CN104710573A - Preparation method of 3D printing material - Google Patents
Preparation method of 3D printing material Download PDFInfo
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- CN104710573A CN104710573A CN201410826768.4A CN201410826768A CN104710573A CN 104710573 A CN104710573 A CN 104710573A CN 201410826768 A CN201410826768 A CN 201410826768A CN 104710573 A CN104710573 A CN 104710573A
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Abstract
The invention provides a method for preparing a 3D printing core material, when the 3D printing material is prepared, functional nanoparticles and a color additive are added in a photosensitive resin monomer, a photosensitive resin prepolymer, a photoinitiator and a terminator, the fluidity and moulding speed of the prepared 3D printing material is matched with a domestic 3D printer, and the problems of low intensity and difficult coloring of the 3D printing material can be solved.
Description
Technical field
The present invention relates to technical field of material chemistry, particularly a kind of preparation method of 3D printed material.
Background technology
3D prints the Industrial Revolution being again described as and overturning traditional manufacture.Its moulding process is: first go out required Computerized three-dimensional curved surface or solid model by software design, then according to processing requirement, it is carried out layering by certain thickness, original threedimensional electronic model is become two dimensional surface information, again the data after layering are carried out certain process, input machined parameters, produce numerical control code: under microcomputer control, digital control system with plane machining mode in an orderly manner Continuous maching go out each thin layer and make their automatic adhesives shaping.
3D printing technique is still in the starting stage at home, production cost is high, without domestic commerical prod, current domestic manufacturer is all from foreign procurement material, not only expensive, there is the problem that mobility is mated and formability is mated in the 3D printer that itself and China produce, simultaneously, existing 3D printed material also also exists insufficient strength, the problem of tint permanence difference, therefore urgently develop a kind of 3D printer mobility, formability of producing with China comparatively to mate, there is the 3D printed material of sufficient intensity and tint permanence simultaneously.
Summary of the invention
In order to overcome the problems referred to above, the present inventor is through studying with keen determination, found that, with the mixture of photosensitive resin polymer monomer and photosensitive resin performed polymer for matrix, add light trigger wherein, terminator, functional nanoparticle, color additives and solubilizing agent, 3D printed material obtained after mixing solves the technical barrier that its mobility is mated and shaping speed mates with 3D printer, solve current commercially available 3D printed material intensity low simultaneously, the problems such as painted difficulty, comprehensively improve the intensity of 3D printed material, the performance such as mobility and release property, and reduce the cost of 3D printed material.
The object of the present invention is to provide following several respects:
First aspect, the invention provides a kind of preparation method of 3D printed material, it is characterized in that, comprise the steps:
(1) prepare prepolymer: be dissolved in solvent by photosensitive resin polymer monomer, light trigger and terminator, carry out prepolymerization reaction at a certain temperature and obtain photosensitive resin prepolymer, make the viscosity of prepolymer be 100 ~ 50000cps;
(2) the photosensitive resin prepolymer that (1) is obtained is mixed with photosensitive resin polymer monomer, light trigger, terminator, functional nanoparticle, color additives, be polymerized at a certain temperature, obtained 3D printed material, makes the viscosity of 3D printed material be 1 ~ 10000cps.
Second aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, step also adds linking agent in (1),
In step (1), solvent for use comprises aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcoholic solvent, ether solvent, esters solvent, ketones solvent, diol, derivatives and/or nitrogen-containing solvent, be preferably benzene, toluene, dimethylbenzene, vinylbenzene, pentane, hexane, octane, hexanaphthene, pimelinketone, toluene pimelinketone, chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetrachloroethylene, trieline, methyl alcohol, ethanol, Virahol, ether, propylene oxide, ethylene glycol ether, ritalin, vinyl acetic monomer, propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol and/or trolamine.
The third aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, in step (1), prepolymerization reaction carries out at temperature is 30 DEG C ~ 200 DEG C, is preferably 50 DEG C ~ 150 DEG C, is more preferably 60 DEG C ~ 120 DEG C.
Fourth aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, step also adds linking agent and solubilizing agent in (2), mixes with photosensitive resin prepolymer, photosensitive resin polymer monomer, light trigger, terminator, functional nanoparticle and color additives.
5th aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, the raw materials used component comprising following weight proportion,
6th aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, the particle diameter of described functional nanoparticle is 1nm ~ 100 μm, it comprises one or more in metal oxide particle, salt particle, silicon-containing compound particle and nano metal powder, wherein
Described metal oxide particle comprises nano aluminium oxide, nano magnesia, nano zine oxide, nano titanium oxide, nano oxidized barium, nano oxidized strontium, oxide nano rare earth, nano manganese oxide, nano-sized iron oxide, nanometer cobalt oxide, nano-nickel oxide, nano cupric oxide, nano cuprous oxide, nano phase ag_2 o, nano chromium oxide, nanoscale molybdenum oxide, nanometer tungsten oxide and nano calcium oxide;
Described salt particle cationic element is selected from rare earth element, titanium elements, ferro element, calcium constituent, magnesium elements, strontium element, aluminium element, zinc element, barium element, manganese element, cobalt element, nickel element, copper, silver element, chromium element, molybdenum element, W elements, elemental lithium, sodium element and potassium element;
In described salt particle, negatively charged ion is selected from phosphate radical, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate radical, silicate, sulfate radical, chlorion, sulfonium ion, nitrate radical, formate and acetate;
Described silicon-containing compound comprises nano-silicon oxide compound, nano silicate and silicic acid;
Described nano metal powder comprises nano scale metal simple substance, the mixture of multiple nano scale metal simple substance and nano level powdered alloy, is preferably one or more mixtures in nanometer iron powder, copper nanoparticle, nano zinc powder, nanometer aluminium powder, nano rare earth powder, nano titanium powder, nanometer manganese powder, nano-nickel powder, nano-silver powder, nano-gold powder, nano Mo powder, Nano-mter Ti-alloy and nano-aluminium alloy.
7th aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, color additives comprises natural inorganic color additives and artificial color additives, wherein,
Natural inorganic color additives is as jet-black, chalk, cinnabar, laterite, realgar and natural iron oxide etc.;
Artificial color additives is selected from metal oxide-type color additives and salt color additives, is preferably metal oxide-type color additives, chromate color additives, carbonate color additives, Sulfates color additives, sulfide-based color additives, Nitrates color additives and acetic acid salt color additives.
Eighth aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, described photosensitive resin polymer monomer is selected from: Epoxy Acrylates compound monomer, methyl acrylic ester compound monomer and acroleic acid polyurethane compounds monomer;
Described photosensitive resin polymkeric substance performed polymer is selected from: the polymerization degree be 5 ~ 1000 Epoxy Acrylates polymkeric substance, the polymerization degree be 5 ~ 1000 methacrylate based polymers and the polymerization degree be 5 ~ 1000 acroleic acid polyurethane base polymer.
9th aspect, the present invention also provides above-mentioned preparation method, it is characterized in that,
Described light trigger is selected from: bitter almond oil camphor and derivative, benzil compounds, alkyl phenones compounds, acyl group phosphorous oxides, benzophenone compound, thioxanthone compounds, salt compounds, metallorganics class and organosilane compounds;
Described terminator is selected from: quinones, nitro-compound, nitroso compound, aryl polyol and sulfocompound, is preferably Resorcinol, p-ten.-butylcatechol, wood tar oil, Sodium dimethyldithiocarbamate 40min, sodium polysulphide and Sodium Nitrite;
Described linking agent is melamine-formaldahyde linking agent, aziridines linking agent, polycarbodiimide class linking agent, polyisocyanic acid class linking agent, alkylene oxides linking agent, metallic-ion crosslinking agent and epoxy resin linking agent.
