Summary of the invention
The present invention is directed to above problem to provide and be a kind ofly coated in the coating of 3D printer worktable and the preparation method of this coating; In addition present invention also offers and a kind ofly prepare the method being attached to 3D printer worktable rete and the 3D printer formed thus.
Be coated in a coating for 3D printer worktable, it is characterized in that being prepared by the component of following mass parts:
Acrylic resin copolymer 10 to 25 mass parts;
Aerosil 0.2 to 0.8 mass parts;
Silane coupling agent 0.2 to 0.6 mass parts;
Thinner 25 to 65 mass parts.
Be further characterized in that: acrylic resin multipolymer at least comprises the one in following monomer: vinylformic acid, butyl acrylate, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, Rocryl 410, tertiary carbonic acid glycidyl ester.
Present invention also offers a kind of preparation method for coating being coated in 3D printer worktable, it is characterized in that comprising the following steps: (1) prepares mixed solution, the component of the mass parts of mixed solution is: acrylic resin multipolymer is 10 to 25 mass parts; Aerosil is 0.2 to 0.8 mass parts; Thinner is 25 to 65 mass parts; (2) silane coupling agent of 0.2 to 0.6 mass parts is added in step (1) mixed solution, after Homogeneous phase mixing, obtain coating.
The 3D of being coated in printer worktable preparation method for coating provided by the invention has the advantages such as process is few, easy to operate, the time is short, can realize large-scale industrial and produce.In addition, the coating use safety obtained by above-mentioned preparation method, environmental friendliness, cheap.
Be further characterized in that: acrylic resin multipolymer at least comprises the one in following monomer: vinylformic acid, butyl acrylate, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, Rocryl 410, tertiary carbonic acid glycidyl ester.
Further be characterised in that the preparation method of the mixed solution of step (1) comprises the following steps: the aerosil of 0.2 to 0.8 mass parts is dissolved in the thinner of 15 to 35 mass parts by (a), after dissolving completely, form solution A; B acrylic resin copolymer 10 to 25 mass parts is dissolved in the thinner of 10 to 30 mass parts by ().Solution B is formed after dissolving completely; C solution A mixes with solution B by (), obtain mixed solution.
The process that employing above-mentioned steps obtains mixed solution is easy, easy handling, and find to adopt this compound method in experimentation, solute dissolves process rapidly, be uniformly dispersed, shorten the preparation time of mixed solution, and in mixed solution, the dispersion effect of solute is better than other compound method.
Present invention also offers a kind of 3D printer, comprise worktable and coating rete on the table, it is characterized in that, coating rete is on the table prepared by the component of following mass parts: acrylic resin multipolymer is 10 to 25 mass parts; 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, has rete on the table, and the surface of rete is Porous Silicon structures, and bottom is fine and close high temperature resistant acrylic resin co-polymer membrane.This rete has possessed following two features, after hot melt materials contacts with rete, temperature starts to decline and can produce a very strong instantaneous sticking power, thus complete the print procedure of object smoothly, after print procedure terminates, object is cooled to room temperature, sticking power between printing objects and rete can diminish, and directly just can take off object with hand.Rete on worktable is after once spraying formation, and long service life, avoid the frequent operation changing film on worktable, printing effect promotes, and cost reduces.
Be further characterized in that: acrylic resin multipolymer at least comprises the one in following monomer: vinylformic acid, butyl acrylate, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, Rocryl 410, tertiary carbonic acid glycidyl ester.
Present invention also offers and a kind ofly prepare the method being coated in rete on 3D printer worktable, it is characterized in that comprising the following steps: (1) prepares mixed solution, the component of the mass parts of mixed solution is: acrylic resin multipolymer is 10 to 25 mass parts; Aerosil is 0.2 to 0.8 mass parts; Thinner is 25 to 65 mass parts; (2) silane coupling agent of 0.2 to 0.6 mass parts is added in step (1) mixed solution, after Homogeneous phase mixing, obtain coating.(3) by the paint spay-coating of step (2) in worktable, 150 DEG C to 180 DEG C baking 60 to 90 minutes.
Be further characterized in that: acrylic resin multipolymer at least comprises the one in following monomer: vinylformic acid, butyl acrylate, 2-EHA, methyl methacrylate, butyl acrylate, methacrylic acid, Rocryl 410, tertiary carbonic acid glycidyl ester.
