D printer table 3 is prepared, the paint is obtained after performing steps S1 to S6 as shown in FIG. 1, and then step S7 is performed, and the paint obtained in step S6 is sprayed on the table 3 of the 3D printer. In the prior art, the table 3 is usually a heat-conductive glass or aluminum plate, and the spraying process can be performed using an existing instrument dedicated to spraying or manually.
如图1和图3所示,执行步骤S7后,接着执行步骤S8,对喷涂在工作台3上的涂料进行烘烤,最终形成能够应用于3D打印机的膜层31。工作台3上的膜层31厚度为任意值,优选的技术方案是,膜层厚度优选50微米到80微米之间。烘烤过程可以将工作台3直接放入干燥箱内,采取电加热、红外、微波等加热方式,烘烤温度设定为150℃至180℃,烘烤时间持续60到90分钟。As shown in FIGS. 1 and 3, after step S7 is performed, step S8 is subsequently performed to bake the paint sprayed on the table 3 to finally form a film layer 31 which can be applied to the 3D printer. The thickness of the film layer 31 on the table 3 is any value. A preferred embodiment is that the film layer thickness is preferably between 50 micrometers and 80 micrometers. In the baking process, the worktable 3 can be directly placed in the dry box, and the heating method of electric heating, infrared, microwave, etc. is adopted, the baking temperature is set to 150 ° C to 180 ° C, and the baking time is 60 to 90 minutes.
如图3所示,工作台3的截面依次包括加热层33、铝板层32和膜层31。在3D打印过程中,工作台3会在加热层33的作用下升温并保持在一个恒定温度,对于不同的打印材料,上述恒定温度会根据材料的性质有所不同。例如,采用ABS材料打印的时候,该温度通常设定为110℃,而如果应用PLA材料,则应该将温度升至70℃。对工作台3进行加热的作用在于防止打印物体出现翘曲或者变形。当温度为220℃的熔融材料与膜层31接触后,熔融材料温度开始下降而转化为固态并会产生一个很强的瞬时附着力,从而顺利完成物体的打印过程。由于本发明的涂料制备过程中添加气相二氧化硅,涂覆在工作台3的膜层分子之间排列疏松,分子间会形成较大的空穴结构,在打印过程结束后,物体冷却至室温,物体与膜层31接触的分子会进入到空穴结构中,而不与膜层分子发生融合或者产生分子间作用力,因此打印物体与膜层31之间的附着力会变小,直接用手便可取下物体。As shown in FIG. 3, the cross section of the table 3 sequentially includes a heating layer 33, an aluminum plate layer 32, and a film layer 31. During the 3D printing process, the table 3 is heated and maintained at a constant temperature by the heating layer 33. The constant temperature may vary depending on the nature of the material for different printed materials. For example, when printing with ABS material, the temperature is usually set to 110 ° C, and if PLA material is applied, the temperature should be raised to 70 ° C. The effect of heating the table 3 is to prevent warpage or deformation of the printed object. When the molten material having a temperature of 220 ° C is in contact with the film layer 31, the temperature of the molten material begins to decrease and is converted into a solid state, and a strong instantaneous adhesion is generated, thereby smoothly completing the printing process of the object. Due to the addition of fumed silica during the preparation of the coating of the present invention, the layers coated on the table 3 are loosely arranged, and a large cavity structure is formed between the molecules. After the printing process, the object is cooled to room temperature. The molecules in contact with the film layer 31 enter the hole structure without being fused with the film molecules or generating an intermolecular force, so the adhesion between the printed object and the film layer 31 becomes small, and the direct use is The object can be removed by hand.
下面介绍在3D打印机上制备膜层的方法。The method of preparing a film layer on a 3D printer will be described below.
实施例8:Example 8
步骤1:使用由东莞市新天地科技有限公司生产的产品型号为WZ510的产品作为丙烯酸树脂共聚物。Step 1: Use the product of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. as the acrylic resin copolymer.
步骤2:将0.8质量份的气相二氧化硅溶于35质量份的稀释剂,完全溶解后形成溶液A。Step 2: 0.8 parts by mass of fumed silica was dissolved in 35 parts by mass of a diluent, and completely dissolved to form a solution A.