Tenth aspect, the present invention also provides above-mentioned preparation method, it is characterized in that, described solubilizing agent is tensio-active agent, comprise cationic surfactant, at least one in aniorfic surfactant and nonionic surface active agent, be preferably, primary amine salt surfactant, secondary amine salt surfactant, quaternary surfactant and tertiary ammonium salt tensio-active agent, heterocyclic tensio-active agent, salt form tensio-active agent, Yelkin TTS tensio-active agent, amino acid type surfactant, betaine type amphoteric surfactant, fatty acid glycerine ester surfactant, span series, TWEEN Series tensio-active agent.
Accompanying drawing explanation
Fig. 1 illustrates the preparation flow figure of 3D printed material.
Embodiment
The present invention is further described below by way of specific embodiment.The features and advantages of the invention can describe along with these and become more clear.But these embodiments are only exemplary, for explaining explanation the present invention, but any restriction is not formed to scope of the present invention.Those skilled in the art should understand that; without prejudice in the spirit and scope of the present invention situation; can modify the present invention in details and/or change and/or equivalencing, these modification/amendment/replacements all should fall in the claimed scope of the present invention.
In the present invention, term used " polymerization degree " refers to the number of the structural unit (that is, photosensitive resin polymer monomer unit) in polymer molecular chain.
In the present invention, term used " viscosity " refers to brookfield viscosity.
The present inventor finds through large quantity research, the viscosity of photosensitive resin prepolymer is larger, velocity of flow is slow, reduce the speed that 3D prints, and the viscosity of photosensitive resin polymer monomer is less, its mobility strengthens, but with photosensitive resin polymer monomer for raw material is polymerized, when 3D prints, set time is long, and also unnecessary polymerization may be caused in 3D print procedure, therefore, simple photosensitive resin prepolymer or the photosensitive resin polymer monomer of using all can not meet the requirement of 3D printer to 3D printed material velocity of flow and curing speed; And the 3D printed material release property existed in prior art is poor, and intensity is little, therefore, the cracky when the demoulding and transportation and storage; In addition, pigment to the color adaptation limited use of 3D printed material of the prior art, and easily takes off in sun exposure hypostome color tolerance.
A part of photosensitive resin polymer monomer is aggregated into the lower photosensitive resin prepolymer of the polymerization degree by the present inventor in advance, again this photosensitive resin prepolymer is mixed by certain weight ratio with photosensitive resin polymer monomer, a certain amount of functional nanoparticle is added again to increase the intensity of 3D printed material after solidification in mixture, add the color that color additives regulates 3D printed material simultaneously, the viscosity of 3D printed material provided by the invention can regulate as required, its flow velocity and 3D printer are matched, and after the solidification of 3D printed material, there is larger intensity, various colors, not fugitive color.
According to first aspect provided by the invention, the preparation method of 3D printed material comprises the following steps:
Step 1, prepares prepolymer: be dissolved in solvent by photosensitive resin polymer monomer, light trigger and terminator, carries out prepolymerization reaction at a certain temperature and obtains prepolymer, makes the viscosity of prepolymer be 100 ~ 50000cps.
Viscosity made by photosensitive resin polymer monomer, light trigger and terminator by the present invention before preparation 3D printed material is that 100 ~ 50000cps makes subsequent reactions quick, and obtained 3D printed material excellent property.
The present invention is not particularly limited to solvent for use, with not with photosensitive resin polymer monomer, light trigger or terminator reaction are preferred, as aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcoholic solvent, ether solvent, esters solvent, ketones solvent, diol, derivatives and/or nitrogen-containing solvent, be preferably benzene, toluene, dimethylbenzene, vinylbenzene, pentane, hexane, octane, hexanaphthene, pimelinketone, toluene pimelinketone, chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetrachloroethylene, trieline, methyl alcohol, ethanol, Virahol, ether, propylene oxide, ethylene glycol ether, ritalin, vinyl acetic monomer, propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol and/or trolamine etc.
The present inventor finds, when temperature is 30 DEG C ~ 200 DEG C, the oligopolymer polymerization degree that photosensitive resin polymer monomer generates is 5 ~ 1000, the polymerization degree be 5 ~ 1000 its viscosity of polymkeric substance be 100 ~ 50000cps, be suitable for the raw material as preparation 3D printed material, therefore, selective polymerization temperature of the present invention is 30 DEG C ~ 200 DEG C, be preferably 50 DEG C ~ 150 DEG C, be more preferably 60 DEG C ~ 120 DEG C.
The present invention selects the time of prepolymerization reaction to be 0.5 ~ 3 hour, is preferably 1 ~ 2.5 hour, is more preferably 1.5 ~ 2 hours.
Step 2, the prepolymer that step 1 is obtained mixes with photosensitive resin polymer monomer, light trigger, terminator, functional nanoparticle, color additives, be polymerized at a certain temperature, obtained 3D printed material, makes the viscosity of 3D printed material be 1 ~ 10000cps.
The present invention is not particularly limited to temperature during mixing, not cause raw material to be polymerized to preferably, as 10 DEG C ~ 40 DEG C, is preferably 15 DEG C ~ 35 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
The present invention is not also particularly limited to mixing time, to be mixed by raw material as preferably, as 1 ~ 10 hour, is preferably 2 ~ 8 hours, is more preferably 3 ~ 6 hours.
3D printed material provided by the invention can also be polymerized at a certain temperature, but still exists in liquid form after polymerization, matches from different printer to meet it.
The raw materials used component comprising following weight proportion in the present invention:
Be preferably,
Preferably, the raw materials used component also comprising following weight proportion in the present invention:
Functional nanoparticle 0.1 ~ 5 weight part,
Color additives 0 ~ 5 weight part,
Solubilizing agent 0.1 ~ 5 weight part,
Be preferably,
Functional nanoparticle 0.5 ~ 3 weight part,
Color additives 0.1 ~ 4 weight part,
Solubilizing agent 0.5 ~ 1.5 weight part.
Photosensitive resin polymer monomer, be selected from Epoxy Acrylates compound, methyl acrylic ester compound and acroleic acid polyurethane compounds, it is as the matrix of 3D printed material, can after the luminous energy absorbing certain wavelength, resolve into free radical or generate free radical with other interaction of molecules, then cause transfer reaction, after reaction terminating, resin is become solid-state from liquid state, thus completes 3D printing.Because the viscosity of photosensitive resin polymer monomer is too small, its mobility is excessive, cause it in 3D print procedure, need higher 3D print speed and the curing speed of material, the i.e. polymerization velocity of photosensitive resin, and need the longer reaction times by monomer as the polyreaction that starting raw material carries out, cause the velocity of flow of 3D printed material not mated with its curing speed, cause the form of product form and the design obtained inconsistent further.
In contrast than be photosensitive resin prepolymer, namely, the polymerization degree is the photosensitive resin oligomer of 5 ~ 1000, the polymerization degree is larger, its viscosity is larger, its viscosity can reach 100 ~ 50000cps, even 5000 ~ 50000cps, the oligopolymer poor fluidity of viscosity in above-mentioned scope, although it requires low to curing speed, needs to consume the longer time-write interval in 3D process, even print the product layering obtained obvious, slickness is low, and therefore, the simple photosensitive resin prepolymer that uses also easily causes printing unsuccessfully as the starting raw material that 3D prints.
Photosensitive resin prepolymer and photosensitive resin polymer monomer are mixed matrix as 3D printed material according to certain weight ratio by the present inventor, by regulating the weight ratio of photosensitive resin prepolymer and photosensitive resin polymer monomer to mate print speed and curing speed, the product regular appearance that printing is obtained.
Owing to add the components such as a certain amount of light trigger, terminator in photosensitive resin prepolymer and photosensitive resin polymer monomer mixture after, its follow-up mix with light trigger, terminator time easily obtain finely dispersed system, therefore, the present invention selects when preparing photosensitive resin prepolymer, add a small amount of light trigger, terminator, function nano particle and color additives, can also add crosslinked.