Further be characterised in that the preparation method of the mixed solution of step (1) comprises the following steps: the aerosil of 0.2 to 0.8 mass parts is dissolved in the thinner of 15 to 35 mass parts by (a), after dissolving completely, form solution A; B acrylic resin copolymer 10 to 25 mass parts is dissolved in the thinner of 10 to 30 mass parts by ().Solution B is formed after dissolving completely; C solution A mixes with solution B by (), obtain mixed solution.
Embodiment
Coating of the present invention, for being coated in the worktable of 3D printer, being coated with the 3D printer of this coating after printing completes object, can being taken off from worktable by the object printed easily.
Be coated in the preparation method of 3D printer worktable coating:
As shown in Figure 1, when preparation is coated in the coating of 3D printer worktable, first perform step S1, acrylic acid synthesizing resin copolymer.Solvent is added in the four-hole boiling flask that agitator, condenser, thermometer and constant pressure funnel are housed, active intermediate tertiary carbonic acid glycidyl ester, by Acrylic Acid Monomer mixing for standby use, Acrylic Acid Monomer can choose in methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), base Propylene glycol monoacrylate (HPMA) one or more, the initiator of monomer polymerization is dissolved in the Acrylic Acid Monomer of mixing.Drip vinylformic acid mix monomer after solvent in flask is warming up to 90 DEG C, within about 2.5 hours, dropwise.Keep homo(io)thermism, continue reaction 3 hours, obtained slightly lurid transparent thick liquid.Then, be cooled to about 60 DEG C, add quantitative amine neutralizing agent 10 to 20 parts, continue stirring 0.5 hour, in the mode dripped, water is added in system, obtained acrylic resin multipolymer.The scheme of further optimization is, can add isocyanate curing agent (GH) in reaction system, to promote the performance of Acrylic Acid Monomer.The scheme further optimized is, the optimal addn of isocyanate curing agent is 0.8% of total reaction system quality, adds isocyanic ester in this ratio, acrylic acid cementability and resistance to elevated temperatures excellence.
As the preferred scheme of another one, acrylic resin multipolymer is provided by Dongguan City new world Science and Technology Ltd., and product type is the product of WZ510.The acrylic resin multipolymer adopting the said firm to provide meets the particular requirement of the present invention for acrylic resin multipolymer, shortens the time of preparing coating.
Then, perform step S2, the acrylic resin multipolymer obtained by step S1 is dissolved in wiring solution-forming A in thinner.The thinner used in the present embodiment can select the mixed solvent of a kind of or two or more solvent in following solvent: vinyl acetic monomer, amyl acetate-n, N-BUTYL ACETATE.While performing step S1 and step S2, perform step S3, aerosil is dissolved in wiring solution-forming B in thinner.
After performing step S1, S2 and step S3, perform step S4, the solution B that the solution A obtained by step S2 and step S3 obtain is mixed to get mixed solution C, and solution A can be instilled solution B by its mixing process, or solution B instillation solution A.Then, perform step S5, the mixed solution C obtained in step S4 and silane coupling agent are mixed to get mixed solution D, and preferred scheme is dropwise joined in mixed solution D by silane coupling agent.Silane coupling agent chooses the mixture of a kind of or two or more reagent in following reagent: β-(3,4-epoxycyclohexyl) ethyl triethoxysilane, γ-glycidyl ether propyl trimethoxy silicane, γ-aminopropyl triethoxysilane.Finally, perform step S6, the mixed solution D obtained by step S5 fully dissolves, disperses to obtain coating.As preferred technical scheme, adopt high speed dispersor to disperse mixed solution D, jitter time is 1 to 2 hour.
The concrete preparation method of 3D printer worktable coating is coated in below by multiple embodiment introduction.
Embodiment 1:
Step 1: by the N methyldiethanol amine (DEMA) of 40 mass parts, the triethylamine (TEA) of 10 mass parts, the tertiary carbonic acid glycidyl ester (E10) of 7.1 mass parts adds in four-hole boiling flask, after being warming up to 90 DEG C, start to drip mixing solutions, this mixing solutions composition is: the methyl methacrylate (MMA) of 27 mass parts, the butyl acrylate (BA) of 6 mass parts, the methacrylic acid (MAA) of 0.4 part of mass parts, the Rocryl 410 (HPMA) of 9 mass parts and benzoyl peroxide (BPO) initiator of 0.4 mass parts, the initiator auxiliary agent B YK of 0.1 mass parts, the time of 2.5 hours is used to drip mix monomer.Keep homo(io)thermism, continue reaction and continue 3 hours, obtained slightly lurid transparent thick liquid, be cooled to about 60 DEG C, add the trolamine of 10 mass parts, continue stirring 0.5 hour, in the mode dripped, the water of 10 mass parts is added in system, obtained acrylic resin multipolymer.