步骤3:将丙烯酸树脂25质量份溶于30质量份的稀释剂,完全溶解后形成溶液B。Step 3: 25 parts by mass of the acrylic resin was dissolved in 30 parts by mass of a diluent, and completely dissolved to form a solution B.
步骤4:将溶液A加入溶液B,再加入0.4质量份的偶联剂,在高速分散机下分散2小时得到涂料。Step 4: Solution A was added to Solution B, and 0.4 part by mass of a coupling agent was further added, and dispersed under a high speed disperser for 2 hours to obtain a coating.
步骤5:将步骤4得到的涂料通过喷涂方式喷涂于工作台上,150℃烘烤90分钟。Step 5: Spray the paint obtained in step 4 onto the workbench by spraying, and bake at 150 ° C for 90 minutes.
实施例9:Example 9
步骤1;将40质量份的N-甲基二乙醇胺(DEMA)、10质量份的三乙胺(TEA)、7.1质量份的叔碳酸缩水甘油酯(E10)加入四口烧瓶中,升温至90℃后,然后滴加由27质量份的甲基丙烯酸甲酯(MMA)、6质量份的丙烯酸丁酯(BA)、0.4份质量份的甲基丙烯酸(MAA)、9质量份的甲基丙烯酸羟丙酯(HPMA)和0.4质量份的过氧化苯甲酰(BPO)作为引发剂、0.1质量份的引发剂助剂BYK组成的混合溶液,约2.5小时滴加完毕。保持温度,继续反应3小时左右,制得略带浅黄色的透明黏稠液体,降温至60℃左右,加入17质量份的三乙醇胺,继续搅拌0.5小时,以滴加的方式将15质量份的水加入体系中,制得丙烯酸树脂共聚物。Step 1; 40 parts by mass of N-methyldiethanolamine (DEMA), 10 parts by mass of triethylamine (TEA), and 7.1 parts by mass of glycidyl tert-carbonate (E10) were placed in a four-necked flask, and the temperature was raised to 90. After ° C, 27 parts by mass of methyl methacrylate (MMA), 6 parts by mass of butyl acrylate (BA), 0.4 parts by mass of methacrylic acid (MAA), and 9 parts by mass of methacrylic acid were then added dropwise. A mixed solution of hydroxypropyl ester (HPMA) and 0.4 parts by mass of benzoyl peroxide (BPO) as an initiator and 0.1 part by mass of an initiator adjuvant BYK was added dropwise over about 2.5 hours. Maintain the temperature, continue to react for about 3 hours, and obtain a slightly pale yellow transparent viscous liquid, cool to about 60 ° C, add 17 parts by mass of triethanolamine, continue to stir for 0.5 hours, and add 15 parts by mass of water by dropping. Into the system, an acrylic resin copolymer was obtained.
步骤2:将步骤1得到的丙烯酸树脂共聚物10质量份溶于10质量份的稀释剂,完全溶解后形成溶液A。Step 2: 10 parts by mass of the acrylic resin copolymer obtained in the step 1 was dissolved in 10 parts by mass of a diluent, and completely dissolved to form a solution A.
步骤3:将0.2份的气相二氧化硅溶于15质量份的醋酸乙酯,完全溶解后形成溶液B。Step 3: 0.2 part of fumed silica was dissolved in 15 parts by mass of ethyl acetate to completely dissolve to form solution B.
步骤4:将溶液A加入溶液B得到混合液C,再加入0.4质量份的偶联剂,高速分散机下分散1小时得到涂料。Step 4: Solution A was added to Solution B to obtain a mixed solution C, and 0.4 part by mass of a coupling agent was further added thereto, and dispersed under a high speed dispersing machine for 1 hour to obtain a coating material.
步骤5:将步骤4得到的涂料通过喷涂方式喷涂于工作台上,180℃烘烤60分钟。Step 5: Spray the paint obtained in step 4 onto the workbench by spraying, and bake at 180 ° C for 60 minutes.
实施例10:Example 10:
步骤1:使用东莞市新天地科技有限公司生产的产品型号为WZ510的丙烯酸树脂共聚物25质量份溶于20质量份的醋酸丁酯,完全溶解后形成溶液A。Step 1: 25 parts by mass of an acrylic resin copolymer of the product type WZ510 produced by Dongguan Xintiandi Technology Co., Ltd. was dissolved in 20 parts by mass of butyl acetate, and completely dissolved to form a solution A.
