CN109517440A - 3 D-printing material and its preparation method and application - Google Patents

3 D-printing material and its preparation method and application Download PDF

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Publication number
CN109517440A
CN109517440A CN201811435377.4A CN201811435377A CN109517440A CN 109517440 A CN109517440 A CN 109517440A CN 201811435377 A CN201811435377 A CN 201811435377A CN 109517440 A CN109517440 A CN 109517440A
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China
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parts
monomer
photoinitiator
printing
printing material
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王卉
黄蓓青
魏先福
张婉
马乐
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Beijing Hande Image Equipment Co ltd
Beijing Institute of Graphic Communication
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Beijing Institute of Graphic Communication
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)

Abstract

The present invention provides a kind of 3 D-printing materials and its preparation method and application.3 D-printing material includes 15-25 parts of mill base, 40-75 parts of free radical monomer, free based prepolymers 2-4 parts, 8-12 parts of free radical photo-initiation, 4-8 parts of cationic monomer, 0.2-3 parts of cationic prepolymer polymers, 0.5-2 parts of cationic initiator, 1-4 parts of reactive amines, 0.2-2 parts of levelling agent.Preparation method: pigment is uniformly added in monomer and dispersant afterwards, stirs pre-dispersed and then grinding and obtains mill base；Each raw material is mixed evenly, 3 D-printing material is obtained by filtration.The application of 3 D-printing material carries out 3 D-printing for UV-LED inkjet printing technology.Using 3 D-printing material provided by the present application, surface tension and modest viscosity, cubical contraction are small, curing rate is fast, color density is high, good dispersion.

Description

3 D-printing material and its preparation method and application
Technical field
The present invention relates to 3D printing fields, in particular to a kind of 3 D-printing material and its preparation method and application.
Background technique
3 D-printing is as a kind of increases material manufacturing technology, and growth momentum is swift and violent in recent years.Wherein, true color 3 D-printing skill Art is one kind based on three-dimensional modeling data and color data, can be while 3 D-printing moulding, and true reappearance is three-dimensional The important technology of target object color has extensive in fields such as artistic notion, decoration, historical relic's protection, education, advertisements Application value and development space.
In various color three dimension printing techniques, UV-LED inkjet printing technology is that by real color three dimension printing One of effective means.The principle of UV-LED inkjet printing technology is the photocuring reaction caused based on ultraviolet radiation, is had The 3 D-printing material of light sensitivity forms drop through spray head, is injected in behind substrate or primer surface under the action of uv light Film-forming is layering to form 3D solid by layer-by-layer printing.Colored UV-LED ink-jet 3 D-printing material It is mainly made of colouring component and light-cured components, the curing molding by way of ultraviolet radiation, without heating, without using Organic solvent or drier containing metallic element, therefore UV-LED inkjet printing technology is a kind of green, environmental protection, energy-efficient beats Print and molding mode.
Suitable for the color three dimension printed material of UV-LED inkjet printing, it is necessary to meet following condition: (1) higher solidification Speed；(2) there is surface tension appropriate；(3) lower viscosity；(4) material has smaller before and after photocuring reaction occurs Volume change, so that it is guaranteed that Forming Quality；(5) good dispersibility and particle diameter distribution appropriate, to guarantee material energy It is enough successfully to be sprayed from spray head；Otherwise unfavorable to Forming Quality, and there is the risk of blocking spray head；(6) there is good color Color characteristic makes the product of printing shaping color density with higher.
