WO2017185508A1 - 3d喷墨打印用墨水组合物、墨水组及其制备方法 - Google Patents

3d喷墨打印用墨水组合物、墨水组及其制备方法 Download PDF

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Publication number
WO2017185508A1
WO2017185508A1 PCT/CN2016/087019 CN2016087019W WO2017185508A1 WO 2017185508 A1 WO2017185508 A1 WO 2017185508A1 CN 2016087019 W CN2016087019 W CN 2016087019W WO 2017185508 A1 WO2017185508 A1 WO 2017185508A1
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ink composition
parts
ink
acrylate
colorant
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PCT/CN2016/087019
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English (en)
French (fr)
Inventor
王风
王丽坤
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珠海赛纳打印科技股份有限公司
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Publication of WO2017185508A1 publication Critical patent/WO2017185508A1/zh

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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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to printing technology, and more particularly to an ink composition for 3D inkjet printing, an ink set, and a method of preparing the same.
  • 3D inkjet printing technology is based on the working principle of the inkjet printer, under the excitation of the digital signal, the liquid (molding material) in the nozzle chamber is instantaneously formed into droplets, and is ejected from the nozzle at a certain speed and frequency.
  • the layer is solidified layer by layer according to the specified path to finally obtain a 3D object.
  • the molding materials used in the inkjet printing of the existing 3D inkjet printer can be classified into two types: temperature curing materials and UV light curing materials, wherein the temperature curing materials are mainly wax-containing materials, and the solid or semi-solid wax materials are heated.
  • the temperature control device Melting into a fluid-like material into the printhead nozzle for inkjet printing, when the wax droplets are ejected from the printhead nozzle onto the previous carrier, the temperature control device has a cooling process for the newly ejected wax droplets.
  • the wax droplets are solidified on the specified trajectory.
  • the model data of the 3D object the next layer is superimposed and solidified on the previous layer in the same manner to form the target 3D object, but the wax is affected by temperature, especially at high temperature. The melting is prone to occur, which results in a range of applications.
  • the UV-curable material contains at least a photosensitive resin and an initiator.
  • European Patent No. 1,458,825 B1 discloses a radiation-curable composition comprising at least one UV-curable urethane methacrylic resin, at least one wax, at least one a methacrylic acid diluent, at least one photoinitiator and at least one polymerization initiator, which is used in ink jet printing to raise the temperature of the composition to 70-90 ° C, and the composition is ejected from the print head A cooling environment is then provided to convert the dispensed composition material to a solid, which is then irradiated with UV light to form a layer of the 3D object, after which the foregoing steps are repeated to form a 3D object.
  • the composition needs high temperature to be melted during use, the print head mounted at the time of printer design must be able to withstand high temperatures, thereby affecting the service life of the print head on the one hand, and energy consumption on the other hand, and the composition It contains wax and resin materials, which are two kinds of materials with completely different properties. They are carried out in two steps during the curing process. The composition is not fully cured by cooling, and then further cured by UV light. The former is after the physical process. Is a chemical process, which leads to a combination The use of things is complicated.
  • the present invention provides an ink composition for 3D inkjet printing, an ink set, and a method of manufacturing the same, the 3D object manufactured by the ink composition has good stability, does not deform due to temperature factors, and can Reduce the operating temperature of the print head and make the curing process simple.
  • the present invention provides an ink composition for 3D inkjet printing comprising the following components by weight: 45-75 parts of an acrylic oligomer, 20-45 parts of an acrylic monomer, 1-9 parts of a photoinitiator, and an auxiliary agent 0.2- 10 parts, 0 to 4 parts of a colorant;
  • the acrylic oligomer is selected from one or more of urethane acrylate, polyester acrylate and polyether acrylate;
  • the ink composition has a viscosity at room temperature of between 25 and 70 cps; the ink composition has a viscosity at at least one jetting temperature of between 9 and 14.5 cps.
  • the ink composition of the present invention in the process of performing inkjet printing, a light source is irradiated on the formed 3D object sheet layer, and the photoinitiator in the ink composition is induced to generate radicals, thereby promoting the acrylic oligomer and the acrylic monomer.
  • a polymerization reaction occurs.
  • the acrylic oligomer can enhance the wear resistance and flexibility of the 3D object
  • the acrylic monomer can rapidly polymerize
  • the photoinitiator can induce the polymerization of the ink composition under the illumination of the light source, when the amount of the colorant is zero, It is a clear ink composition.
  • Appropriate amounts of auxiliaries and colorants can optimize the printing effect of 3D objects.
  • the coloring agent hinders the polymerization of the ink composition.
  • the mechanical properties of the printed 3D object are degraded, and therefore, the weight fraction of the colorant cannot be greater than 4, wherein when the colorant is 0, it is a clear ink composition.
  • the light source may be an ultraviolet light source or a visible light source, etc., and the specific selection is determined according to the initiation wavelength of the photoinitiator used. For example, when the photoinitiator can generate a large amount of radicals under ultraviolet light, the ink is used in the ink.
  • the initiator should use ultraviolet light to irradiate the ink during the photocuring reaction; when the photoinitiator can generate a large amount of free radicals under visible light irradiation, it is indicated that the initiator used in the ink should be selected from the visible light to perform the photocuring reaction. Irradiation.
  • the acrylic oligomer is selected from one or more of the group consisting of urethane acrylate, polyester acrylate and polyether acrylate.
  • the acrylic oligomer is a mixture of the above three compounds, the ratio of the above three compounds is not limited in the present invention.
  • the urethane acrylate selected by the present invention mainly means a urethane bond (-NHCOO-)
  • the oligomer can form a plurality of hydrogen bonds between the polymer chains, so that the cured film has excellent wear resistance and flexibility, high elongation at break, and better overall performance. It can be prepared by itself or commercially available, such as CN9110NS, CN963B80, CN966J75NS, CN985B88, CN991NS, CN9167, CN970A60NS, CN975NS, etc.
  • the polyester acrylate of the invention is obtained by acrylation of a low molecular weight polyester diol, has low odor, low irritancy, good flexibility and pigment wettability, and can be selected from commercially available products such as sand.
  • CN 2262, CN2283NS, CN8200, CN8201NS, etc. 6320, 6325-100, 6327-100, 6328, 6333-100, 6351, 6364-1, 6372, 6382, DR-E850, etc. of Taiwan Changxing Company, Cytec Corporation EB81, EB810, etc.
  • the present invention can also select polyether acrylates having good flexibility and yellowing resistance, and such materials are also commercially available, such as the amine modified polyether acrylates CN550 and CN551 of Sartomer, and the low grade of the company.
  • Viscosity polyether acrylates Genomer 3364, Genomer 3414, Genomer 3497, ECECRYL 81 from Cytec, EBECRYL 810, Polyether polyol triacrylate M3130 from Cody.
  • the ink composition of the present invention has a simple composition, does not contain any waxy material, and can be photocured directly under light irradiation, and the curing process is simple.