The polymer monomer of photosensitive resin described in the present invention is selected from: Epoxy Acrylates compound monomer, methyl acrylic ester compound monomer and acroleic acid polyurethane compounds monomer, as: dimethacrylate, ethylene glycol methyl ether acrylate, two (tetramethylolmethane) five acrylate, two (tetramethylolmethane) six acrylate, ethoxylated trimethylolpropane triacrylate, Viscoat 295, glycol diacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol A methacrylic acid diesters, trimethylolpropane trimethacrylate, ethoxylated bisphenol a diacrylate, tetramethylol methane tetraacrylate, double pentaerythritol methacrylate, ethylene glycol monomethyl ether methacrylic ester and oxyethyl group glycerol tri-acrylate, be preferably ethylene glycol methyl ether acrylate, two (tetramethylolmethane) six acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol A methacrylic acid diesters, ethoxylated bisphenol a diacrylate, double pentaerythritol methacrylate, ethylene glycol monomethyl ether methacrylic ester and oxyethyl group glycerol tri-acrylate.
Described photosensitive resin polymkeric substance performed polymer is selected from: the polymerization degree is the Epoxy Acrylates polymkeric substance of 5 ~ 1000, the polymerization degree be 5 ~ 1000 methacrylate based polymers and the polymerization degree be 5 ~ 1000 acroleic acid polyurethane base polymer, as: the polymerization degree is the ethylene glycol methyl ether acrylate polymkeric substance of 5 ~ 1000, the polymerization degree is two (tetramethylolmethane) five acrylic ester polymer of 5 ~ 1000, the polymerization degree is two (tetramethylolmethane) six acrylic ester polymer of 5 ~ 1000, the polymerization degree is the ethoxylated trimethylolpropane triacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the trimethylolpropane trimethacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the glycol diacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is two (TriMethylolPropane(TMP)) tetraacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the ethylene glycol dimethacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the ethoxylated bisphenol A methacrylic acid diester polymer of 5 ~ 1000, the polymerization degree is the ethoxylated bisphenol a diacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the tetramethylol methane tetraacrylate polymkeric substance of 5 ~ 1000, the polymerization degree is the double pentaerythritol methacrylate polymkeric substance of 5 ~ 1000, the polymerization degree be 5 ~ 1000 ethylene glycol monomethyl ether methacrylate polymers and the polymerization degree be 5 ~ 1000 oxyethyl group glycerol tri-acrylate polymkeric substance.
The present inventor finds after deliberation, when the viscosity of 3D printed material is 1 ~ 10000cps, be preferably 5 ~ 8000cps, be more preferably 10 ~ 5000cps, further preferably 50 ~ 3000cps time, its viscosity and curing speed match, according to above-mentioned viscosity, the present invention selects the weight part of photosensitive resin prepolymer to be 10 ~ 70 parts, is preferably 20 ~ 60 parts, photosensitive resin polymer monomer weight part is 15 ~ 60 parts, is preferably 20 ~ 50 parts.
Photosensitive resin monomer after polymerisation, the molecular structure formed is just as the line of a rule length, intensity is low, easily break, and there is no elasticity, and linking agent exists multiple can functional group interactional with thread-like molecule, therefore, linking agent can make thread-like molecule be connected with each other by these functional groups, forms reticulated structure, thus improves intensity and the elasticity of the rear product of photosensitive resin solidification.
Light trigger, also known as photosensitizers or light curing agent, it is a class can absorb certain wavelength energy at ultraviolet region (250 ~ 420nm) or visible region (400 ~ 800nm), produce free radical, positively charged ion etc., thus the compound of trigger monomer polymerization crosslinking solidification, comprise the kind such as free radical photo-initiation, cation light initiator, wherein radical photoinitiator can be divided into crack type photoinitiator and hydrogen-capture-type light initiator by the mechanism of action producing free radical.
The present invention's light trigger used is selected from: bitter almond oil camphor and derivative, benzil compounds, alkyl phenones compounds, acyl group phosphorous oxides, benzophenone compound, thioxanthone compounds, salt compounds, metallorganics class and organosilane compounds; it at initiated polymerization under UV-irradiation, can complete the solidification of photosensitive resin polymer monomer and performed polymer.
The present invention's light trigger used is preferably selected from: bitter almond oil camphor (Benzoin), benzil (Benzil), α, α '-acetophenone (DEAP), Darocure1173 (HMPP), Darocure2959 (HHMP), Darocure184 (HCPK), Irgacure907 (MMMP), Irgacure369 (BDMB), acylphosphine oxide (TEPO), 2, 4, 6-trimethylbenzoyl-titanium dioxide phosphorus (TPO), Irgacure819 (BAPO), benzophenone (BP), 4-methyl benzophenone, 2, 4, 6-tri-methyl benzophenone, tetramethyl-Michler's keton (MK), tetraethyl-Michler's keton (DEMK), first and second base Michler's ketons (MEMK), isopropyl thioxanthone (ITX), 2-chlorothiaxanthenone (CTX), 1-chloro-4-propoxy-thioxanthone (CPTX), 2, 4-diethyl thioxanthone (DETX), 4-dimethyl ethyl aminobenzoate (EDAB) and Quantacure DMB etc.
Terminator, is also called chain terminator, stopper or polymerization stabilizer, and it in the polymerization can the material that proceeds of termination reaction, these substances with cause free radical and Propagating Radical reacts, make them lose activity thus the growth of terminating chain.
The present invention's terminator used is selected from: quinones, nitro-compound, nitroso compound, aryl polyol and sulfocompound, as Resorcinol, p-ten.-butylcatechol, wood tar oil, Sodium dimethyldithiocarbamate 40min, sodium polysulphide and Sodium Nitrite etc., its effect is the intensity and the mechanical property that regulate photosensitive resin.
Functional nanoparticle is selected from: inorganic, metal oxide particle, class bone inorganic nano-particle and bionic nano particle, and its effect is the performance of gaining in strength, improving texture, improving 3D printed product, makes it to be applied to the medical field such as orthopaedics, dentistry.
In the present invention, described functional nanoparticle preferably includes one or more in metal oxide particle, salt particle, silicon-containing compound particle and nano metal powder.
The present inventor finds, in 3D printed material, add metal oxide particle, and not only the viscosity of 3D printed material reduces, and mobility increases, and the print speed of the 3D printer can produced with China matches; And, after the solidification of 3D printed material, the physical strength of obtained product increases, that is, the present invention can, by regulating the add-on of the metal oxide particle micro-viscosity regulating 3D printed material on the one hand, regulate 3D printed material to obtain the physical strength of product on the other hand.
Described metal oxide particle comprises nano aluminium oxide, nano magnesia, nano zine oxide, nano titanium oxide, nano oxidized barium, nano oxidized strontium, oxide nano rare earth, nano manganese oxide, nano-sized iron oxide, nanometer cobalt oxide, nano-nickel oxide, nano cupric oxide, nano cuprous oxide, nano phase ag_2 o, nano chromium oxide, nanoscale molybdenum oxide, nanometer tungsten oxide and nano calcium oxide etc., wherein, described oxide nano rare earth is preferably the oxide compound of lanthanon, as nano lanthanum oxide, nano-cerium oxide, nano oxidized praseodymium, Nanometer-sized Neodymium Oxide, nano oxidized promethium, nano oxidized samarium, nano europium oxide, nano oxidized gadolinium, nano oxidized terbium, nano oxidized dysprosium, nano oxidized holmium, nano oxidized erbium, nano oxidized thulium, nano oxidized ytterbium and nano oxidized lutetium etc.