Patent CN107304318A discloses a kind of 3D ink composition for ink-jet printing, ink group and preparation method thereof, The defect of the technology is: monomer, prepolymer and initiator are all based on free radical polymerization system, often generate biggish body Product shrinking percentage；Patent CN106700729A discloses formula and its preparation side of a kind of ink-jet 3D printing material of automatic equating The defect of method, the technology is: monomer, prepolymer and initiator are all based on free radical polymerization system, often generate larger Cubical contraction；In addition, adding of colorants is difficult to obtain higher color density when being not higher than 5%.Patent CN107109091A disclose it is a kind of for the printing ink composition of 3D printing, 3D printer and the method for controlling it, the technology Defect is: (1) monomer, prepolymer and initiator are all based on radical photopolymerization system, often generate biggish volume Shrinking percentage；(2) organic solvent has been used, volatile organic matter (VOCs) discharge can be generated during making and using, is unfavorable for Environmental protection and personnel health；(3) inorganic particle modified by surface is contained in formula, modification procedure is cumbersome, high-content Inorganic particle the viscosity and rheological behaviour of ink are had an impact, and then influence jetting performance, furthermore particle be easy blocking spray Head.105949881 A of patent CN discloses a kind of 3D printing UV cured printing ink, and the defect of the technology is: (1) needing to make Standby drying oil alkyd resin modified polyurethane acrylic resin, preparation process is cumbersome, and has used Mono-n-butyltin, two fourths The organic tins compound conduct such as base tin oxide, dibutyl tin dilaurate, dibutyl tin acetate or monobutyl-tin-trichloride Esterification catalyst, to environmental and human health impacts, there are larger harm；(2) photocuring system is radical photopolymerization system, often Biggish cubical contraction can be generated, Forming Quality is reduced.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of 3 D-printing material, surface tension and modest viscosity, volume contraction Rate is small, curing rate is fast, color density is high, good dispersion.
The second object of the present invention is to provide a kind of preparation method of 3 D-printing material, and this method simple process is green Colour circle is protected.
The third object of the present invention is to provide a kind of application of 3 D-printing material, applied to UV-LED inkjet printing skill Art carries out 3 D-printing.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of 3 D-printing material, based on parts by weight, comprising: 15-25 parts of mill base, 40-75 parts of free radical monomer, freely 2-4 parts of based prepolymers, 8-12 parts of free radical photo-initiation, 4-8 parts of cationic monomer, 0.2-3 parts of cationic prepolymer polymers, cation 0.5-2 parts of initiator, 1-4 parts of reactive amines, 0.2-2 parts of levelling agent；
The mill base, based on parts by weight, comprising: 15-24 parts of pigment, 45-75 parts of monomer, 4-10 parts of dispersing agent.
Mill base, free radical monomer, free based prepolymers, free radical photo-initiation, cationic monomer, cationic prepolymer polymers, The use of cationic initiator, reactive amines, levelling agent can well solve caused by single polymers, monomer, initiator The problem of surface tension and viscosity are improper, cubical contraction is big, curing rate is slow, color density is low, bad dispersibility.Using certainly By base/cationic hybrid Photopolymer System, the advantage for having cubical contraction small compared to simple radical photopolymerization system； The advantage for having curing rate fast compared to simple cationic photopolymerization system.
3 D-printing material provided by the present application, being includes that free radical polymerization system and cationic polymerization system mix light Curing system；Free radical polymerization system includes free radical photo-initiation, free radical monomer, free based prepolymers and reactive amines；Sun Ionic polymerization system includes cation light initiator, cationic monomer and cationic prepolymer polymers.Free radical polymerization system and sun from There is more significant impact, best weights to the printing of 3 D-printing material and processability index for the ratio of subparadigm system Amount ratio is 9:1.
Preferably, the pigment is selected from one of quinacridone magenta, bronze red, paratonere G, paratonere 171 or more Kind；The monomer is one of the single functionality containing active polymerisable carbon-to-carbon double bond or bifunctionality monomer or a variety of, excellent Select ethoxyethoxy ethyl acrylate, 1,6- hexanediyl ester, tripropylene glycol diacrylate, neopentyl glycol dipropyl Olefin(e) acid ester, dipropylene glycol diacrylate, acryloyl morpholine；The dispersing agent is selected from BYK9077, BYK9151 or BYK9150.
In order to obtain the preferable magenta 3 D-printing material of performance, pigment carries out preferred.Monomer and pigment, dispersing agent Cooperation, can prepare the mill base of good dispersion, even particle size distribution, this is to obtain the color three dimension printing material haveing excellent performance The basis of material.