  • the formed ink composition has better application properties and printing effects by selecting the raw materials of the composition, for example, a viscosity of 25 to 70 cps at room temperature (25 ° C) and a viscosity of 9 to 14.5 at at least one ejection temperature. Cps, so that the ink composition of the present invention provides more excellent printing effects and operational suitability.
  • the viscosity can be reduced to 9 to 14.5 cps, that is, the viscosity of the printing jet is suitable, so the temperature resistance of the ink composition to the print head can be controlled at 40 to 60 ° C, without The temperature-resistant printhead not only saves energy but also extends the life of the printhead. Further, when printing is carried out at 40 to 60 ° C, the surface tension of the ink composition is as low as 20 to 35 dyn, which contributes to rapid setting of the ink composition, and the resulting 3D composition is excellent in stability.
  • the acrylic oligomer comprises a hyperbranched spherical acrylate oligomer having a viscosity of less than 500 cps at 25 °C.
  • a hyperbranched spherical acrylate oligomer can be selected as in Formula 1 At least one dendritic hyperbranched oligomer is shown, wherein A in formula 1 may be acryloxy, methacryloxy, hydroxy, carboxy, epoxy, azide, amino, benzene a base, an ester group, or a more branched carbon chain and having at least one photocurable acryloxy or methacryloyloxy group in the carbon chain.
  • the steric hindrance effect of the spherical molecular shape during polymerization can effectively reduce shrinkage, and therefore, the overall molded part has a low shrinkage rate and a volume shrinkage ratio of less than 5.0. %, the workpiece has no warping deformation.
  • the hyperbranched spherical acrylate oligomer can control the shrinkage rate of the ink composition in the polymerization reaction, avoid the shrinkage which occurs when a large amount of monomers are polymerized, and enhance the stability of the 3D object.
  • the content of the hyperbranched spherical acrylate compound may be controlled to be 30 to 60 parts by weight.
  • the acrylic monomer is more preferably one or more selected from the group consisting of a monofunctional acrylate, a difunctional acrylate, a polyfunctional acrylate, and a vinyl ether monomer.
  • the monofunctional acrylate of the present invention may be an alkyl acrylate, a (meth) acrylate having a cyclic structure or a benzene ring structure, or the like.
  • the alkyl acrylate may be isodecyl acrylate, commercially available products such as EM219, EM2191, EM309, etc. of Taiwan Changxing Co., Ltd.; may be lauryl acrylate, commercially available products such as EM215 of Changxing, Taiwan; etc.; may be ethoxy ethoxy acrylate Ethyl ethyl ester, commercially available products such as EOEOEA of DSM Company, EM211 of Changxing, etc.
  • the structural (meth) acrylate may be isobornyl acrylate IBOA, commercially available products such as SR506NS of Sartomer, EM70 of Changxing, IBXA of Osaka Chemical, etc.; may be tetrahydrofuran (meth) acrylate, commercially available products such as Changxing EM214, EM314, Saudi Arabia's SR285, SR203, etc.; may be phenoxy acrylate, commercially available products such as Changxing 2-phenoxyethyl acrylate EM210, ethoxylated phenoxy acrylate EM2103 and so on.
  • the difunctional acrylate of the present invention may be a propylene glycol diacrylate such as dipropylene glycol diacrylate (DPGDA), a commercially available product such as SR508NS of Sartomer, EM222 of Changxing, etc.; such as tripropylene glycol diacrylate ( TPGDA), commercially available products such as SR306NS from Sartomer, EM223 from Changxing, etc.; other diol diacrylates such as 1,6-hexanediol diacrylate (HDDA), commercially available products such as Shado Ma's SR238NS, Changxing's EM221, DSM's HDDA, etc.; may be a methanol acrylate with a heterocyclic ring, such as tricyclodecane dimethanol diacrylate, commercially available products such as Saudi Arabia's SR833S, Changxing's EM2204, etc. .
  • DPGDA dipropylene glycol diacrylate
  • the polyfunctional acrylate of the present invention comprises a trifunctional monomer and a polyfunctional monomer, wherein the trifunctional monomer may be ethoxylated trimethylolpropane triacrylate (TMPTA), and a commercially available product such as Changxing EM2382, etc. It may be a propoxyglycerol triacrylate, a commercially available product such as Changxing EM8327, etc.; the polyfunctional monomer may be dipentaerythritol pentaacrylate, a commercially available product such as SR399LV NS of Sartomer; notably, polyfunctional
  • TMPTA ethoxylated trimethylolpropane triacrylate
  • a commercially available product such as Changxing EM2382, etc.
  • the polyfunctional monomer may be dipentaerythritol pentaacrylate, a commercially available product such as SR399LV NS of Sartomer
  • polyfunctional The monomer alone does not exceed five functionalities in
  • the acrylic monomer of the present invention further includes a monofunctional acrylate having a specific structure, and may be, for example, acryloylmorpholine ACMO, 3,3,5-trimethylcyclohexane acrylate, a commercially available product such as SR420 of Sartomer, EM2104 of Changxing, etc.; Trimethylolpropane acetal acrylate, commercially available products such as Osaka Chemical's Viscoat #200; may be caprolactone grafted hydroxy acrylate, commercially available products such as Guangzhou Boxing B-30 and so on.
  • a monofunctional acrylate having a specific structure may be, for example, acryloylmorpholine ACMO, 3,3,5-trimethylcyclohexane acrylate, a commercially available product such as SR420 of Sartomer, EM2104 of Changxing, etc.; Trimethylolpropane acetal acrylate, commercially available products such as Osaka Chemical's Viscoat #200;
  • the acrylic monomer is at least two of the monofunctional acrylate, the bifunctional acrylate, the polyfunctional acrylate, and the vinyl ether monomer
  • the acrylic monomer is the most abundant
  • the compound is present in an amount of from 20 to 30 parts by weight, and the most abundant compound has a viscosity at 25 ° C of less than 15 cps.
  • the shrinkage rate of the 3D object can be further controlled by controlling the content and viscosity of various compounds in the acrylic monomer.
  • the colorant is one selected from the group consisting of white, red, yellow, blue, and black self-dispersing nano-scale pigment pastes.
  • the invention adopts a self-dispersing nano-scale pigment paste as a coloring agent because the surface of the self-dispersing nano-scale pigment paste is chemically modified, thereby preventing the pigment from flocculation and sedimentation, thereby ensuring the stability of the ink composition. .
  • the coloring agent is selected from the group consisting of a self-dispersing nano-scale pigment color paste, specifically a self-dispersing nano-scale inorganic pigment color paste or a self-dispersing nano-scale organic pigment color paste, wherein the self-dispersing nano-scale inorganic pigment color paste may be
  • the white pigment paste is specifically titanium dioxide, zinc oxide, zinc antimony white, lead white, etc., and may be a black pigment paste, specifically carbon black, graphite, iron oxide black, aniline black, carbon black, etc.; self-dispersing nano-scale organic pigment
  • the color paste can be a color pigment paste, specifically gold red (PR21), Lisol red (PR49:1), pigment red G (PR37), pigment red 171 (PR171), fast yellow G (PY1), Hansha Yellow R (PY10), permanent yellow GR (PY13), Pigment Yellow 129 (PY129), Pigment Yellow 150 (PY150), Pigment Yellow 185 (PY185), Phthalocyanine Blue (PB15), An
  • the pigment particles in the self-dispersing nano-scale pigment paste have a diameter of less than 500 nm, so that the chance of clogging of the nozzle of the print head can be effectively reduced.