Described salt particle cationic element is selected from titanium elements, ferro element, calcium constituent, magnesium elements, rare earth element, titanium elements, ferro element, calcium constituent, magnesium elements, strontium element, aluminium element, zinc element, barium element, manganese element, cobalt element, nickel element, copper, silver element, chromium element, molybdenum element, W elements, elemental lithium, sodium element and potassium element, wherein, described rare earth element is preferably lanthanon, as lanthanum element, Ce elements, praseodymium element, neodymium element, promethium element, samarium element, europium element, gadolinium element, terbium element, dysprosium element, holmium element, er element, thulium element, ytterbium element and lutetium element etc., be preferably titanium elements, ferro element, calcium constituent and magnesium elements.
In described salt particle, negatively charged ion is selected from phosphate radical, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate radical, silicate, sulfate radical, chlorion, sulfonium ion, nitrate radical, formate and acetate, is preferably selected from phosphate radical, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate radical and silicate.
The present invention's salt particle used is one or more salt compounds particles be made up of described positively charged ion and described negatively charged ion, as: calcium phosphate, sodium phosphate, potassiumphosphate, sodium hydrogen phosphate, potassium primary phosphate, magnesiumcarbonate, sodium bicarbonate, water glass, ferric sulfate, manganous sulfate, single nickel salt, copper sulfate, Tai-Ace S 150, barium sulfate, molybdenum chloride, cobalt chloride, silver chloride, zinc chloride, strontium nitrate, Titanium Nitrate, sodium formiate and sodium-acetate etc.
The present inventor finds, add above-mentioned salt particle in 3D printed material after, the physical strength of obtained 3D printed product increases, and wear resistance obviously strengthens, aging life-span significant prolongation.
Described silicon-containing compound comprises nano-silicon oxide compound, nano silicate and silicic acid, is preferably nano silicon and nanometer water glass.
Described nano metal powder comprises nano scale metal simple substance, the mixture of multiple nano scale metal simple substance and nano level powdered alloy, be preferably nanometer iron powder, copper nanoparticle, nano zinc powder, nanometer aluminium powder, nano rare earth powder, nano titanium powder, nanometer manganese powder, nano-nickel powder, nano-silver powder, nano-gold powder, nano Mo powder, one or more mixtures in Nano-mter Ti-alloy and nano-aluminium alloy etc., wherein, described rare earth powder is preferably lanthanide series metal powder, as nanometer lanthanum powder, nano cerium powder, nanometer praseodymium powder, nanometer neodymium powder, nanometer promethium powder, nanometer samarium powder, nanometer europium powder, nanometer gadolinium powder, nanometer terbium powder, nanometer dysprosium powder, nanometer holmium powder, nanometer erbium powder, nanometer thulium powder, nanometer ytterbium powder and nanometer lutetium powder etc.
The present inventor also finds, after adding above-mentioned functions nanoparticle in 3D printed material, 3D printed material curing and demolding improves, namely, easily the product be cured can be taken off from pallet, and do not formed residual on pallet, keep the integrity of product.
The present inventor also finds, the particle diameter of described functional nanoparticle is less, it disperses more even in 3D printed material, macroscopic solid granule is there is not in obtained product, and, the particle diameter of functional nanoparticle is less, it is less to the effect such as scattering of light, refraction, thus reduce the loss of the light for initiated polymerization, the light simultaneously avoided for initiated polymerization causes not needing light-initiated region to be polymerized in 3D material due to scattering or refraction, and then improves the precision of 3D printed product.
Further, the present inventor also finds, the particle diameter of described functional nanoparticle is less, and it is more obvious that 3D prints the intensity enhancing obtaining product.
Therefore, the particle diameter of selection function nanoparticle of the present invention is less than 100 μm, but the particle diameter of functional nanoparticle is less, its production difficulty is larger, cost is higher, and the too small functional nanoparticle of particle diameter is easily reunited in 3D printed material, it is caused to disperse in 3D printed material uneven, and then the quality printing obtained product is also uneven, even there is macroscopic agglomerate, reduce the quality of product, therefore, the particle diameter of selection function nanoparticle of the present invention is 1nm ~ 100 μm, be preferably 5nm ~ 80 μm, be more preferably 10nm ~ 60 μ nm, as 50nm ~ 10 μm.
The present inventor finds, adds the functional nanoparticle of more than 5 weight parts in 3D printed material, and it is large that 3D prints obtained product physical strength, but snappiness declines, and matter is crisp easily broken, and product is fragile; And add 0.1 weight part following functions nanoparticle, it is good that 3D prints the product snappiness obtained, but physical strength is little, product is yielding, not resistance to compression, therefore, the present invention selects the functional nanoparticle adding 0.1 ~ 5 weight part in 3D printed material, preferably add the functional nanoparticle of 0.5 ~ 3 weight part, as 2 weight parts.
Color additives, uses organic color additive and/or the inorganic color additives, particularly inorganic, metal oxide class pigment of environmental protection (green/nontoxic/novel), meets the outward appearance demand of 3D printed product.
The present inventor find, there is serious COLOR FASTNESS PROBLEM in the color additives of adding in existing 3D printed material, that is, 3D print product color relation within a short period of time obtained can be thin out, even variable color, loses the original color of product.
The present inventor finds, adds in 3D printed material using inorganic dyestuff as dye additive, and the color of 3D printed product keeps lasting, and therefore, selection inorganic dyestuff of the present invention is as color additives.
The color additives that the present invention selects comprises natural inorganic color additives and artificial color additives, wherein,
Natural inorganic color additives is as jet-black, chalk, cinnabar, laterite, realgar and natural iron oxide etc.;
Artificial color additives is selected from metal oxide-type color additives and salt color additives, be preferably metal oxide-type color additives, chromate color additives, carbonate color additives, Sulfates color additives, sulfide-based color additives, Nitrates color additives and acetic acid salt color additives etc., be more preferably metal oxide-type color additives, carbonate color additives, Sulfates color additives, Nitrates color additives and acetic acid salt color additives etc., as:
Titanium dioxide, zinc oxide, magnesium oxide, cobalt oxide, iron protoxide, ferric oxide, cupric oxide, Sodium chromate, potassiumchromate, lead chromate, zinc chromate, magnesium chromate, yellow ultramarine, strontium yellow, baryta yellow, silver chromate, mercury chromate, cupric chromate, sodium carbonate, salt of wormwood, zinc carbonate, magnesiumcarbonate, calcium carbonate, Strontium carbonate powder, barium carbonate, ventilation breather, sodium sulfate, potassium sulfate, lead sulfate, zinc sulfate, magnesium sulfate, calcium sulfate, Strontium Sulphate, barium sulfate, Sulfuric acid disilver salt, Mercury bisulfate, copper sulfate, sodium sulphite, Iron sulfuret, potassium sulphide, zinc sulphide, cerium sulphide, lead nitrate, chromium nitrate, SODIUMNITRATE, saltpetre, nickelous nitrate, plumbic acetate, sulfuration cadmium red, sulfuration cadmium yellow and arbitrary composition etc. thereof,
Preferably, titanium dioxide, zinc oxide, magnesium oxide, iron protoxide, ferric oxide, cupric oxide, sodium carbonate, salt of wormwood, zinc carbonate, magnesiumcarbonate, calcium carbonate, Strontium carbonate powder, barium carbonate, ventilation breather, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, calcium sulfate, Strontium Sulphate, barium sulfate, Sulfuric acid disilver salt, Mercury bisulfate, copper sulfate, SODIUMNITRATE, saltpetre, plumbic acetate and arbitrary composition thereof etc.
The present inventor finds after deliberation, above-mentioned inorganic color additives can not be miscible mutually with other organic composition in 3D printed material, only can be scattered in 3D printed material with short grained form, when the particle diameter of inorganic color additives is greater than 100 μm, it is poor that 3D prints the product colour uniformity coefficient obtained, and when the particle diameter of inorganic color additives is less than 1nm, its coloration ability in 3D printed product weakens, therefore, the present invention selects the particle diameter of inorganic color additives to be 1nm ~ 100 μm.