步骤2:将0.4份的气相二氧化硅溶于35质量份的醋酸丁酯,完全溶解后形成溶液B。Step 2: 0.4 part of fumed silica was dissolved in 35 parts by mass of butyl acetate, and completely dissolved to form a solution B.
步骤3:将溶液B加入溶液A得到混合液C,再加入0.3质量份的γ-氨丙基三乙氧基硅烷,高速分散机下分散2小时得到涂料。Step 3: Solution B was added to Solution A to obtain a mixed solution C, and 0.3 parts by mass of γ-aminopropyltriethoxysilane was further added thereto, and dispersed under a high-speed dispersing machine for 2 hours to obtain a coating material.
步骤4:将步骤:3得到的涂料通过喷涂方式喷涂于工作台上,170℃烘烤80分钟。Step 4: The coating obtained in the step: 3 is sprayed on a workbench by spraying, and baked at 170 ° C for 80 minutes.
工业实用性Industrial applicability
本发明提供的涂料可用于涂覆在3D打印机的工作台上,涂覆有这种涂料的3D打印机在打印完成物体后,可以方便地将打印完成的物体从工作台上取下。另外,本发明提供上述涂料的制备方法,使用上述方法制备上述涂料工艺简单,并且生产成本低。 The paint provided by the present invention can be used for coating on a workbench of a 3D printer, and the 3D printer coated with such paint can conveniently remove the printed object from the workbench after printing the finished object. In addition, the present invention provides a method for preparing the above-mentioned coating material, which is simple in process and low in production cost by using the above method.

Claims (10)

  1. 一种涂覆在3D打印机工作台的涂料,其特征在于:由以下质量份的组分制备获得: A coating applied to a 3D printer table, characterized in that it is prepared from the following parts by mass:
    丙烯酸树脂共聚物 10至25质量份;Acrylic resin copolymer 10 to 25 parts by mass;
    气相二氧化硅 0.2至0.8质量份;Fumed silica of 0.2 to 0.8 parts by mass;
    硅烷偶联剂 0.2至0.6质量份;a silane coupling agent of 0.2 to 0.6 parts by mass;
    稀释剂 25至65质量份。The diluent is 25 to 65 parts by mass.
  2. 根据权利要求1所述的涂料,其特征在于:所述丙烯酸树脂共聚物至少包括以下单体中的一种:丙烯酸、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯、叔碳酸缩水甘油酯。The coating material according to claim 1, wherein said acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid. Butyl ester, methacrylic acid, hydroxypropyl methacrylate, glycidyl tert-carbonate.
  3. 一种涂覆在3D打印机工作台涂料的制备方法,其特征在于包括以下步骤:A method of preparing a coating applied to a 3D printer table, comprising the steps of:
    (1)制备混合液,所述混合液的质量份的组分为:(1) preparing a mixed liquid, the components of the mass fraction of which are:
    丙烯酸树脂共聚物 10至25质量份;Acrylic resin copolymer 10 to 25 parts by mass;
    气相二氧化硅 0.2至0.8质量份;Fumed silica of 0.2 to 0.8 parts by mass;
    稀释剂 25至65质量份;Thinner 25 to 65 parts by mass;
    (2)将0.2至0.6质量份的硅烷偶联剂加入步骤(1)所述混合液中,均匀混合后得到涂料。(2) 0.2 to 0.6 parts by mass of a silane coupling agent is added to the mixed liquid of the step (1), and uniformly mixed to obtain a coating.
  4. 根据权利要求3所述的方法,其特征在于:所述丙烯酸树脂共聚物至少包括以下单体中的一种:丙烯酸、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯、叔碳酸缩水甘油酯。 The method according to claim 3, wherein said acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid. Butyl ester, methacrylic acid, hydroxypropyl methacrylate, glycidyl tert-carbonate.