  • the photoinitiator is a hydrogen abstraction type radical photoinitiator and/or a cleavage type radical photoinitiator;
  • the hydrogen abstraction type radical photoinitiator is selected from the group consisting of benzophenone/tertiary amines and sulfur One or more of a fluorenone/tertiary amine;
  • the cleavage type free radical photoinitiator is one selected from the group consisting of an ⁇ -hydroxy ketone, an ⁇ -amino ketone, an acylphosphine oxide, and an oxime esterkind or more.
  • the photoinitiator in the present invention may be any compound as long as it generates a radical under irradiation of a light source, and induces polymerization of the ink composition.
  • a hydrogen abstraction type free radical initiator such as benzophenone/tertiary amine, thioxanthone/tertiary amine, thioxanthone is preferably ITX (isopropyl thioxanthone), and tertiary amine is a co-initiator.
  • a tertiary amine having at least one aH in structure which is a hydrogen donor of a hydrogen abstraction type photoinitiator, preferably a tertiary amine benzoate, a reactive amine or the like in the present invention, and a tertiary amine benzoate having a N , N-dimethylbenzoic acid ethyl ester, N,N-dimethylbenzoic acid 2-ethylhexyl ester, dimethylaminoethyl benzoate, etc.; the active amine is a tertiary amine with an acryloyloxy group, It can participate in the cross-linking reaction.
  • the cleavage type radical photoinitiator may be an ⁇ -hydroxy ketone such as a trade name of 1173 (2-hydroxy-2-methyl-1-phenylacetone) or 184 (1-hydroxy-cyclohexyl benzophenone).
  • 2959 (2-hydroxy-2-A a product such as keto-1-p-hydroxyethylether phenylacetone); may be an ⁇ -amino ketone such as 907(2-methyl-1-[4-methylthiophenyl]-2-morpholinyl -1-acetone), 369 (2-benzyl-2-dimethylamino-1-(4-morpholinyl)-1-butanone) and the like; may be an acylphosphine oxide such as the trade name TEPO ( 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide), TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide), 819 (double (2) , 4,6-trimethylbenzoyl)phenylphosphine oxide) and other products; oxime esters such as BASF's Irgacure OXE 01 and Irgacure OXE 02, the structural formula is
  • auxiliary agent is selected from one or more of a toughening agent, an antifoaming agent, a leveling agent, and a stabilizer.
  • the toughening agent can be polycaprolactone triol and polyol products, such as 305T, 205N of the company, Goodech GT8003 of Gudi, etc.; the type of defoamer is not limited, as long as it can eliminate the filtration And the bubbles generated during the printing process, to avoid the occurrence of bubbles affecting the printing fluency, for example, the optional defoaming agent is BYK silicone and polymer defoamer BYK-088, modified polysiloxane Copolymer solution BYK-1798, etc., Digo's silicone-free defoamer TEGO Airex 920, TEGO Airex 921, etc.; leveling agent is mainly to promote the surface level of printing ink, reduce shrinkage, traces and other defects, Thereby obtaining a smooth and flat surface; the leveling agent used in the invention may be BYK-333, BYK-371, BYK-377, etc.
  • the stabilizer that is, the polymerization inhibitor, prevents the ink from being deposited and ensures the ink storage process.
  • the commonly used stabilizers may be GENORAD 16, GenoRAD 18, GENORAD 20, GENORAD 22, etc. of the company.
  • the present invention also provides an ink set, wherein the ink set is a combination of at least two ink compositions in any one of the above ink compositions, wherein the at least two ink compositions contain colorants of different colors And the content of the colorant in the at least two ink compositions of the different colorants satisfies the following relationship:
  • the ink set is a combination of at least two ink compositions of different colors.
  • the absorption of light energy is different because the pigments of different colors absorb light.
  • the intensity of the absorbed light energy is black > yellow > blue > red > white, that is, the black absorption is the strongest and the reaction is the least. Therefore, the black ink composition is used to minimize the volumetric shrinkage when printing 3D objects. While increasing the pigment concentration, the color of the ink composition is deepened, and the higher color depth causes the printed 3D object to rapidly decrease in the illumination energy along the illumination direction, the surface of the 3D object shrinks quickly, the inner layer shrinks slowly, and a large internal stress is generated. , resulting in defects such as cracking of 3D objects.
  • the white colorant in the white ink composition in the ink set needs to have a greater weight fraction in the ink composition than the red colorant in the red ink composition.
  • the parts by weight of the red colorant in the ink composition of the red ink composition need to be greater than the parts by weight of the blue colorant in the ink composition of the blue ink composition in parts by weight of the ink composition, blue
  • the amount of the blue colorant in the ink composition in the ink composition is required to be greater than the weight portion of the yellow colorant in the ink composition of the yellow ink composition, and the yellow colorant in the yellow ink composition is in the ink combination thereof.
  • the parts by weight in the black ink composition are required to be larger than the parts by weight of the black colorant in the ink composition. Only the ink set satisfying the above-mentioned parts by weight of the ink composition can ensure that the printed multi-color 3D object has good mechanical properties and is less prone to crack delamination.
  • the present invention also provides a method for preparing the ink composition for 3D inkjet printing according to any of the above, comprising the steps of:
  • the preparation method of the invention can be completed only by mixing and filtering, is simple and easy to operate, and is not only beneficial to form a stable ink composition, but also facilitates liquefaction and ejection of the ink composition, thereby being more convenient to use, and is particularly suitable for use in 3D objects. Print.
  • the preparation of the ink composition of the present invention is preferably carried out in an environment other than the wavelength at which the photoinitiator is used in the ink to avoid polymerization of the light-inducing ink composition in the environment.
  • the filtering is to perform secondary filtration on the third mixture by using a microporous membrane; wherein the first stage filtration uses a glass fiber membrane having a pore diameter of 0.6 ⁇ m, and the second stage filtration uses a polymerization having a pore diameter of 0.2 ⁇ m.
  • Acrylic film (referred to as PP film).
  • the time to control the degassing treatment is not higher than 5h.
  • the operation mode of the degassing treatment is selected from the group consisting of vacuum degassing, atmospheric degassing, and heated degassing.
  • the degassing time is controlled to be 1 to 3 hours.
  • the ink composition of the invention has simple composition and convenient use, and the viscosity of the ink composition can be reduced to the viscosity of the suitable print head at at least one temperature of 40 to 60 ° C, thereby not only saving energy but also prolonging the service life of the print head. .
  • the ink composition of the present invention has a wide application range, and the generated 3D object does not deform due to temperature, and the ink composition does not contain volatile organic solvent, no VOC emission, and no pollution. After the ink composition is sprayed, it can be completely cured by simply irradiating the light source, and the curing process is simple.