In addition, the present inventor also finds, add above-mentioned inorganic color additives in 3D printed material after, the physical strength of 3D printed product strengthens, and wear resistance and resistance of aging strengthen.
The composite coloured additive that the present invention preferably uses organic dye and inorganic color additives to be mixed to get is as the color additives of 3D printed material.
The weight ratio of the present invention to organic dye and inorganic color additives is not particularly limited to.
The present inventor also finds, is used in inorganic color dye to add organic dye and obtain composite dye as color additives, and the 3D printed product color uniformity obtained is high, and color keeps lasting.
The pigment dyestuff that the present invention selects is selected from:
(1) azo pigment: tetrazo class pigment, aphthols pigment, azo lake class pigment, benzimidazolone pigment, azo condensation class pigment, metal complex class pigment;
(2) non-azo pigment: phthalocyanine pigment, thioindigo series pigments, anthraquinone pigment, triazine dioxin pigment;
(3) fragrant methane class pigment: quinophthalone class pigment, Isosorbide-5-Nitrae-pyrrolo-pyrrole-dione series pigments;
Pigment dyestuff is preferably C.I. Pigment Yellow 73 3, C.I. pigment Yellow 12, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 108, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150, C.I. pigment yellow 154, C.I. pigment orange 40, C.I. Pigment red 2, C.I. pigment red 3, C.I. Pigment red 53:1, C.I. Pigment red 168, C.I. Pigment red 181, C.I. Pigment red 208, C.I. Pigment red 255, C.I. pigment Blue 15, C.I. pigment blue 60, C.I. pigment Blue-61, C.I. pigment violet 3 and C.I. pigment Violet 23.The present inventor finds, the color additives adding 5 weight parts in 3D printed material can meet the demand of 3D printed material to color, when the add-on of color additives is greater than 5 weight part, affects light and passes through, cause print speed to reduce; Therefore, the present invention selects the add-on of color additives to be 0 ~ 5 weight part, is preferably 0.1 ~ 4 weight part, is more preferably 0.5 ~ 3 weight part.
The linking agent that the present invention selects is melamine-formaldahyde linking agent, aziridines linking agent, polycarbodiimide class linking agent, polyisocyanic acid class linking agent, alkylene oxides linking agent, metallic-ion crosslinking agent and epoxy resin linking agent, as polyacrylamide, trimeric cyanamide, methyl-etherified trimeric cyanamide, TriMethylolPropane(TMP)-three [3-(2-methylaziridine base)] propionic ester, TriMethylolPropane(TMP)-three (3-'-aziridino) propionic ester, tetramethylolmethane-three (3-'-aziridino) propionic ester, TriMethylolPropane(TMP)-three [3-(2-methylaziridine base) propionic ester], two (4-isocyanic ester butylcyclohexyl) methane, 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, β-(3,4-epoxy-cyclohexane) ethyl triethoxysilane, methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, hexanediamine, m-xylene diamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino diphenyl sulfone, mphenylenediamine etc.
The present inventor finds, add solubilizing agent in 3D printed material after, functional nanoparticle and the color additives dispersed homogeneous degree in 3D printed material increases, and rate of dispersion also increases.
Choice for use tensio-active agent of the present invention, as solubilizing agent, preferably uses and comprises cationic surfactant, in aniorfic surfactant and nonionic surface active agent, the tensio-active agent of at least one, is selected from primary amine salt surfactant, secondary amine salt surfactant, quaternary surfactant and tertiary ammonium salt tensio-active agent, heterocyclic tensio-active agent, salt form tensio-active agent, Yelkin TTS tensio-active agent, amino acid type surfactant, betaine type amphoteric surfactant, fatty acid glycerine ester surfactant, span series, TWEEN Series tensio-active agent, as maleic anhydride, maleic diester, stearic acid, Sodium dodecylbenzene sulfonate, Dodecyl trimethyl ammonium chloride, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, alkylol amide polyethylene oxide ether, Block polyoxyethylene-polyethenoxy ether, alkylol amide, alkyl poly glucoside, polyol ester class, sucrose ester, glycerin fatty acid ester series, Span series or TWEEN Series, be preferably octyl phenol Soxylat A 25-7-10, fatty alcohol-polyoxyethylene ether-7, sorbester p18, tween 80, maleic anhydride and/or maleic diester.
3D printed material provided by the invention can also be polymerized through ageing or at a certain temperature, but still exists in liquid form after ageing or polymerization, matches from different printer to meet it.
The technical process of the preparation method of 3D printed material provided by the invention, as shown in Figure 1, first light trigger, terminator are dissolved in solvent, mix with photosensitive resin polymer monomer in a kettle., there is prepolymerization reaction, obtained prepolymer product, then prepolymer product is mixed with quick resinous polymer monomer, terminator, functional nanoparticle and color additives be namely made as 3D printed material.
According to 3D printed material provided by the invention and method for making thereof, tool has the following advantages:
(1) 3D printed material provided by the invention and 3D printer have flow preferably matching and shaping speed matching;
(2) 3D printed material provided by the invention solves the problems such as the low and painted difficulty of intensity that current 3D printed material exists;
(3) firm, the flexible and not easy fracture of 3D printed material provided by the invention.
Embodiment
It is as follows that what the present embodiment was raw materials used be purchased information:
Dimethacrylate (photosensitive resin polymer monomer): Heng Ran bio tech ltd, Shanghai, purity >=98.5%;
Double pentaerythritol methacrylate (photosensitive resin polymer monomer): Hubei Chu Shengwei Chemical Co., Ltd., content >=98%;
Ethylene glycol methyl ether acrylate (photosensitive resin polymer monomer): Jiang Lai bio tech ltd, Shanghai;
Tetramethylol methane tetraacrylate (photosensitive resin polymer monomer): Chunan, Shanghai International Trading Company Ltd, trade(brand)name EM241;
Trimethylolpropane trimethacrylate (photosensitive resin polymer monomer): Shanghai Zhi Xin Chemical Co., Ltd.;
Two (TriMethylolPropane(TMP)) tetraacrylate (photosensitive resin polymer monomer): Rui Pu novel material company limited, content >=99%;
4-methyl benzophenone (light trigger): Heng Li Chemical Co., Ltd. of Shenzhen;
Bitter almond oil camphor (Benzoin) (light trigger): Hong Tai Chemical Co., Ltd., model C HC-11;
Irgacure369 (BDMB) (light trigger): Shanghai Hou Cheng Fine Chemical Co., Ltd;
Darocure184 (light trigger): Switzerland ciba;
α, α '-acetophenone (DEAP) (light trigger): Switzerland ciba;
EDAB (light trigger): Nanjing Jin Lu Chemical Co., Ltd.;
Resorcinol (terminator): Yancheng Heng Yuyuan Chemicals company limited;
Sodium dimethyldithiocarbamate 40min (terminator): Jiaozuo City Wei Lian Fine Chemical Co., Ltd, content >=99%;
Sodium Nitrite (terminator): the prosperous salt made from earth containing a comparatively high percentage of sodium chloride company limited in Weifang;
Methyl-etherified trimeric cyanamide (linking agent): Dongguan City Jun Yi Chemical Industry Science Co., Ltd, content >=80%;
Quadrol (linking agent): Jinan Yi Fan Chemical Co., Ltd., content >=70%;
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane (linking agent): Nanjing Lian Gui Chemical Co., Ltd.;
Methylhexahydrophthalic anhydride (linking agent): Jiaxing City orientalizes factory;
Polyacrylamide (linking agent): industrial chemicals company limited is full of in Zhengzhou hundred;
4,4 '-diamino diphenyl sulfone (linking agent): Suzhou Yin Sheng chemical company;
Wood tar oil (terminator): Shandong is won space and to be refined company limited;
Nano aluminium oxide (functional nanoparticle): space high-tech new material technology company limited is won in Beijing;
Nano titanium oxide (functional nanoparticle): Henan Huarong Environmental Protection Technology Co., Ltd;
Nano-calcium phosphate (functional nanoparticle): the nonmetal raw material company limited of U.S. lime goods is built in Pingnan County, Guangxi;
Nanometer SODIUM PHOSPHATE, MONOBASIC (functional nanoparticle): the purple chemical reagent work in Shanghai;
Nanometer water glass (functional nanoparticle): Xinghua City Condar auxiliary reagent factory;
Nano-calcium carbonate (functional nanoparticle): Lingshou County Jin Chuan mineral products processing factory;
Cobalt oxide (color additives): Xiangtan City Ke Le pigment company limited;
Titanium dioxide (color additives): good luck source, Shanghai Chemical Co., Ltd., Rutile type Titanium Dioxide R978;
Copper sulfate (color additives): Ruan Shi chemical industry (Changshu) company limited;
Sulfuration cadmium red (color additives): Shenyang City's reagent five factory;
C.I. Pigment red 208 (color additives): the Far East, Yancheng Chemical Co., Ltd.;
Octyl phenol Soxylat A 25-7-10 (solubilizing agent): Guangzhou Bao Jili Chemical Co., Ltd.;
Fatty alcohol-polyoxyethylene ether-7 (solubilizing agent): Guangzhou Xi Lu Chemical Co., Ltd.;
Sorbester p18 (solubilizing agent): Guangzhou Run Hua foodstuff additive limited liability company;
Tween 80 (solubilizing agent): Jiangsu Hai'an Petrochemical Plant.