Step 2: vinyl acetic monomer acrylic resin copolymer 10 mass parts that step 1 is obtained being dissolved in 10 mass parts, forms solution A after dissolving completely.
Step 3: the vinyl acetic monomer aerosil of 0.2 part being dissolved in 15 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B and obtain mixed solution C, then add the coupling agent of 0.4 mass parts, obtain mixed solution D.
Step 5: mixed solution D is disperseed under high speed dispersor obtain coating in 1 hour.
Embodiment 2:
Step 1: use the product type produced by Dongguan City new world Science and Technology Ltd. to be the amyl acetate-n that acrylic resin copolymer 10 mass parts of WZ510 is dissolved in 10 mass parts, form solution A after dissolving completely.
Step 2: the amyl acetate-n aerosil of 0.4 part being dissolved in 15 mass parts, forms solution B after dissolving completely.
Step 3: solution A is added solution B and obtain mixed solution C, then the γ-glycidyl ether propyl trimethoxy silicane adding 0.4 mass parts, obtain mixed solution D.
Step 4: mixed solution D is disperseed under high speed dispersor obtain coating in 1.5 hours.
Embodiment 3:
Step 1: use the product type produced by Dongguan City new world Science and Technology Ltd. to be the N-BUTYL ACETATE that acrylic resin copolymer 10 mass parts of WZ510 is dissolved in 10 mass parts, form solution A after dissolving completely.
Step 2: the N-BUTYL ACETATE aerosil of 0.2 part being dissolved in 25 mass parts, forms solution B after dissolving completely.
Step 3: solution B is added solution A and obtain mixed solution C, then add the γ-aminopropyl triethoxysilane of 0.2 mass parts, obtain mixed solution D.
Step 4: mixed solution D is disperseed under high speed dispersor obtain coating in 2 hours.
Embodiment 4:
Step 1: add 100 mass parts N methyldiethanol amines (DEMA) in the four-hole boiling flask that agitator, condenser, thermometer and constant pressure funnel are housed, the tertiary carbonic acid glycidyl ester of 2 mass parts, again the Acrylic Acid Monomer of 100 mass parts is mixed, Acrylic Acid Monomer can choose in methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), base Propylene glycol monoacrylate (HPMA) one or more, benzoyl peroxide (BPO) initiator of 1 mass parts is dissolved in the Acrylic Acid Monomer of mixing.Drip vinylformic acid mix monomer after solvent in flask is warming up to 90 DEG C, within about 2.5 hours, dropwise.Keep homo(io)thermism, continue reaction 3 hours, obtained slightly lurid transparent thick liquid.Then, be cooled to about 60 DEG C, add trolamine 20 parts, continue stirring 0.5 hour, in the mode dripped, the water of 20 parts is added in system, obtained acrylic resin multipolymer.
Step 2: N-BUTYL ACETATE acrylic resin copolymer 15 mass parts that step 1 is obtained being dissolved in 20 mass parts, forms solution A after dissolving completely.
Step 3: the vinyl acetic monomer aerosil of 0.5 part being dissolved in 25 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B and obtain mixed solution C, then add the γ-aminopropyl triethoxysilane of 0.6 mass parts, obtain mixed solution D.
Step 5: mixed solution D is disperseed under high speed dispersor obtain coating in 1.2 hours.
Embodiment 5:
Step 1: by the N methyldiethanol amine (DEMA) of 40 mass parts, the triethylamine (TEA) of 10 mass parts, the tertiary carbonic acid glycidyl ester (E10) of 7.1 mass parts adds in four-hole boiling flask, be warming up to 90 DEG C, then mixing solutions is dripped, mixing solutions comprises the vinylformic acid (AA) of 27 mass parts, the butyl acrylate (BA) of 6 mass parts, the 2-EHA (2-EHA) of 3 mass parts, the benzoyl peroxide (BPO) of 0.4 mass parts is as initiator, the initiator auxiliary agent B YK of 0.1 mass parts and the isocyanate curing agent (GH) of 0.7 mass parts, within about 2.5 hours, dropwise.Keep temperature, continue reaction 3 hours, obtained slightly lurid transparent thick liquid, be cooled to about 60 DEG C, add the trolamine of 15 mass parts, continue stirring 0.5 hour, in the mode dripped, the water of 15 mass parts is added in system, obtained acrylic resin multipolymer.
Step 2: acrylic resin copolymer 15 mass parts step 1 obtained is dissolved in the amyl acetate-n of 20 mass parts, forms solution A after dissolving completely.