  • the ink composition of the present invention can effectively prevent the pigment from flocculation, not only ensuring the stability of the ink composition, but also avoiding the risk of the nozzle of the print head being clogged.
  • the 3D object produced by using the ink composition of the present invention and the ink set has a low shrinkage rate, a volume shrinkage ratio of less than 5%, and no warpage deformation of the article.
  • the preparation method of the ink composition of the invention is simple, easy to control, does not require assistance from large equipment, and has low production cost.
  • the particle size distribution of the ink composition is tested by using an Occidental LS900 laser particle size analyzer
  • the ink composition of the present embodiment is applied to a 3D photocurable inkjet printer of an industrial nozzle,
  • the wavelength of the light source was set to 395 nm, and the ink fluency test and the accuracy test of the molded part were carried out at the injection temperatures of 40 ° C, 50 ° C and 60 ° C respectively.
  • the accuracy test was mainly reflected by the volume shrinkage rate.
  • the test method was:
  • the density ⁇ 1 before curing of the photosensitive resin and the density ⁇ 2 after curing were measured at 25 ° C with water as reference, and the volume shrinkage was calculated by the following formula:
  • the preparation method of the ink composition in this embodiment was basically the same as that in the first embodiment except that the time for deaeration under reduced pressure was adjusted to 2 hours, and finally a yellow ink composition applied to 3D inkjet printing was obtained.
  • the preparation method of the ink composition in this embodiment was basically the same as that in the first embodiment except that the time for deaeration under reduced pressure was adjusted to 3 hours, and finally a blue ink composition applied to 3D inkjet printing was obtained.
  • the preparation method of the ink composition in this embodiment is basically the same as that in the first embodiment except that the degassing treatment is carried out by standing degassing under normal pressure, and finally a white ink composition applied to 3D inkjet printing is obtained.
  • the preparation method of the ink composition in this embodiment is basically the same as that in the first embodiment except that the temperature of the ink composition is heated to 40-60 ° C for degassing by means of heating and degassing, and finally the black applied to the 3D inkjet printing is obtained.
  • Ink composition is basically the same as that in the first embodiment except that the temperature of the ink composition is heated to 40-60 ° C for degassing by means of heating and degassing, and finally the black applied to the 3D inkjet printing is obtained. Ink composition.
  • the preparation method of the ink composition in this embodiment is basically the same as that in the first embodiment except that the degassing treatment is carried out by standing degassing under normal pressure, and finally a transparent ink composition applied to 3D inkjet printing is obtained.
  • the preparation method of the ink composition in this embodiment was basically the same as that in the first embodiment except that the time for deaeration under reduced pressure was adjusted to 3 hours, and finally a white ink composition applied to 3D inkjet printing was obtained.
  • the preparation method of the ink composition in this embodiment was basically the same as that in the first embodiment except that the time for deaeration under reduced pressure was adjusted to 2 hours, and finally a yellow ink composition applied to 3D inkjet printing was obtained.