embodiment 1
(1) prepolymer is prepared: be dissolved in 100mL methylene dichloride by 48.8g photosensitive resin polymer monomer dimethacrylate, 0.2g light trigger Irgacure369 (BDMB) and 1.0g terminator Resorcinol and 10.0g linking agent methyl-etherified trimeric cyanamide, at 150 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 10000cps;
(2) by prepolymer obtained in (1) and 28.5g photosensitive resin polymer monomer dimethacrylate, 0.3g light trigger Irgacure369 (BDMB), 1.0g terminator Resorcinol, 10.0g linking agent methyl-etherified trimeric cyanamide, 1.0g functional nanoparticle calcium carbonate (particle diameter 20 ~ 40nm), 1.0g color additives TiO
2(particle diameter 20 ~ 40 μm) and 0.1g solubilizing agent octyl phenol Soxylat A 25-7-10 at room temperature mix, obtained 3D printed material.
The viscosity of the 3D printed material that the present embodiment obtains is about 500cps.
embodiment 2
(1) prepolymer is prepared: be dissolved in 200mL chloroform by 60.0g photosensitive resin polymer monomer double pentaerythritol methacrylate, 2.0g light trigger 4-methyl benzophenone, 2.0g terminator Sodium dimethyldithiocarbamate 40min and 5.0g linking agent methyl-etherified trimeric cyanamide, at 100 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 8000cps;
(2) prepolymer obtained in (1) is at room temperature mixed with 40.0g photosensitive resin polymer monomer dipentaerythritol vinylformic acid six ester, 8.0g light trigger 4-methyl benzophenone, 3.0g terminator Sodium dimethyldithiocarbamate 40min, 5.0g linking agent methyl-etherified trimeric cyanamide, 5.0g functional nanoparticle calcium phosphate (particle diameter 80 ~ 100 μm), 5.0g color additives cobalt blue and 2.0g solubilizing agent fatty alcohol-polyoxyethylene ether-7, obtained 3D printed material, the viscosity of obtained 3D printed material is about 300cps.
embodiment 3
(1) prepolymer is prepared: be dissolved in 150mL acetone by 10.0g photosensitive resin polymer monomer ethylene glycol methyl ether acrylate, 0.05g light trigger bitter almond oil camphor (Benzoin) and 1.0g terminator Sodium dimethyldithiocarbamate 40min and 40.0g linking agent quadrol, at 80 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 3000cps;
(2) by prepolymer obtained in (1) and 40.0g photosensitive resin polymer monomer dipentaerythritol vinylformic acid six ester, 0.05g light trigger bitter almond oil camphor (Benzoin), 2.0g terminator Sodium dimethyldithiocarbamate 40min, 10.0g linking agent quadrol, 0.1g functional nanoparticle nano aluminium oxide (particle diameter 600 ~ 800nm), 0.5g color additives CuSO
4with the mixing of 0.5g solubilizing agent tween 80, at room temperature mix, obtained 3D printed material, the viscosity of obtained 3D printed material is about 50cps.
embodiment 4
(1) prepolymer is prepared: by 70.0g photosensitive resin polymer monomer tetramethylol methane tetraacrylate, 0.1g light trigger Darocure184 and 0.1g terminator Sodium Nitrite and 15.0g linking agent 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane is dissolved in 250mL chloroform, at 200 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 3000cps;
(2) by prepolymer 70.0g obtained in (1) and 40.0g photosensitive resin polymer monomer tetramethylolmethane vinylformic acid four ester, 0.2g light trigger Darocure184, 0.2g terminator Sodium Nitrite, 8.0g linking agent 3-(2, 3-epoxy third oxygen) propyl trimethoxy silicane, 3.0g functional nanoparticle nanometer water glass (particle diameter 50nm ~ 10 μm), color additives 1.0gC.I. Pigment red 208, 2.0g copper sulfate and the mixing of 1.5g solubilizing agent sorbester p18, at room temperature mix, obtained 3D printed material, the viscosity of obtained 3D printed material is about 100cps.
embodiment 5
(1) prepolymer is prepared: by 20.0g photosensitive resin polymer monomer trimethylolpropane trimethacrylate, 3.0g light trigger α, α '-acetophenone (DEAP) and 0.5g terminator Sodium Nitrite and 40.0g linking agent methylhexahydrophthalic anhydride are dissolved in 150mL methylene dichloride, at 120 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 3000cps;
(2) by prepolymer obtained in (1) and 40.0g photosensitive resin polymer monomer TriMethylolPropane(TMP) methacrylic acid three ester, 5.0g light trigger α, α '-acetophenone (DEAP), 0.5g terminator Sodium Nitrite, 10.0g linking agent methylhexahydrophthalic anhydride, 0.5g functional nanoparticle nanometer SODIUM PHOSPHATE, MONOBASIC (particle diameter 10 ~ 50nm), 0.1g color additives sulfuration cadmium red and 1.2g solubilizing agent tween 80 mix, at room temperature mix, obtained 3D printed material, the viscosity of obtained 3D printed material is about 9cps.
the preparation of embodiment 6JC-021
(1) prepolymer is prepared: be dissolved in 150mL acetone by 50.0g photosensitive resin polymer monomer ethylene glycol methyl ether acrylate, 0.05g light trigger bitter almond oil camphor (Benzoin) and 1.0g terminator Sodium dimethyldithiocarbamate 40min and 20.0g linking agent quadrol, at 80 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 3000cps;
(2) prepolymer obtained in (1) is mixed with 30.0g photosensitive resin polymer monomer dipentaerythritol vinylformic acid six ester, 0.05g light trigger bitter almond oil camphor (Benzoin), 2.0g terminator Sodium dimethyldithiocarbamate 40min, 10.0g linking agent quadrol, 0.1g functional nanoparticle nano aluminium oxide (particle diameter 600 ~ 800nm) and 0.5g solubilizing agent tween 80, at room temperature mix, obtained 3D printed material, the viscosity of obtained 3D printed material is about 350cps.
the preparation of embodiment 7CJ-054
(1) prepolymer is prepared: be dissolved in 100mL methylene dichloride by 48.8g photosensitive resin polymer monomer dimethacrylate, 0.2g light trigger Irgacure369 (BDMB) and 1.0g terminator Resorcinol and 10.0g linking agent methyl-etherified trimeric cyanamide, at 150 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 10000cps;
(2) by prepolymer obtained in (1) and 28.5g photosensitive resin polymer monomer dimethacrylate, 0.3g light trigger Irgacure369 (BDMB), 1.0g terminator Resorcinol, 10.0g linking agent methyl-etherified trimeric cyanamide, 3.0g functional nanoparticle calcium carbonate (particle diameter 20 ~ 40nm), 3.0g color additives TiO
2(particle diameter 20 ~ 40 μm) and 0.3g solubilizing agent octyl phenol Soxylat A 25-7-10 at room temperature mix, obtained 3D printed material.