  5. 根据权利要求3所述的方法,其特征在于:所述步骤(1)的所述混合液的制备方法包括以下步骤:The method according to claim 3, wherein the method for preparing the mixed liquid of the step (1) comprises the steps of:
    (a)将0.2至0.8质量份的气相二氧化硅溶于15至35质量份的稀释剂,完全溶解后形成溶液A;(a) 0.2 to 0.8 parts by mass of fumed silica is dissolved in 15 to 35 parts by mass of a diluent, completely dissolved to form a solution A;
    (b)将丙烯酸树脂共聚物10至25质量份溶于10至30质量份的稀释剂,完全溶解后形成溶液B;(b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of the diluent, completely dissolved to form a solution B;
    (c)将所述溶液A与所述溶液B混合,得到所述混合液。(c) mixing the solution A with the solution B to obtain the mixed solution.
  6. 一种3D打印机,包括工作台,所述工作台上涂覆有膜层,其特征在于:所述膜层由以下质量份的组分制备获得:A 3D printer comprising a table coated with a film layer, characterized in that the film layer is prepared from the following parts by mass:
    丙烯酸树脂共聚物 10至25质量份;Acrylic resin copolymer 10 to 25 parts by mass;
    气相二氧化硅 0.2至0.8质量份;Fumed silica of 0.2 to 0.8 parts by mass;
    硅烷偶联剂 0.2至0.6质量份。The silane coupling agent is 0.2 to 0.6 parts by mass.
  7. 根据权利要求6所述的打印机,其特征在于:所述丙烯酸树脂共聚物至少包括以下单体中的一种:丙烯酸、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯、叔碳酸缩水甘油酯。 The printer according to claim 6, wherein said acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid. Butyl ester, methacrylic acid, hydroxypropyl methacrylate, glycidyl tert-carbonate.
  8. 一种制备涂覆在3D打印机工作台上膜的方法,其特征在于包括以下步骤:A method of preparing a film coated on a 3D printer stage, comprising the steps of:
    (1)制备混合液,所述混合液的质量份的组分为:(1) preparing a mixed liquid, the components of the mass fraction of which are:
    丙烯酸树脂共聚物 10至25质量份;Acrylic resin copolymer 10 to 25 parts by mass;
    气相二氧化硅 0.2至0.8质量份;Fumed silica of 0.2 to 0.8 parts by mass;
    稀释剂 25至65质量份;Thinner 25 to 65 parts by mass;
    (2)将0.2至0.6质量份的硅烷偶联剂加入步骤(1)所述混合液中,均匀混合后得到涂料;(2) adding 0.2 to 0.6 parts by mass of a silane coupling agent to the mixed liquid of the step (1), and uniformly mixing to obtain a coating;
    (3)将步骤(2)的所述涂料喷涂于工作台,在150℃至180℃温度下烘烤60至90分钟。(3) The coating of the step (2) is sprayed on a workbench and baked at a temperature of 150 ° C to 180 ° C for 60 to 90 minutes.
  9. 根据权利要求8所述的方法,其特征在于:所述丙烯酸树脂共聚物至少包括以下单体中的一种:丙烯酸、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸羟丙酯、叔碳酸缩水甘油酯。 The method according to claim 8, wherein said acrylic resin copolymer comprises at least one of the following monomers: acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid. Butyl ester, methacrylic acid, hydroxypropyl methacrylate, glycidyl tert-carbonate.
  10. 根据权利要求8所述的方法,其特征在于所述步骤(1)的所述混合液的制备方法包括以下步骤:The method according to claim 8, wherein the method for preparing the mixed liquid of the step (1) comprises the steps of:
    (a)将0.2至0.8质量份的气相二氧化硅溶于15至35质量份的稀释剂,完全溶解后形成溶液A;(a) 0.2 to 0.8 parts by mass of fumed silica is dissolved in 15 to 35 parts by mass of a diluent, completely dissolved to form a solution A;
    (b)将丙烯酸树脂共聚物10至25质量份溶于10至30质量份的稀释剂,完全溶解后形成溶液B;(b) 10 to 25 parts by mass of the acrylic resin copolymer is dissolved in 10 to 30 parts by mass of the diluent, completely dissolved to form a solution B;
    (c)将所述溶液A与所述溶液B混合,得到所述混合液。(c) mixing the solution A with the solution B to obtain the mixed solution.
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