  • the preparation method of the ink composition in this embodiment is basically the same as that in the first embodiment except that the degassing treatment is carried out by standing degassing under normal pressure, and finally a transparent ink composition applied to 3D inkjet printing is obtained.
  • the ink composition of the present invention has a viscosity at room temperature of less than 70 cps, and the viscosity thereof is remarkably lowered as the temperature is raised, and the viscosity of the suitable print head ejection can be attained at at least one of 40 to 60 ° C. Eliminates the need for high temperature printheads and extends printhead life.
  • the ink composition of the present invention has a moderate surface tension, so that the deformation of the 3D object formed during printing may be low.
  • the ink composition of the present invention has a low shrinkage rate, so that the formed molded article of the 3D object has a low shrinkage rate and does not undergo warpage.
  • the ink composition of the present invention has good fluidity, wherein the particle size is small, so that the stability of the ink composition can be ensured, and the problem of clogging of the print head nozzle during printing is avoided.
  • the ink composition in each of the above embodiments can constitute a combination of ink set conditions, firstly, the ink composition has the same normal ejection temperature, and secondly, the amount of the colorant contained in each ink composition in the ink set satisfies the white coloring agent>red coloring.
  • the ink composition in each of the above embodiments may constitute any combination of two or more ink compositions of the first embodiment, the fifth embodiment, the seventh embodiment and the eighth embodiment; and the second embodiment and the third embodiment Any combination of two or more of the ink compositions of the fourth embodiment and the fifth embodiment.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

一种3D喷墨打印用墨水组合物、墨水组及其制备方法，墨水组合物包括如下重量份的成分：丙烯酸低聚物45～75份，丙烯酸单体20～45份，光引发剂1～9份，助剂0.2～10份，着色剂0～4份；丙烯酸低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯和聚醚丙烯酸酯中的一种或多种；所述墨水组合物在室温下所具有的粘度位于25～70cps之间；所述墨水组合物在喷射温度下所具有的表面张力位于20～35dyn之间；所述墨水组合物在至少一个喷射温度下所具有的粘度位于9～14.5cps之间。所述墨水组合物组成简单，能够延长打印头的使用寿命，并且固化过程简单，无VOC排放，无污染，制件无翘曲变形。

Description

3D喷墨打印用墨水组合物、墨水组及其制备方法 技术领域
本发明涉及打印技术，尤其涉及一种3D喷墨打印用墨水组合物、墨水组及其制备方法。
背景技术
3D喷墨打印技术是根据喷墨打印机的工作原理，在数字信号的激励下使喷嘴腔室中的液体(成型材料)在瞬间形成液滴，并以一定的速度和频率从喷嘴中喷出，按指定路径逐层固化成型，最终得到3D物体。
现有3D喷墨打印机进行喷墨打印所用的成型材料可分为温度固化材料和UV光固化材料两大类，其中温度固化材料主要为含有蜡的材料，固体或半固体的蜡状材料通过加热熔融变为流体状材料进入打印头喷嘴进行喷墨打印，当蜡液滴从打印头喷嘴喷出落到前一承载体上时，温控装置对刚喷出的蜡液滴具有一个降温的过程使蜡液滴在指定轨迹上固化，根据3D物体的模型数据后一层按照同样的方式叠加固化在前一层上，最终形成目标3D物体，但是由于蜡受温度影响较大，尤其在高温情况下容易发生熔融，因而导致其应用范围受到影响。
UV光固化材料至少含有光敏树脂和引发剂，例如欧洲专利EP1458825B1公开了一种辐射固化组合物，其中包含至少一种可UV辐射固化的尿烷甲基丙烯酸树脂，至少一种蜡，至少一种甲基丙烯酸稀释剂，至少一种光引发剂和至少一种聚合引发剂，该组合物用于喷墨打印时需将组合物的温度升高至70-90℃，组合物从打印头喷出后提供一个降温环境将分配的组合物材料转变为固体，之后用UV光进行辐射形成3D物体的层，之后重复前述的步骤形成3D物体。由于该组合物使用时需要高温使其融化因此在打印机设计时其安装的打印头必须能耐高温，由此一方面高温对打印头的使用寿命造成影响，另一方面能耗较高，且组合物中含有蜡和树脂材料，这是两类性质完全不同的材料，在进行固化过程中分两步进行，先通过降温使组合物不完全固化，再经过UV光进行进一步固化，前者是物理过程后者是化学过程，这导致组合 物使用复杂。
发明内容
针对上述技术缺陷，本发明提供一种3D喷墨打印用墨水组合物、墨水组及其制备方法，该墨水组合物制造的3D物体的稳定性佳，不会由于温度因素而发生形变，并且能够降低打印头的工作温度，固化过程简单。
本发明提供一种3D喷墨打印用墨水组合物，包括如下重量份的成分：丙烯酸低聚物45～75份，丙烯酸单体20～45份，光引发剂1～9份，助剂0.2～10份，着色剂0～4份；所述丙烯酸低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯和聚醚丙烯酸酯中的一种或多种；
所述墨水组合物在室温下所具有的粘度位于25～70cps之间；所述墨水组合物在至少一个喷射温度下所具有的粘度位于9～14.5cps之间。