The viscosity of the 3D printed material that the present embodiment obtains is about 440cps.
the preparation of embodiment 8CS-033
(1) prepolymer is prepared: by 70.0g photosensitive resin polymer monomer tetramethylol methane tetraacrylate, 0.1g light trigger Darocure184 and 0.1g terminator Sodium Nitrite and 15.0g linking agent 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane is dissolved in 250mL chloroform, at 200 DEG C, carry out prepolymerization reaction obtain the prepolymer that the polymerization degree is 50 ~ 200, the viscosity of prepolymer is about 3000cps;
(2) by prepolymer 70.0g obtained in (1) and 20.0g photosensitive resin polymer monomer tetramethylolmethane vinylformic acid four ester, 0.2g light trigger Darocure184,0.2g terminator Sodium Nitrite, 8.0g linking agent 3-(2,3-epoxy third oxygen) mixing of propyl trimethoxy silicane, 5.0g functional nanoparticle nanometer water glass (particle diameter 50 ~ 100nm), color additives 1.0gC.I. Pigment red 208,2.0g copper sulfate and 1.5g solubilizing agent sorbester p18, at room temperature mix, obtained 3D printed material, the viscosity of obtained 3D printed material is about 460cps.
Comparative example
comparative example 1 does not add photosensitive resin prepolymer
By 78.5g photosensitive resin polymer monomer dimethacrylate, 0.5g light trigger Irgacure369 (BDMB), 2.0g terminator Resorcinol, 1.0g functional nanoparticle Nano-meter CaCO3
3(particle diameter 50 ~ 100nm), 1.0g color additives TiO
2, 20.0g linking agent two (TriMethylolPropane(TMP)) vinylformic acid four ester and 0.1g solubilizing agent octyl phenol Soxylat A 25-7-10, at room temperature mix, obtained 3D printed material.
The viscosity of the 3D printed material that this comparative example obtains is about 5cps, compared with its 3D printed material obtained with embodiment 1, shaping speed in use reduces greatly, serious reduction print speed, increase the time-write interval 5 times, and after solidification, the intensity of material also obtains the intensity after material cured far below embodiment 1.
comparative example 2 does not add photosensitive resin polymerization single polymerization monomer
(1) by 80.0g photosensitive resin polymer monomer dipentaerythritol vinylformic acid six ester, 5.0g light trigger 4-methyl benzophenone and the mixing of 1.0g terminator Sodium dimethyldithiocarbamate 40min, 2.0g functional nanoparticle calcium phosphate (particle diameter 100 ~ 300nm), 1.0g color additives cobalt blue and 2.0g solubilizing agent fatty alcohol-polyoxyethylene ether-7, be dissolved in 100mL chloroform, at 100 DEG C, carry out polyreaction obtain the polymkeric substance that the polymerization degree is 50 ~ 200, i.e. 3D printed material, its viscosity is about 8000cps.
Compared with the 3D printed material that the 3D printed material that this comparative example obtains is obtained with embodiment 2, viscosity obviously increases, this excessive viscosity makes 3D printed material not easily flow in the process printed, thus causes the consequence of time-write interval length and print member excalation.
comparative example 3 does not add functional nanoparticle
This comparative example is identical with embodiment 3 method therefor, and difference is only in step (2), do not add functional nanoparticle nano aluminium oxide (particle diameter 600 ~ 800nm), and the viscosity of this 3D printed material is about 40cps.
The 3D printed material obtained by this comparative example prints the object obtained, and after its solidification, flexural strength is 3 ~ 8MPa, is significantly less than the flexural strength 25 ~ 28MPa after the obtained 3D printed material solidification of embodiment 3, namely fragile.
comparative example 4 uses merely organic dye as color additives
This comparative example is identical with embodiment 4 method therefor, and difference is only that the color additives used in step (2) is 1.0gC.I. Pigment red 208, and the viscosity of this 3D printed material is about 85cps.
The 3D printed material obtained by this comparative example prints the object obtained, and fades serious after its solidification through one week in direct sunlight.
Experimental example
experimental example 13D printed material product photosensitive resin performance index
The testing method of solid property: ASTM-D790M after photocuring.
Test result is as shown in table 1 below:
Table 13D printed material product photosensitive resin the performance test results
experimental example 2 different 3D file printing accuracy test
Experimental technique:
1, use work of nature II type printer, adopt embodiment and comparative example material, print the solid cubes of 1cm × 1cm × 1cm;
2, in cubes six faces, select the most coarse position (position that namely smoothness is the poorest, adjacent locations is uneven), measure its surface height difference, as printing precision index;
Result is as shown in table 2 below:
Table 23D printed material accuracy test result
the experimental example 33D printed material color hold-time measures
Experimental technique:
1, use work of nature II type printer, adopt embodiment and comparative example material, print the solid cubes of 1cm × 1cm × 1cm;
2, printing 12:00 at rear noon on the same day, uses the camera of the subsidiary computer of printer to take pictures;
3, sample is placed on balcony, daytime direct sunlight one week;
4, after one week noon 12:00, use the camera of the subsidiary computer of printer to take pictures;
5, use picture analyzing software, comprehensively analyze the brightness of sample in two photos in front and back, tone, three primary colors change, calculate comprehensive similarity (with 100 for 100%, identical, with 0 for 0%, to be bleached by black).
Result is as shown in table 3 below:
Table 33D printed material color hold-time test result
experimental example 43D printed product aging life-span measures
Experimental technique:
1, use work of nature II type printer, adopt embodiment and comparative example material, print 10cm × 1cm × 2mm thin slice;
2, after printing, the same day tests flexural strength, modulus in flexure, elastic recovery interval, elongation at break;
3, sample is placed on balcony, daytime direct sunlight one week;
4, after one week, test flexural strength, modulus in flexure, elastic recovery are interval, elongation at break;
5, twice test result before and after comprehensive analysis, (with 0 for 0%, performance is completely unchanged to calculate comprehensive aging rate; With 100 for 100%, solid powders).
Result is as shown in table 4 below:
Table 43D printed product aging life-span result
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a preparation method for 3D printed material, is characterized in that, comprises the steps:
(1) prepare prepolymer: be dissolved in solvent by photosensitive resin polymer monomer, light trigger and terminator, carry out prepolymerization reaction at a certain temperature and obtain photosensitive resin prepolymer, make the viscosity of prepolymer be 100 ~ 50000cps;
(2) the photosensitive resin prepolymer that (1) is obtained is mixed with photosensitive resin polymer monomer, light trigger, terminator, functional nanoparticle, color additives, be polymerized at a certain temperature, obtained 3D printed material, makes the viscosity of 3D printed material be 1 ~ 10000cps.
2. preparation method according to claim 1, is characterized in that, step also adds linking agent in (1),
In step (1), solvent for use comprises aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcoholic solvent, ether solvent, esters solvent, ketones solvent, diol, derivatives and/or nitrogen-containing solvent, be preferably benzene, toluene, dimethylbenzene, vinylbenzene, pentane, hexane, octane, hexanaphthene, pimelinketone, toluene pimelinketone, chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetrachloroethylene, trieline, methyl alcohol, ethanol, Virahol, ether, propylene oxide, ethylene glycol ether, ritalin, vinyl acetic monomer, propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol and/or trolamine.