Preferably, the free radical monomer is the single functionality containing active polymerisable carbon-to-carbon double bond or bifunctionality list One of body is a variety of, preferably ethoxyethoxy ethyl acrylate, 1,6- hexanediyl ester, tripropylene glycol dipropyl Olefin(e) acid ester, neopentylglycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine.
It is further preferred that the free based prepolymers are one in the unsaturated oligomers containing polymerizable carbon-carbon's double bond Kind is a variety of, preferably epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic resin, polyoxyalkylene acrylate resin, third Acrylic resin, vinylite or the hyperbranched oligomer of olefin(e) acid esterification, the preferred hyper-branched polyester of hyperbranched oligomer Acrylate V400, hyperbranched polyester acrylic ester V100, aliphatic polyurethane Eudragit E B270, polyester acrylic tree Rouge EB870, hyperbranched polyester acrylic ester EB150；The cationic prepolymer polymers is in the oligomer for can be carried out cationic polymerization One or more, preferred epoxy, vinyl ether resin.
It is further preferred that the free radical photo-initiation is that cracking type free radical photo-initiation or hydrogen-abstraction are light-initiated Bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of agent, preferably phenyl, thio-phenyl-to oxygen azo-cycle acetone, photoinitiator 2773, Photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, One of photoinitiator 389, photoinitiator 1508, isopropyl thioxanthone, 2,4- diethyl thioxanthene -9- ketone are a variety of； The cationic initiator is initiator PAG-2.
It is further preferable that the cationic monomer is in the compound that ring-opening polymerisation occurs under radical cation effect One or more, preferably 3,4- epoxycyclohexyl-methyl methacrylate, 3,4- epoxycyclohexyl-methyl 3,4- epoxide ring Hexyl formic acid esters, 3- Oxyranyle 7- oxabicyclo [4.1.0] heptane, bis- ((3,4- epoxycyclohexyl) methyl) adipic acids Bis- [3- ethyl] oxetanes of ester, 3- ethyl -3- hydroxymethyl-oxetane, 3,3- [oxygroup dimethylene].
Free radical monomer, free based prepolymers, cationic prepolymer polymers, free radical photo-initiation, cationic initiator, sun from Sub- monomer preferably ensure that 3 D-printing material can obtain better performance.
It is further preferred that the levelling agent is TEGO 410 or TEGO 432；The reactive amines are 2- phenyl benzyl -2- Dimethyl amine -1- (4- morpholine benzyl phenyl) butanone.
The use of levelling agent and reactive amines, so that 3 D-printing material has better surface tension and viscosity, while excellent Change the cooperation between each component.In addition, reactive amines and hydrogen-abstraction free radical photo-initiation are used cooperatively and can be improved curing rate, The influence of oxygen inhibition is reduced, solidification effect is improved.
A kind of preparation method of the 3 D-printing material, comprising the following steps:
By the monomer and the dispersant it is uniform after, be added the pigment, stir it is pre-dispersed obtains it is pre-dispersed mixed Object is closed, then grinds, obtains the mill base；
By the mill base, the free radical monomer, the free based prepolymers, the free radical photo-initiation, the sun Ion monomer, the cationic prepolymer polymers, the cationic initiator, the reactive amines, levelling agent mixing, stirring are equal It is even, the 3 D-printing material is obtained by filtration.
This method is simple, and organotin catalysts and any organic solvent, tool are not used in 3 D-printing material preparation process There is environmentally protective advantage.Firstly the need of pinkish red mill base of the preparation based on pigment, prepared using the mill base as colorant component color Color 3 D-printing material can be realized higher color density compared with selection dyestuff is as the prior art of colorant.Mill base with Granules of pigments or micelle by the modified preparation in surface are compared, and can be obtained lesser particle diameter distribution, are not easy to plug spray head.Mill base Preparation process can be realized using the raw material of commercialization by physical grinding, the preparation process of 3 D-printing material uses quotient The raw material of product can be realized by simple electromagnetic agitation or mechanical stirring, does not need cumbersome chemical modification and synthesized Journey has advantage easy to operate.
Preferably, the stirring pre-dispersed time is 30-60min, and the time of the grinding is 90-180min；It carries out Before the grinding, pick pearl is added in the pre-dispersed mixture, the additional amount of the pick pearl is the pre-dispersed mixture 3-5 times of total volume.