本发明的墨水组合物在进行喷墨打印的过程中，光源照射在已形成的3D物体片层上，诱发墨水组合物中的光引发剂产生自由基，从而促使丙烯酸低聚物和丙烯酸单体发生聚合反应。其中，丙烯酸低聚物能够增强3D物体的耐磨性和柔韧性，丙烯酸单体能够快速发生聚合反应，光引发剂能够诱发墨水组合物在光源照射下发生聚合，当着色剂用量为零时即为透明墨水组合物。而适量的助剂以及着色剂能够优化3D物体的打印效果，由于增大着色剂浓度会减少墨水组合物用于打印3D物体时的体积收缩，但是着色剂又会阻碍墨水组合物发生聚合反应，从而导致打印的3D物体力学性能下降，因此，着色剂的重量份不能大于4，其中，当着色剂为0时即为透明墨水组合物。本发明中光源可以为紫外光光源或可见光光源等，具体选择根据所用的光引发剂的引发波长来确定，例如，当光引发剂在紫外光照射下能产生大量自由基时说明墨水中使用该引发剂在进行光固化反应时应该选用紫外光对墨水进行照射；当光引发剂在可见光照射下能产生大量自由基时说明墨水中使用该引发剂在进行光固化反应时应该选用可见光对墨水进行照射。
其中，丙烯酸低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯和聚醚丙烯酸酯中的一种或多种。当丙烯酸低聚物为上述三种化合物的混合物时，本发明对上述三种化合物的比例不做限制。
具体地，本发明选择的聚氨酯丙烯酸酯主要是指含有氨酯键(-NHCOO-) 的低聚物，它能在高分子链间形成多种氢键，使固化膜具有优异的耐磨性和柔韧性，断裂伸长率高，具有较佳的综合性能。可以自行制备，也可以商购，例如沙多玛的CN9110NS、CN963B80、CN966J75NS、CN985B88、CN991NS、CN9167、CN970A60NS、CN975NS等，台湾长兴公司的聚氨酯丙烯酸低聚物6101、6103、6153-1、6155W、6185、5104D、DR-U011、DR-U012、DR-U250、DR-U381等，润奥的Unicryl R-7162，锐昂的Genomer 1122、Genomer 4297、Greatech GT8010、Greatech GT8440、Greatech GT-8220、Greatech GT-8270等。
本发明的聚酯丙烯酸酯是由低分子量聚酯二醇经丙烯酸酯化而制得，具有低气味、低刺激性、较好的柔韧性和颜料润湿性，可以选择商购产品例如沙多玛公司的CN2262、CN2283NS、CN8200、CN8201NS等，台湾长兴公司的6320、6325-100、6327-100、6328、6333-100、6351、6364-1、6372、6382、DR-E850等，氰特公司的EB81、EB810等。
本发明还可以选择具有良好柔韧性和耐黄变性的聚醚丙烯酸酯，此类材料亦可选择商购，例如沙多玛公司的胺改性聚醚丙烯酸酯CN550、CN551，锐昂公司的低粘度聚醚丙烯酸酯Genomer 3364、Genomer 3414、Genomer 3497，氰特公司的EBECRYL 81、EBECRYL 810，古迪公司的聚醚多元醇三丙烯酸酯M3130等。
本发明的墨水组合物组成简单，不含有任何蜡质材料，能够直接在光照射下进行光固化，固化过程简单。通过对组合物原料的选择使形成的墨水组合物具有更优的应用性能和打印效果，例如，室温(25℃)时粘度为25～70cps，在至少一个喷射温度时，其粘度为9～14.5cps，从而使本发明的墨水组合物提供更优异的打印效果和操作适性。
具体在40～60℃时，其粘度就能够降低至9～14.5cps，即适宜进行打印喷射的粘度，因此该墨水组合物对打印头的耐温性要求控制在40～60℃即可，无需耐温性强的打印头，不仅能够节约能耗还能够有效延长打印头的使用寿命。并且在40～60℃进行打印时，该墨水组合物的表面张力低至20～35dyn，因此有助于墨水组合物的快速定型，生成的3D组合物稳定性佳。
进一步地，所述丙烯酸低聚物中包含在25℃时粘度小于500cps的超支化球型丙烯酸酯低聚物。例如，超支化球型丙烯酸酯低聚物可以选择如式1 所示的至少一种树枝状超支化低聚物，其中，式1中的A可以为丙烯酰氧基、甲基丙烯酰氧基、羟基、羧基、环氧基、叠氮基、氨基、苯基、酯基，或支化度更高的碳链且碳链中至少含有一种可进行光固化的丙烯酰氧基或甲基丙烯酰氧基。
[式1]
Figure PCTCN2016087019-appb-000001
采用低粘度的超支化球型丙烯酸酯低聚物，其球状分子外形在聚合反应时所产生的位阻效应能够有效降低收缩，因此，整体成型件收缩率低，并且其体积收缩率低于5.0％，制件无翘曲变形。同时，超支化球型丙烯酸酯低聚物能够控制墨水组合物在发生聚合反应时的收缩率，避免了现有采用大量单体聚合时产生的收缩，增强了3D物体的稳定性。在本发明的实施方案，45～75份丙烯酸低聚物中，可以控制所述超支化球型丙烯酸酯类化合物的重量份数为30～60份。目前市售的在25℃时粘度小于500cps的超支化球型丙烯酸酯低聚物产品很多，如深圳撒比斯公司的功能性球型丙烯酸酯SPC-1495等，沙多玛的多官能度的聚酯类超支化低聚物CN2302、CN2303等、台湾长兴公司的6361-100等。
进一步地，所述丙烯酸单体更好是选自单官能团丙烯酸酯、双官能团丙烯酸酯、多官能团丙烯酸酯和乙烯基醚类单体中的一种或多种。
具体地，本发明的单官能团丙烯酸酯可以是丙烯酸烷基酯、带有环状结构或苯环结构的(甲基)丙烯酸酯等。丙烯酸烷基酯可以为丙烯酸异癸酯，市售产品如台湾长兴公司的EM219、EM2191、EM309等；可以是丙烯酸月桂酯，市售产品如台湾长兴的EM215等；可以是丙烯酸乙氧基乙氧基乙酯，市售产品如DSM公司的EOEOEA、长兴的EM211等。带有环状结构或苯环 结构的(甲基)丙烯酸酯可以是丙烯酸异冰片酯IBOA，市售产品如沙多玛的SR506NS，长兴的EM70，大阪化学的IBXA等；可以是四氢呋喃(甲基)丙烯酸酯，市售产品如长兴的EM214、EM314，沙多玛的SR285、SR203等；可以是苯氧基丙烯酸酯，市售产品如长兴的2-苯氧基乙基丙烯酸酯EM210、乙氧化苯氧基丙烯酸酯EM2103等。
本发明的双官能团丙烯酸酯可以是丙二醇类二丙烯酸酯，如二丙二醇二丙烯酸酯(DPGDA)，市售产品如沙多玛公司的SR508NS，长兴的EM222等；如二缩三丙二醇二丙烯酸酯(TPGDA)，市售产品如沙多玛公司的SR306NS，长兴的EM223等；可以是其他二醇类二丙烯酸酯，如1,6-己二醇二丙烯酸酯(HDDA)，市售产品如沙多玛的SR238NS，长兴的EM221，DSM公司的HDDA等；可以是带有杂环的甲醇丙烯酸酯，如三环癸烷二甲醇二丙烯酸酯，市售产品如沙多玛的SR833S，长兴的EM2204等。
本发明的多官能团丙烯酸酯包括三官能度单体和多官能度单体，其中三官能度单体可以是乙氧化三羟甲基丙烷三丙烯酸酯(TMPTA)，市售产品如长兴的EM2382等；可以是丙氧化甘油三丙烯酸酯，市售产品如长兴的EM8327等；多官能度单体可以是二季戊四醇五丙烯酸酯，市售产品如沙多玛的SR399LV NS；值得注意的是，多官能度单体在本发明中不超过五官能度，否则打印的3D物体体积收缩率会很大，将超过20％。
本发明的乙烯基醚类单体是指含有-O-CH＝CH2或-O-CH2CH＝CH2结构的单体，可以是正丁基缩水甘油醚、三乙二醇二乙烯基醚(DVE-3)等。
除此之外，本发明的丙烯酸单体还包括含有特殊结构的单官能团丙烯酸酯，例如可以是丙烯酰吗啉ACMO，3,3,5-三甲基环己烷丙烯酸酯，市售产品如沙多玛的SR420、长兴的EM2104等；三羟甲基丙烷缩甲醛丙烯酸酯，市售产品如大阪化学的Viscoat#200；可以是己内酯接枝丙烯酸羟酯，市售产品如广州博兴B-30等。
进一步地，当所述丙烯酸单体为所述单官能团丙烯酸酯、双官能团丙烯酸酯、多官能团丙烯酸酯和乙烯基醚类单体中的至少两种化合物时，所述丙烯酸单体中含量最多的化合物的重量份数为20～30份，且所述含量最多的化合物在25℃时的粘度小于15cps。通过控制丙烯酸单体中各种化合物的含量和粘度，能够进一步控制3D物体的收缩率。
进一步地，所述着色剂选自白色、红色、黄色、蓝色和黑色的自分散型纳米级颜料色浆中的一种。本发明采用自分散型纳米级颜料色浆作为着色剂原因在于，自分散型纳米级颜料色浆的表面经过了化学修饰，因此能够防止颜料发生絮凝聚沉，从而保证了墨水组合物的稳定性。
本发明中着色剂选自自分散型纳米级颜料色浆，具体为自分散型纳米级无机颜料色浆或自分散型纳米级有机颜料色浆，其中自分散型纳米级无机颜料色浆可以是白色颜料色浆具体有二氧化钛、氧化锌、锌钡白、铅白等，可以是黑色颜料色浆具体有炭黑、石墨、氧化铁黑、苯胺黑，炭黑等；自分散型纳米级有机颜料色浆可以是彩色颜料色浆具体有金光红(PR21)、立索尔大红(PR49：1)、颜料红G(PR37)、颜料红171(PR171)、耐晒黄G(PY1)、汉沙黄R(PY10)、永固黄GR(PY13)、颜料黄129(PY129)、颜料黄150(PY150)、颜料黄185(PY185)、酞菁蓝(PB15)、靛蒽酮(PB60)等。需要注意的是，每个墨水组合物是单色的，也就是说一个墨水组合物中只含有一种颜色的着色剂。