3. preparation method according to claim 1, is characterized in that, in step (1), prepolymerization reaction carries out at temperature is 30 DEG C ~ 200 DEG C, is preferably 50 DEG C ~ 150 DEG C, is more preferably 60 DEG C ~ 120 DEG C.
4. preparation method according to claim 1, it is characterized in that, step also adds linking agent and solubilizing agent in (2), mixes with photosensitive resin prepolymer, photosensitive resin polymer monomer, light trigger, terminator, functional nanoparticle and color additives.
5. preparation method according to claim 1, is characterized in that, the raw materials used component comprising following weight proportion,
6. according to the preparation method one of Claims 1 to 5 Suo Shu, it is characterized in that, the particle diameter of described functional nanoparticle is 1nm ~ 100 μm, and it comprises one or more in metal oxide particle, salt particle, silicon-containing compound particle and nano metal powder, wherein
Described metal oxide particle comprises nano aluminium oxide, nano magnesia, nano zine oxide, nano titanium oxide, nano oxidized barium, nano oxidized strontium, oxide nano rare earth, nano manganese oxide, nano-sized iron oxide, nanometer cobalt oxide, nano-nickel oxide, nano cupric oxide, nano cuprous oxide, nano phase ag_2 o, nano chromium oxide, nanoscale molybdenum oxide, nanometer tungsten oxide and nano calcium oxide;
Described salt particle cationic element is selected from rare earth element, titanium elements, ferro element, calcium constituent, magnesium elements, strontium element, aluminium element, zinc element, barium element, manganese element, cobalt element, nickel element, copper, silver element, chromium element, molybdenum element, W elements, elemental lithium, sodium element and potassium element;
In described salt particle, negatively charged ion is selected from phosphate radical, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate radical, silicate, sulfate radical, chlorion, sulfonium ion, nitrate radical, formate and acetate;
Described silicon-containing compound comprises nano-silicon oxide compound, nano silicate and silicic acid;
Described nano metal powder comprises nano scale metal simple substance, the mixture of multiple nano scale metal simple substance and nano level powdered alloy, is preferably one or more mixtures in nanometer iron powder, copper nanoparticle, nano zinc powder, nanometer aluminium powder, nano rare earth powder, nano titanium powder, nanometer manganese powder, nano-nickel powder, nano-silver powder, nano-gold powder, nano Mo powder, Nano-mter Ti-alloy and nano-aluminium alloy.
7. according to the preparation method one of Claims 1 to 5 Suo Shu, it is characterized in that, color additives comprises natural inorganic color additives and artificial color additives, wherein,
Natural inorganic color additives is selected from jet-black, chalk, cinnabar, laterite, realgar and natural iron oxide;
Artificial color additives is selected from metal oxide-type color additives and salt color additives, is preferably metal oxide-type color additives, chromate color additives, carbonate color additives, Sulfates color additives, sulfide-based color additives, Nitrates color additives and acetic acid salt color additives.
8., according to the preparation method one of Claims 1 to 5 Suo Shu, it is characterized in that,
Described photosensitive resin polymer monomer is selected from: Epoxy Acrylates compound monomer, methyl acrylic ester compound monomer and acroleic acid polyurethane compounds monomer;
Described photosensitive resin polymkeric substance performed polymer is selected from: the polymerization degree be 5 ~ 1000 Epoxy Acrylates polymkeric substance, the polymerization degree be 5 ~ 1000 methacrylate based polymers and the polymerization degree be 5 ~ 1000 acroleic acid polyurethane base polymer.
9., according to the preparation method one of Claims 1 to 5 Suo Shu, it is characterized in that,
Described light trigger is selected from: bitter almond oil camphor and derivative, benzil compounds, alkyl phenones compounds, acyl group phosphorous oxides, benzophenone compound, thioxanthone compounds, salt compounds, metallorganics class and organosilane compounds;
Described terminator is selected from: quinones, nitro-compound, nitroso compound, aryl polyol and sulfocompound, is preferably Resorcinol, p-ten.-butylcatechol, wood tar oil, Sodium dimethyldithiocarbamate 40min, sodium polysulphide and Sodium Nitrite;
Described linking agent is melamine-formaldahyde linking agent, aziridines linking agent, polycarbodiimide class linking agent, polyisocyanic acid class linking agent, alkylene oxides linking agent, metallic-ion crosslinking agent and epoxy resin linking agent.
10. according to the preparation method one of Claims 1 to 5 Suo Shu, it is characterized in that, described solubilizing agent is tensio-active agent, comprise cationic surfactant, at least one in aniorfic surfactant and nonionic surface active agent, be preferably, primary amine salt surfactant, secondary amine salt surfactant, quaternary surfactant and tertiary ammonium salt tensio-active agent, heterocyclic tensio-active agent, salt form tensio-active agent, Yelkin TTS tensio-active agent, amino acid type surfactant, betaine type amphoteric surfactant, fatty acid glycerine ester surfactant, span series and TWEEN Series tensio-active agent.
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| CN105085833A (en) * | 2015-08-20 | 2015-11-25 | 上海交通大学 | 3D printing material with thermochromic property |
| CN105085833B (en) * | 2015-08-20 | 2018-02-09 | 上海交通大学 | A kind of 3D printing material with thermochromic properties |
| CN104997645B (en) * | 2015-09-01 | 2017-12-12 | 河北润达环保科技有限公司 | A kind of method that 3D printing makes Cosmetic pack |
| CN104997645A (en) * | 2015-09-01 | 2015-10-28 | 河北润达环保科技有限公司 | Method for making makeup mask by 3D (three dimensional) printing |
| CN106243290A (en) * | 2016-05-11 | 2016-12-21 | 杭州乐新材料科技有限公司 | A kind of rubber-type photocuring 3D printed material and preparation method thereof |
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| CN106543705A (en) * | 2016-10-24 | 2017-03-29 | 上海臣光工业介质有限公司 | A kind of low temperature resistant photocuring 3D printing material and preparation method thereof |
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| CN108559037A (en) * | 2018-02-07 | 2018-09-21 | 重庆大学 | A kind of 3D printing photosensitive resin of nano modification and its preparation method and application |
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| CN108658607A (en) * | 2018-05-17 | 2018-10-16 | 广东工业大学 | Ceramics and the application of a kind of new ceramics slurry and its preparation |
| TWI760818B (en) * | 2019-08-21 | 2022-04-11 | 美商應用材料股份有限公司 | Additive manufacturing of polishing pads |
| US11965103B2 (en) | 2019-08-21 | 2024-04-23 | Applied Materials, Inc. | Additive manufacturing of polishing pads |
| CN112480293A (en) * | 2019-09-12 | 2021-03-12 | 中国科学院化学研究所 | Self-repairing or recyclable photocuring 3D printing part and preparation method and application thereof |
| CN112480293B (en) * | 2019-09-12 | 2022-05-13 | 中国科学院化学研究所 | Self-repairable or recyclable photocuring 3D printing part and preparation method and application thereof |
| CN114394848A (en) * | 2021-04-02 | 2022-04-26 | 东莞慧瓷智造打印科技有限公司 | Method for manufacturing ceramic filter for casting based on photocuring 3D printing technology |
| CN114394848B (en) * | 2021-04-02 | 2022-09-30 | 东莞慧瓷智造打印科技有限公司 | Method for manufacturing ceramic filter for casting based on photocuring 3D printing technology |
| CN116333235A (en) * | 2023-04-10 | 2023-06-27 | 深圳永昌和科技有限公司 | Photo-curing acrylic resin material for 3D printing and preparation method thereof |
| CN116333235B (en) * | 2023-04-10 | 2024-01-12 | 深圳永昌和科技有限公司 | Photo-curing acrylic resin material for 3D printing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104710548B (en) | 2017-09-29 |
| CN104710573B (en) | 2017-07-07 |
| CN104710548A (en) | 2015-06-17 |
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