Control stirring, the parameter of grinding, addition pick pearl are ground, and the more excellent product of size distribution can be obtained.
A kind of application of the 3 D-printing material, carries out 3 D-printing for UV-LED inkjet printing technology.
Compared with prior art, the invention has the benefit that
(1) surface tension and modest viscosity of 3 D-printing material, cubical contraction is small, curing rate is fast, color density is high, Good dispersion；
(2) preparation method is simple, easy to operate, environmentally protective；
(3) 3 D-printing material is applied to 3 D-printing, functional, can obtain good 3 D-printing product.
Specific embodiment
The condition met is needed to be illustrated the color three dimension printed material for being suitable for UV-LED inkjet printing first:
(1) higher curing rate.After droplets of materials sprays, instantaneously solidify under the radiation of UV-LED light source, to send out Raw liquid forms 3D solid to solid transformation by way of being layering；If the curing rate of material is insufficient, material Phenomena such as flowing during molding, the accuracy of manufacture of product is seriously affected, or even cause product that can not form.
(2) there is surface tension appropriate.Excessive surface tension will lead to material and flow directly out, too low surface tension Will cause spray head can not spray, and block spray head, be unable to reach eject request.Suitable surface tension can guarantee 3 D-printing material Material has enough power to spray from nozzle, forms the uniform drop of volume and drop and substrate can be made to be formed when contacting suitably Contact angle, generally between 20-22mN/m.
(3) lower viscosity.If the viscosity of material is excessively high, will lead to spray head material can not normally spray, and can seriously go out Now blocking spray head causes printing device to damage；If material viscosity is too low, it will lead to material and directly flowed out from spray head, is unable to control The discharge of material, the printing shaping precision of badly damaged printed material.Therefore viscosity range about 10mPa.s-25mPa.s it Between (temperature be 25 degrees Celsius when).
(4) 3 D-printing material has lesser volume change before and after photocuring reaction occurs, so that it is guaranteed that molding Quality.Photo-curing material is when crosslinking solidification, material is transformed into solid film layer by liquid molecule, between liquid molecule Since the operating distance of Van der Waals force is greater than the covalent bond effect distance of solid-state molecular, so photo-curing material becomes from liquid Certain volume contraction effect can be generated when solid-state.Volume contraction, which occurs, for photo-curing material will cause forming part size generation mistake Difference, or even buckling deformation occurs, so the low photo-curing material system of selection shrinking percentage in the formulation design, for reducing material Cure shrinkage effect and improve forming part formed precision have very important meaning.
(5) good dispersibility and particle diameter distribution appropriate, to guarantee that material can successfully be sprayed from spray head；It is no It is then unfavorable to Forming Quality, and there is the risk of blocking spray head.
(6) there is good chromatic characteristic, make the product of printing shaping color density with higher.