进一步地，所述自分散型纳米级颜料色浆中的颜料颗粒直径小于500nm，从而能够有效减少打印头的喷嘴发生堵塞的机会。
进一步地，所述光引发剂为夺氢型自由基光引发剂和/或裂解型自由基光引发剂；所述夺氢型自由基光引发剂选自二苯甲酮/叔胺类和硫杂蒽酮/叔胺类中的一种或多种；所述裂解型自由基光引发剂选自α-羟基酮类、α－胺基酮类、酰基膦氧化物和肟酯类中的一种或多种。
本发明中光引发剂可以是任意化合物，只要其在光源照射下能产生自由基，诱发墨水组合物发生聚合反应即可。其中，夺氢型自由基引发剂如二苯甲酮/叔胺、硫杂蒽酮/叔胺类，硫杂蒽酮优选ITX(异丙基硫杂蒽酮)，叔胺类为助引发剂，在结构上至少含有一个a-H的叔胺，是夺氢型自由基光引发剂的供氢体，本发明优选叔胺性苯甲酸酯、活性胺等，叔胺性苯甲酸酯有N,N-二甲基苯甲酸乙酯、N,N-二甲基苯甲酸-2-乙基己酯、苯甲酸二甲氨基乙酯等；活性胺为带有丙烯酰氧基的叔胺，可参与交联反应，市售产品有长兴的反应型三级胺助引发剂6420、锐昂的Genomer 5142、氰特的EBECRYL 7100等。另外，裂解型自由基光引发剂可以是α－羟基酮类例如商品名为1173(2-羟基-2-甲基-1-苯基丙酮)、184(1-羟基-环己基苯甲酮)、2959(2-羟基-2-甲 基-1-对羟乙基醚基苯基丙酮)等产品；可以是α－胺基酮类例如907(2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮)、369(2-苄基-2-二甲氨基-1-(4-吗啉苯基)-1-丁酮)等产品；可以是酰基膦氧化物例如商品名为TEPO(2,4,6-三甲基苯甲酰基-乙氧基-苯基氧化膦)，TPO(2,4,6-三甲基苯甲酰基-二苯基氧化膦)、819(双(2,4,6-三甲基苯甲酰基)苯基氧化膦)等产品；肟酯类例如巴斯夫的Irgacure OXE 01及Irgacure OXE 02，其结构式分别为
Figure PCTCN2016087019-appb-000002
等。
进一步地，所述助剂选自增韧剂、消泡剂、流平剂和稳定剂中的一种或多种。
其中，增韧剂可以为聚己内酯三元醇及多元醇类产品，如易生公司的305T、205N,古迪公司的Greatech GT8003等；消泡剂种类不受限制，只要其能消除过滤及打印过程中所产生的气泡，避免产生的气泡影响打印流畅性即可，例如可选择的消泡剂为BYK公司的有机硅和聚合物消泡剂BYK-088等、改性聚硅氧烷共聚物溶液BYK-1798等，迪高的不含有机硅消泡剂TEGO Airex 920、TEGO Airex 921等；流平剂主要作用是为了促进打印墨水表面流平，减少缩孔、痕道等弊病，从而获得光滑平整的表面；本发明采用的流平剂可以为毕克公司的BYK-333、BYK-371、BYK-377等；稳定剂即阻聚剂可防止墨水发生沉积，保证墨水储存过程中的稳定性，常用的稳定剂可以是锐昂公司的GENORAD 16、GENORAD 18、GENORAD 20、GENORAD 22等。
本发明还提供一种墨水组，所述墨水组为上述任一所述墨水组合物中的至少两种墨水组合物的组合，其中，所述至少两种墨水组合物中含有不同颜色的着色剂，并且所述不同颜色着色剂在所述至少两种墨水组合物中着色剂的含量满足如下关系：
白色着色剂＞红色着色剂＞蓝色着色剂＞黄色着色剂＞黑色着色剂。
由于在进行打印的时候，需要将墨水组合物放入打印机的墨水盒中，如果即将打印的物体是多色的，则需要将多个不同颜色的墨水组合物分别放入 打印机的数个墨水盒中，此时的多个不同颜色的墨水组合物便构成了墨水组。所以说，墨水组是至少两个不同颜色的墨水组合物的组合。
当使用墨水组进行打印作业时，由于不同颜色的颜料对光的吸收程度不一样，其吸收光能量强弱为黑色>黄色>蓝色>红色>白色，即黑色吸收最强，反应最不充分，所以黑色墨水组合物用于打印3D物体时体积收缩最小。在增大颜料浓度的同时墨水组合物的颜色加深，而较高的颜色深度会导致打印的3D物体沿照射方向光照能量迅速递减，3D物体表层收缩快，内层收缩慢，产生较大内应力，由此造成3D物体开裂等缺陷。为了克服上述缺陷，在使用不同颜色的墨水组合物进行墨水组组合时，墨水组中的白色墨水组合物中白色着色剂在其墨水组合物中的重量份需要大于红色墨水组合物中红色着色剂在其墨水组合物中的重量份，红色墨水组合物中红色着色剂在其墨水组合物中的重量份需要大于蓝色墨水组合物中蓝色着色剂在其墨水组合物中的重量份，蓝色墨水组合物中蓝色着色剂在其墨水组合物中的重量份需要大于黄色墨水组合物中黄色着色剂在其墨水组合物中的重量份，黄色墨水组合物中黄色着色剂在其墨水组合物中的重量份需要大于黑色墨水组合物中黑色着色剂在其墨水组合物中的重量份。只有满足上述重量份的墨水组合物的墨水组，才能保证打印出来的多色的3D物体力学性能佳，不易发生断裂分层等现象。
本发明还提供一种上述任一所述3D喷墨打印用墨水组合物的制备方法，包括如下步骤：
1)将45～75份丙烯酸低聚物、20～45份丙烯酸单体和0.2～10份助剂混合均匀，生成第一混合物；随后向所述第一混合物中加入1～9份光引发剂直至所述光引发剂溶解完全，生成第二混合物；向所述第二混合物中加入0～4份着色剂并混合均匀，生成第三混合物；
2)过滤所述第三混合物，收集滤液，得到所述墨水组合物。
当将着色剂加入至第二混合物中后，可以使用高速剪切分散机使混合均匀，从而得到第三混合物。本发明的制备方法只通过混合、过滤便可完成，简单易操作，不仅有利于形成稳定的墨水组合物，还有利于墨水组合物的液化以及喷射，从而使用更加方便，特别适合用于3D物体的打印。
本发明中墨水组合物的制备优选在墨水中所用光引发剂引发波长之外的环境下进行，避免环境中的光诱发墨水组合物发生聚合反应。
进一步地，所述过滤为采用微孔滤膜对所述第三混合物进行二级过滤；其中，第一级过滤采用孔径为0.6μm的玻璃纤维膜，第二级过滤采用孔径为0.2μm的聚丙烯膜(简称PP膜)。
进一步地，还包括对所收集的滤液进行脱气处理。控制脱气处理的时间不高于5h。脱气处理的操作方式选自减压脱气、常压脱气和加热脱气中的一种，优选的，将脱气时间控制在1～3h。通过对墨水组合物进行脱气处理，使墨水组合物在使用过程中流畅性好，不会因为墨水组合物中气泡的干扰而引起打印断线，最终影响3D物体的成型精度。
本发明的实施，至少具有以下优势：
1、本发明的墨水组合物组成简单，使用方便，40～60℃中至少一个温度下其粘度便可降低至适宜打印头喷射的粘度，因此不仅节约能耗还能有效延长打印头的使用寿命。
2、本发明的墨水组合物应用范围广，生成的3D物体不会因为温度原因而发生形变，并且墨水组合物中不含有挥发性有机溶剂，无VOC排放，无污染。墨水组合物经过喷射后，只需经过光源照射便能全部固化，固化过程简单。
3、本发明的墨水组合物能够有效避免颜料发生絮凝聚沉，不仅保证了墨水组合物的稳定性，也避免了打印头喷嘴被堵塞的风险。
4、利用本发明的墨水组合物以及墨水组生成的3D物体收缩率低，体积收缩率低于5％，制件无翘曲变形。
5、本发明墨水组合物的制备方法简单，易于控制，无需大型设备协助，生产成本低。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例的墨水组合物，按照重量份包括如下组分：
Figure PCTCN2016087019-appb-000003
制备方法：
(1)称取30份聚酯类超支化低聚物CN2302、23.8份单官能聚氨酯丙烯酸酯CN975S、15份1,6-己二醇二丙烯酸酯SR238NS、25份3,3,5-三甲基环己烷丙烯酸酯SR420以及0.3份GENORAD16、0.5g BYK-333于玻璃容器中，采用搅拌器进行搅拌至各材料混合均匀后，生成第一混合物；称取光引发剂TPO 1.6份、184 2份至第一混合物中，之后继续进行搅拌至光引发剂完全溶解得到第二混合物，最后向第二混合物中加入1.8份金光红(PR21)红色颜料后转移至VFF-230智能型分散砂磨机中中进行高速剪切分散，至混合均匀，得到第三混合物；
(2)用0.6μm的玻璃纤维膜对第三混合物进行一级过滤后，再用0.2μm的PP膜进行二级过滤，得到滤液；随后在0.1MPa真空度下，对滤液减压抽滤1小时，除去滤液中的气泡，最后得到应用于3D喷墨打印的红色墨水组合物。
对本实施例1中的墨水组合物进行性能测试：