Step 3: the amyl acetate-n aerosil of 0.5 part being dissolved in 25 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B and obtain mixed solution C, then β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane adding 0.4 mass parts, obtain mixed solution D.
Step 5: mixed solution D is disperseed under high speed dispersor obtain coating in 1 hour.
Embodiment 6:
Step 1: add in four-hole boiling flask by the triethylamine (TEA) of the N methyldiethanol amine (DEMA) of 40 mass parts, 10 mass parts, the tertiary carbonic acid glycidyl ester (E10) of 7.1 mass parts, using the initiator auxiliary agent B YK mixing for standby use of the benzoyl peroxide (BPO) of the methacrylic acid (MAA) of the methyl methacrylate (MMA) of 27 mass parts, the butyl acrylate (BA) of 6 mass parts, 0.4 part of mass parts, the Rocryl 410 (HPMA) of 9 mass parts and 0.4 mass parts as initiator, 0.1 mass parts.Drip mixing solutions after solvent in flask is warming up to 90 DEG C, within about 2.5 hours, dropwise.Temperature of reaction is 90 DEG C, continues reaction 3 hours, obtained slightly lurid transparent thick liquid, be cooled to about 60 DEG C, add the trolamine of 20 mass parts, continue stirring 0.5 hour, in the mode dripped, the water of 18 mass parts is added in system, obtained acrylic resin multipolymer.
Step 2: acrylic resin copolymer 10 mass parts step 1 obtained is dissolved in the vinyl acetic monomer of 10 mass parts, forms solution A after dissolving completely.
Step 3: the vinyl acetic monomer aerosil of 0.2 part being dissolved in 15 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B and obtain mixed solution C, then add the coupling agent of 0.5 mass parts, obtain mixed solution D.
Step 5: mixed solution D is disperseed under high speed dispersor obtain coating in 1 hour.
Embodiment 7:
Step 1: add in four-hole boiling flask by the triethylamine (TEA) of the N methyldiethanol amine (DEMA) of 40 mass parts, 10 mass parts, the tertiary carbonic acid glycidyl ester (E10) of 7.1 mass parts, using the initiator auxiliary agent B YK mixing for standby use of the benzoyl peroxide (BPO) of the methacrylic acid (MAA) of the methyl methacrylate (MMA) of 27 mass parts, the butyl acrylate (BA) of 6 mass parts, 0.4 part of mass parts, the Rocryl 410 (HPMA) of 9 mass parts and 0.4 mass parts as initiator, 0.1 mass parts.Mixing solutions is dripped after solvent in flask is warming up to 90 DEG C, within about 2.5 hours, dropwise, keep temperature, continue reaction 3 hours, obtained slightly lurid transparent thick liquid, is cooled to about 60 DEG C, add quantitative amine neutralizing agent, continue stirring 0.5 hour, in the mode dripped, quantitative water is added in system, obtained acrylic resin multipolymer.
Step 2: thinner acrylic resin copolymer 15 mass parts that step 1 is obtained being dissolved in 15 mass parts.Solution A is formed after dissolving completely.
The aerosil of 0.6 part is dissolved in the vinyl acetic monomer of 45 mass parts by step 3., forms solution B after dissolving completely.
Solution A is added solution B and obtains mixed solution C by step 4., then adds the coupling agent of 0.4 mass parts, obtains mixed solution D.
Mixed solution D disperses to obtain coating in 1 hour by step 5. under high speed dispersor.
Introduce the method that the above-mentioned coating preparation of application is coated in rete on 3D printer worktable below, and introduce the 3D printer with this rete.
As shown in Figure 2,3D printer of the present invention comprises containment structure 1, printhead 2, worktable 3.Printhead 2 can in the plane at worktable 3 place transverse direction or vertically move, can move along plummet direction at the effect lower table 3 of hoisting appliance.3D printer adopts the mode successively printed, and constantly regulate the position of printhead 2 and worktable 3, the melting material that printhead 2 squeezes out such as ABS or PLA just can form three-dimensional body on worktable 3.
When preparation is coated in the rete of 3D printer worktable 3, obtain coating after performing step S1 to S6 as shown in Figure 1, then perform step S7, the paint spay-coating obtained by step S6 is on the worktable 3 of 3D printer.In prior art, worktable 3 is generally glass or the aluminium sheet of heat conduction, and spraying process can use and is existingly exclusively used in the instrument of spraying or manually completes.