Based on this cognition, the application provides a kind of 3 D-printing material and its preparation method and application.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
In order to clearly express the scheme of the application, the source of embodiment agents useful for same is presented below:
Free radical monomer: ethoxyethoxy ethyl acrylate EOEOEA, 1,6 hexanediol diacrylate HDDA, 3 third Omega-diol diacrylate TPGDA, neopentylglycol diacrylate NPGDA, dipropylene glycol diacrylate DPGDA, acryloyl Quinoline ACMO etc. is purchased from Tianjin proud son of heaven radiation curing material Co., Ltd；
Free based prepolymers: hyperbranched polyester acrylic ester EB150, V400, V100, aliphatic polyurethane acrylic resin EB270, polyester acrylate resin EB870 etc. are purchased from Zhan Xin resin (Shanghai) Co., Ltd.；
Free radical photo-initiation: bis- (2,4,6- trimethylbenzoyl) phosphine oxides (819) of phenyl, thio-phenyl-are to oxygen Azo-cycle acetone (907), photoinitiator 2773, photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, photoinitiator 389, photoinitiator 1508 etc. are purchased from the long day new material stock in Tianjin Part Co., Ltd；Isopropyl thioxanthone (ITX), 2,4- diethyl thioxanthene -9- ketone (DETX) are sent out purchased from Beijing English power science and technology Open up Co., Ltd；
Cationic initiator: (5- tolysulfonyl oxygen imines -5H- thiophene -2- subunit)-(4- methoxyphenyl)-acetonitrile (PAG-2) it is purchased from Hubei Gu Run Science and Technology Co., Ltd.；Other cationic initiators that can be used, in wavelength 385- Principle is absorbed as at 395nm；
Cationic monomer: 3,4- epoxycyclohexyl-methyl methacrylate (TTA-15), 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters (TTA-21), 3- Oxyranyle 7- oxabicyclo [4.1.0] heptane (TTA-22), it is bis- ((3, 4- epoxycyclohexyl) methyl) adipate ester (TTA-26) be purchased from Jiangsu Tai Teer chemical industry, 3- ethyl -3- methylol oxa- ring fourth Alkane (OXT-1), bis- [3- ethyl] oxetanes (OXT-3) of 3,3- [oxygroup dimethylene] have purchased from Hubei Gu Run science and technology share Limit company；
Levelling agent TEGO410,432 are purchased from Degussa TEGO；
Reactive amines 2- phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl phenyl) butanone (EHA) is sent out purchased from Beijing English power science and technology Open up Co., Ltd.
Embodiment 1
(1) preparation of mill base
Take RTS18 parts of magenta pigment quinacridone magenta Magenta, monomeric acrylic ethoxy ethoxyethyl acrylate (EOEOEA) 72 parts and dispersant B YK9150 10 parts.
Firstly, being uniformly mixed after monomer and dispersant using constant temperature blender with magnetic force.Then, it is added thereto Magenta pigment, pre-dispersed 30 minutes using mechanical agitator.Finally, pre-dispersed good pre-dispersed mixture is placed in grinder In, and the pick pearl of 4 times of pre-dispersed mixture total volume is added, high speed grinding 180 minutes, pinkish red mill base can be obtained.
(2) preparation of 3 D-printing material
20 parts of pinkish red mill base, 21.48 parts of dipropylene glycol diacrylate (DPGDA), acryloyl morpholine (ACMO) 19.77 Part, 13.83 parts of ethoxyethoxy ethyl acrylate (EOEOEA), 3- Oxyranyle 7- oxabicyclo [4.1.0] heptane (TTA-22) 6.68 parts, aliphatic polyurethane Eudragit E B270 takes 1.44 parts, hyperbranched polyester acrylic ester V400 takes 1.44 parts, epoxy resin E44 take 0.32 part, photoinitiator 2777 take 3.02 parts, photoinitiator 2671 take 5.04 parts, photoinitiator 898 take 2.02 parts, initiator PAG-2 take 0.96 part, reactive amines 2- phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl phenyl) fourth Ketone (EHA) take 3.60 parts, levelling agent TEGO432 take 0.4 part.
Above-mentioned raw materials are mixed, is placed on mechanical agitator and stirs 30 minutes to uniform, three-dimensional beat can be obtained after filtering Print material.
Embodiment 2
(1) preparation of mill base
Take 15 parts of magenta pigment bronze red (PR21), monomer 1,6- hexanediyl ester, tripropylene glycol diacrylate Ester takes 4 parts for totally 75 parts and dispersant B YK9077.
Firstly, being uniformly mixed after monomer and dispersant using constant temperature blender with magnetic force.Then, it is added thereto Magenta pigment, pre-dispersed 60 minutes using mechanical agitator.Finally, pre-dispersed good pre-dispersed mixture is placed in grinder In, and the pick pearl of 3 times of pre-dispersed mixture total volume is added, high speed grinding 90 minutes, pinkish red mill base can be obtained.
(2) preparation of 3 D-printing material
15 parts of pinkish red mill base, 75 parts of 1,6 hexanediol diacrylate, 3,4- epoxycyclohexyl-methyl methacrylate With 3,4- epoxycyclohexyl-methyl 3, totally 8 parts of 4- epoxycyclohexyl formic acid esters, epoxy acrylic resin take 2 parts, vinyl ethers tree Rouge take 0.2 part, bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl take 8 parts, initiator PAG-2 take 0.5 part, reactive amines 2- Phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl phenyl) butanone (EHA) take 1 part, levelling agent TEGO410 take 2 parts.
Above-mentioned raw materials are mixed, is placed on mechanical agitator and stirs 30 minutes to uniform, three-dimensional beat can be obtained after filtering Print material.
Embodiment 3
(1) preparation of mill base
Take magenta pigment paratonere G (PR37) and totally 24 parts of paratonere 171 (PR171), monomer neopentyl glycol diacrylate Ester, dipropylene glycol diacrylate, acryloyl morpholine take 6 parts for totally 45 parts and dispersant B YK9151.
Firstly, being uniformly mixed after monomer and dispersant using constant temperature blender with magnetic force.Then, it is added thereto Magenta pigment, pre-dispersed 50 minutes using mechanical agitator.Finally, pre-dispersed good pre-dispersed mixture is placed in grinder In, and the pick pearl of 5 times of pre-dispersed mixture total volume is added, high speed grinding 120 minutes, pinkish red mill base can be obtained.
(2) preparation of 3 D-printing material
Totally 40 parts of 25 parts of pinkish red mill base, tripropylene glycol diacrylate, neopentylglycol diacrylate, bis- ((3,4- epoxies Cyclohexyl) methyl) adipate ester, 3- ethyl -3- hydroxymethyl-oxetane, bis- [3- ethyl] oxygen of 3,3- [oxygroup dimethylene] Totally 4 parts of azetidine, polyester acrylic resin, totally 4 parts of polyoxyalkylene acrylate resin, epoxy resin E51 take 3 parts, thio-phenyl-it is right Oxygen azo-cycle acetone and totally 12 parts of isopropyl thioxanthone, initiator PAG-2 take 2 parts, reactive amines 2- phenyl benzyl -2- dimethyl amine - 1- (4- morpholine benzyl phenyl) butanone (EHA) take 4 parts, levelling agent TEGO432 take 0.2 part.
Above-mentioned raw materials are mixed, is placed on mechanical agitator and stirs 30 minutes to uniform, three-dimensional beat can be obtained after filtering Print material.
The 3 D-printing material that embodiment 1 obtains is tested for the property, result is as follows:
(1) it surface tension: is tested using the full-automatic surface tension instrument of K100 (German KRUSS company), unit mN/m.
Test result: surface tension 22.34mN/m.
(2) it viscosity: is tested under 25 DEG C of constant temperatures using AR2000ex type rheometer (TA company, the U.S.), uses diameter For the aluminum rotor of 60mm, taking in shear rate is the viscosity numerical value at 1s-1.
Test result: viscosity 12.99mPas.
(3) it cubical contraction (Shrinkage Ratio, SR): is carried out according to the pertinent regulations in international standard ISO3521 Test, the numerical value of SR are calculated by formula (1):
In formula, ρ1And ρ2The respectively density of fluid sample and the solid material after solidifying, is measured by 10mL specific gravity bottle.
Test result: cubical contraction 1.2%.
(4) curing rate: prepared fluid sample is uniformly coated in PET film with No. 0 silk stick at room temperature, is set Solidified in UV-LED curing (according to Vata precision Photoelectric Co., Ltd.), takes fingers-touch method observation solidification situation later. UV-LED light source is 385nm and 395nm double-wavelength light source.
Test result: the radiant energy density of UV-LED light source is 1.2W/cm2When, curing rate 880cm/min.
(5) color density: solid using X-rite X-528 type Spectrodensiotometer (Ai Seli color Science and Technology Ltd.) test Change the color density of rear film, chooses five different positions and tested respectively, using its average value as color density test result.
Test result: color density 0.7.
(6) dispersed: it uses Microtrac S3500 laser particle size analyzer (Microtrac Co., Ltd, the U.S.), with Ethyl alcohol is solvent, tests the equivalent diameter of the largest particles when cumulative distribution is 95% in size distribution curve.
Test result: granulometry value is 0.88 micron.