As shown in figures 1 and 3, after performing step S7, then perform step S8, toast the coating be sprayed on worktable 3, final formation can be applied to the rete 31 of 3D printer.Rete 31 thickness on worktable 3 is arbitrary value, and preferred technical scheme is, preferred 50um to the 80um of thicknesses of layers.Worktable 3 directly can be put into loft drier by bake process, and take the type of heating such as electrically heated, infrared, microwave, storing temperature is set as 150 DEG C to 180 DEG C, and baking time continues 60 to 90 minutes.
As shown in Figure 3, the cross section of worktable 3 comprises zone of heating 33, aluminum layer 32 and rete 31 successively.In 3D print procedure, worktable 3 can heat up and remain on a steady temperature under the effect of zone of heating 33, and for different printed materials, above-mentioned steady temperature can be different according to the character of material.Such as, adopt ABS material print time, this temperature is set as 110 DEG C usually, and if application PLA material, then temperature should be risen to 70 DEG C.Be to prevent printing objects from occurring warpage or distortion to the effect that worktable 3 heats.After the temperature melting material that is 220 DEG C contacts with rete 31, melting material temperature starts to decline and is converted into solid-state and can produces a very strong instantaneous sticking power, thus completes the print procedure of object smoothly.Owing to adding aerosil in dope preparing process of the present invention, between the rete molecule being coated in worktable 3, arrangement is loose, intermolecularly can form larger void structure, after print procedure terminates, object is cooled to room temperature, object contact with rete 31 molecule can enter into void structure, and there is not to merge or produce Intermolecular Forces with rete molecule, therefore the sticking power between printing objects and rete 31 can diminish, and directly just can take off object with hand.
Introduce the method preparing rete on 3D printer below.
Embodiment 8:
Step 1: use the product type produced by Dongguan City new world Science and Technology Ltd. to be that the product of WZ510 is as acrylic resin multipolymer.
Step 2: the thinner aerosil of 0.8 mass parts being dissolved in 35 mass parts, forms solution A after dissolving completely.
Step 3: thinner acrylic resin 25 mass parts being dissolved in 30 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B, then the coupling agent adding 0.4 mass parts, under high speed dispersor, dispersion obtains coating in 2 hours.
Step 5: coating step 4 obtained is sprayed on worktable by spraying method, 150 DEG C are toasted 90 minutes.
Embodiment 9:
Step 1, by the N methyldiethanol amine (DEMA) of 40 mass parts, the triethylamine (TEA) of 10 mass parts, the tertiary carbonic acid glycidyl ester (E10) of 7.1 mass parts adds in four-hole boiling flask, after being warming up to 90 DEG C, then drip by the methyl methacrylate of 27 mass parts (MMA), the butyl acrylate (BA) of 6 mass parts, the methacrylic acid (MAA) of 0.4 part of mass parts, the Rocryl 410 (HPMA) of 9 mass parts and the benzoyl peroxide (BPO) of 0.4 mass parts are as initiator, the mixing solutions of the initiator auxiliary agent B YK composition of 0.1 mass parts, within about 2.5 hours, dropwise.Keep temperature, continue reaction 3 hours, obtained slightly lurid transparent thick liquid, be cooled to about 60 DEG C, add the trolamine of 17 mass parts, continue stirring 0.5 hour, in the mode dripped, the water of 15 mass parts is added in system, obtained acrylic resin multipolymer.
Step 2: acrylic resin copolymer 10 mass parts step 1 obtained is dissolved in the thinner of 10 mass parts, forms solution A after dissolving completely.
Step 3: the vinyl acetic monomer aerosil of 0.2 part being dissolved in 15 mass parts, forms solution B after dissolving completely.
Step 4: solution A is added solution B and obtain mixed solution C, then add the coupling agent of 0.4 mass parts, under high speed dispersor, dispersion obtains coating in 1 hour.
Step 5: coating step 4 obtained is sprayed on worktable by spraying method, 180 DEG C are toasted 60 minutes.
Embodiment 10:
Step 1: acrylic resin multipolymer 25 mass parts that the product type using Dongguan City new world Science and Technology Ltd. to produce is WZ510 is dissolved in the N-BUTYL ACETATE of 20 mass parts, forms solution A after dissolving completely.
Step 2: the N-BUTYL ACETATE aerosil of 0.4 part being dissolved in 35 mass parts, forms solution B after dissolving completely.
Step 3: solution B is added solution A and obtain mixed solution C, then add the γ-aminopropyl triethoxysilane of 0.3 mass parts, under high speed dispersor, dispersion obtains coating in 2 hours.
Step 4: by step: 3 coating obtained are sprayed on worktable by spraying method, 170 DEG C are toasted 80 minutes.