The 3 D-printing material that embodiment 1-3 is obtained injects UV-LED ink-jet three-dimensional printer (Beijing coloured silk rhythm number section Skill Co., Ltd), the 3D solid of magenta can be printed.The radiating light source wavelength of UV-LED ink-jet three-dimensional printer is 395nm。
For the effect of clearer expression 3 D-printing material provided by the present application, check experiment is carried out, it is following to compare Example:
Comparative example 1
Compared with Example 1, difference is only that, using pinkish red 20 parts of mill base, dipropylene glycol diacrylate in step (2) (DPGDA) 21.48 parts, 19.77 parts of acryloyl morpholine (ACMO), 13.83 parts of ethoxyethoxy ethyl acrylate (EOEOEA), Aliphatic polyurethane Eudragit E B270 take 1.44 parts, hyperbranched polyester acrylic ester V400 take 1.44 parts, photoinitiator 2777 take 3.02 parts, photoinitiator 2671 take 5.04 parts, photoinitiator 898 take 2.02 parts, reactive amines 2- phenyl benzyl -2- dimethyl Amine -1- (4- morpholine benzyl phenyl) butanone (EHA) take 3.60 parts, levelling agent TEGO 432 take 0.4 part.
I.e. only with free radical polymerization system.
Comparative example 2
Compared with Example 1, difference is only that, using pinkish red 20 parts of mill base, 3- Oxyranyle 7- oxa- in step (2) 6.68 parts of two rings [4.1.0] heptane (TTA-22), epoxy resin E44 take 0.32 part, photoinitiator PAG-2 take 0.96 part, levelling Agent TEGO 432 takes 0.4 part.
I.e. only with cationic polymerization system.
Comparative example 3
Compared with Example 1, difference is only that, is used in step (2): 20 parts of pinkish red mill base, dipropylene glycol diacrylate 21.48 parts of ester (DPGDA), 19.77 parts of acryloyl morpholine (ACMO), ethoxyethoxy ethyl acrylate (EOEOEA) 13.83 Part, aliphatic polyurethane Eudragit E B270 take 1.44 parts, hyperbranched polyester acrylic ester V400 take 1.44 parts, 3- epoxy 3.34 parts of ethyl group 7- oxabicyclo [4.1.0] heptane (TTA-22), epoxy resin E44 take 0.16 part, photoinitiator 2777 takes 3.02 parts, photoinitiator 2671 take 5.04 parts, photoinitiator 898 take 2.02 parts, initiator PAG-2 take 0.48 part, reactive amines 2- Phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl phenyl) butanone (EHA) take 3.60 parts, levelling agent TEGO432 take 0.4 part.
The mass ratio for changing free radical polymerization system and cationic polymerization system is 18:1.
Comparative example 4
Compared with Example 1, difference is only that, in step (2) photoinitiator 2777 take 1 part, photoinitiator 2671 take 2 Part, photoinitiator 898 take 1 part, initiator PAG-2 take 0.4 part.
Reduce the total content of initiator.
It is tested for the property according to preceding method, it is as shown in table 1 below to obtain performance data:
1 performance data of table
By upper table 1 it is found that the light that mixes provided by the present application including free radical polymerization system and cationic polymerization system is consolidated The 3 D-printing material of change system, has excellent performance.
The 3 D-printing material that the preparation method of 3 D-printing material provided by the present application obtains, surface tension and viscosity are suitable In, cubical contraction is small, curing rate is fast, color density is high, good dispersion, be highly suitable for UV-LED ink-jet three-dimensional printer Carry out 3 D-printing.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

1. a kind of 3 D-printing material, which is characterized in that based on parts by weight, comprising: 15-25 parts of mill base, free radical monomer 40- 75 parts, free based prepolymers 2-4 parts, 8-12 parts of free radical photo-initiation, 4-8 parts of cationic monomer, cationic prepolymer polymers 0.2-3 Part, 0.5-2 parts of cationic initiator, 1-4 parts of reactive amines, 0.2-2 parts of levelling agent；
The mill base, based on parts by weight, comprising: 15-24 parts of pigment, 45-75 parts of monomer, 4-10 parts of dispersing agent.
2. 3 D-printing material according to claim 1, which is characterized in that the pigment is selected from quinacridone magenta, gold Light is red, one of paratonere G, paratonere 171 or a variety of；The monomer is single official containing active polymerisable carbon-to-carbon double bond One of energy degree or bifunctionality monomer are a variety of, preferably ethoxyethoxy ethyl acrylate, 1,6- hexylene glycol, two propylene Acid esters, tripropylene glycol diacrylate, neopentylglycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine；It is described Dispersing agent is selected from BYK9077, BYK9151 or BYK9150.
3. 3 D-printing material according to claim 1, which is characterized in that the free radical monomer is gathered containing active Close single functionality or one of bifunctionality monomer or a variety of of carbon-to-carbon double bond, preferably ethoxyethoxy ethyl acrylate, 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, dipropylene glycol diacrylate Ester, acryloyl morpholine.
4. 3 D-printing material according to claim 3, which is characterized in that the free based prepolymers are containing polymerizable One of unsaturated oligomers of carbon-to-carbon double bond are a variety of, preferably epoxy acrylic resin, polyurethane acrylic resin, poly- Ester acroleic acid resin, polyoxyalkylene acrylate resin, the acrylic resin of acroleic acid esterification, vinylite or hyperbranched oligomer, The preferred hyperbranched polyester acrylic ester V400 of the hyperbranched oligomer, hyperbranched polyester acrylic ester V100, aliphatic poly ammonia Ester Eudragit E B270, polyester acrylate resin EB870, hyperbranched polyester acrylic ester EB150；The cation pre-polymerization Object is to can be carried out one of oligomer of cationic polymerization or a variety of, preferred epoxy, vinyl ether resin.
5. 3 D-printing material according to claim 4, which is characterized in that the free radical photo-initiation be cracking type from By base photoinitiator or hydrogen-capture-type light initiator, preferably phenyl bis- (2,4,6- trimethylbenzoyl) phosphine oxides, thio-phenyl- To oxygen azo-cycle acetone, photoinitiator 2773, photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, photoinitiator 389, photoinitiator 1508, isopropyl thioxanthone, 2,4- diethyl One of base thioxanthene -9- ketone is a variety of；The cationic initiator is initiator PAG-2.
6. 3 D-printing material according to claim 5, which is characterized in that the cationic monomer is cationic free Base effect is lower to occur one of compound of ring-opening polymerisation or a variety of, preferably 3,4- epoxycyclohexyl-methyl methacrylic acid Ester, 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, 3- Oxyranyle 7- oxabicyclo [4.1.0] heptane, Bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, 3- ethyl -3- hydroxymethyl-oxetane, 3,3- [oxygroup dimethylene] Bis- [3- ethyl] oxetanes.
7. 3 D-printing material according to claim 6, which is characterized in that the levelling agent is TEGO 410 or TEGO 432；The reactive amines are 2- phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl phenyl) butanone.
8. a kind of preparation method of the described in any item 3 D-printing materials of claim 1-7, which is characterized in that including following step It is rapid:
By the monomer and the dispersant it is uniform after, be added the pigment, stir it is pre-dispersed obtains pre-dispersed mixture, Then it grinds, obtains the mill base；
By the mill base, the free radical monomer, the free based prepolymers, the free radical photo-initiation, the cation Monomer, the cationic prepolymer polymers, the cationic initiator, the reactive amines, levelling agent mixing, stir evenly, mistake Filter obtains the 3 D-printing material.
9. preparation method according to claim 8, which is characterized in that the stirring pre-dispersed time is 30-60min, The time of the grinding is 90-180min；Before carrying out the grinding, pick pearl is added in the pre-dispersed mixture, it is described The additional amount of pick pearl is 3-5 times of the pre-dispersed mixture total volume.
10. a kind of application of the described in any item 3 D-printing materials of claim 1-7, which is characterized in that sprayed for UV-LED Black printing technique carries out 3 D-printing.
CN201811435377.4A 2018-11-28 2018-11-28 3 D-printing material and its preparation method and application Pending CN109517440A (en)

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