1、采用DV-I数显粘度计和BZY-1全自动表面张力仪对本实施例中的墨水组合物在室温和喷射温度40℃-60℃下的粘度和表面张力进行测试。
2、采用欧美克LS900激光粒度分析仪测试墨水组合物的粒径分布；
3、将本实施例的墨水组合物应用于工业喷头的3D光固化喷墨打印机上， 并将光源波长设为395nm，分别在喷射温度40℃、50℃和60℃下进行墨水流畅性测试以及成型件的精度测试，该精度测试主要通过体积收缩率来反映，测试方法为：
采用比重瓶法，以水为参比，在25℃下测定光敏树脂固化前的密度ρ1及其完全固化后的密度ρ2，以下式计算体积收缩率：
Figure PCTCN2016087019-appb-000004
各测试结果见下表1。
实施例2
Figure PCTCN2016087019-appb-000005
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是将减压脱气的时间调整为2小时，最后得到应用于3D喷墨打印的黄色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例3
Figure PCTCN2016087019-appb-000006
Figure PCTCN2016087019-appb-000007
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是将减压脱气的时间调整为3小时，最后得到应用于3D喷墨打印的蓝色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例4
Figure PCTCN2016087019-appb-000008
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是采用常压静置脱气进行脱气处理，最后得到应用于3D喷墨打印的白色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例5
Figure PCTCN2016087019-appb-000009
Figure PCTCN2016087019-appb-000010
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是采用加热脱气的方式将墨水组合物温度加热到40-60℃进行脱气处理，最后得到应用于3D喷墨打印的黑色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例6
Figure PCTCN2016087019-appb-000011
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是采用常压静置脱气进行脱气处理，最后得到应用于3D喷墨打印的透明墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例7
Figure PCTCN2016087019-appb-000012
Figure PCTCN2016087019-appb-000013
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是将减压脱气的时间调整为3小时，最后得到应用于3D喷墨打印的白色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例8
Figure PCTCN2016087019-appb-000014
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是将减压脱气的时间调整为2小时，最后得到应用于3D喷墨打印的黄色墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
实施例9
Figure PCTCN2016087019-appb-000015
制备方法：
本实施例中墨水组合物的制备方法与实施例一基本相同，只是采用常压静置脱气进行脱气处理，最后得到应用于3D喷墨打印的透明墨水组合物。
按照与实施例1相同的测试方法，对本实施例中的墨水组合物进行性能测试，测试结果见表1。
表1各实施例中墨水组合物的性能参数
Figure PCTCN2016087019-appb-000016
Figure PCTCN2016087019-appb-000017
“-”表示墨水组合物在对应温度下不适用而未进行测试
由表1结果可知:
1、本发明的墨水组合物在室温下粘度均小于70cps，并且随着温度的升高其粘度显著降低，在40～60℃中的至少一个温度时便能达到适宜打印头喷射的粘度，因此无需使用耐高温打印头，并且能够有效延长打印头的使用寿命。
2、本发明的墨水组合物表面张力适中，因此在打印过程中形成的3D物体形变可能较低。
3、本发明的墨水组合物收缩率低，因此制成的3D物体整体成型件收缩率低，不会发生翘曲变形。
4、本发明的墨水组合物流畅性好，其中的颗粒粒径小，因此能够保证墨水组合物的稳定性，并且避免了打印过程中打印头喷嘴堵塞问题的发生。
以上各实施例中的墨水组合物能够构成墨水组组合使用的条件，首先是墨水组合物正常喷射温度相同，其次是墨水组中各墨水组合物所含着色剂的量满足白色着色剂＞红色着色剂＞蓝色着色剂＞黄色着色剂＞黑色着色剂；
上述各实施例中的墨水组合物可以构成墨水组的有实施例一、实施例五、实施例七和实施例八中任意两种或多种墨水组合物组合；以及实施例二、实施例三、实施例四和实施例五中任意两种或多种墨水组合物组合。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (16)

  1. 一种3D喷墨打印用墨水组合物，其特征在于，包括如下重量份的成分：丙烯酸低聚物45～75份，丙烯酸单体20～45份，光引发剂1～9份，助剂0.2～10份，着色剂0～4份；所述丙烯酸低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯和聚醚丙烯酸酯中的一种或多种；
    所述墨水组合物在室温下所具有的粘度位于25～70cps之间；所述墨水组合物在至少一个喷射温度下所具有的粘度位于9～14.5cps之间。
  2. 根据权利要求1所述的墨水组合物，其特征在于，所述喷射温度位于40～60℃之间。
  3. 根据权利要求2所述的墨水组合物，其特征在于，所述墨水组合物在40～60℃之间表面张力为20～45dyn。
  4. 根据权利要求3所述的墨水组合物，其特征在于，所述丙烯酸低聚物中包含在25℃时粘度小于500cps的超支化球型丙烯酸酯低聚物。
  5. 根据权利要求4所述的墨水组合物，其特征在于，所述超支化球型丙烯酸酯低聚物的重量份数为30～60份。
  6. 根据权利要求3所述的墨水组合物，其特征在于，所述丙烯酸单体选自单官能团丙烯酸酯、双官能团丙烯酸酯、多官能团丙烯酸酯和乙烯基醚类单体中的一种或多种。
  7. 根据权利要求6所述的墨水组合物，其特征在于，所述多官能团丙烯酸酯中，官能团度≤5。
  8. 根据权利要求6-7中任一所述的墨水组合物，其特征在于，所述丙烯酸单体为所述单官能团丙烯酸酯、双官能团丙烯酸酯、多官能团丙烯酸酯和乙烯基醚类单体中的至少两种化合物，所述丙烯酸单体中含量最多的化合物的重量份数为20～30份，且所述含量最多的化合物在25℃时的粘度小于15cps。
  9. 根据权利要求3所述的墨水组合物，其特征在于，所述着色剂选自白色、红色、黄色、蓝色和黑色的自分散型纳米级颜料色浆中的一种。
  10. 根据权利要求9所述的墨水组合物，其特征在于，所述自分散型纳米级颜料色浆中的颜料颗粒直径小于500nm。
  11. 根据权利要求3所述的墨水组合物，其特征在于，所述光引发剂为 夺氢型自由基光引发剂和/或裂解型自由基光引发剂；
    所述夺氢型自由基光引发剂选自二苯甲酮/叔胺类和硫杂蒽酮/叔胺类中的一种或多种；所述裂解型自由基光引发剂选自α-羟基酮类、α－胺基酮类、酰基膦氧化物和肟酯类中的一种或多种。
  12. 根据权利要求3所述的的墨水组合物，其特征在于，所述助剂选自增韧剂、消泡剂、流平剂和稳定剂中的一种或多种。
  13. 一种墨水组，其特征在于，所述墨水组为权利要求1～12中任一所述的墨水组合物中至少两种墨水组合物的组合，其中，所述至少两种墨水组合物中含有不同颜色的着色剂，并且所述不同颜色着色剂在所述至少两种墨水组合物中着色剂的含量满足如下关系：
    白色着色剂＞红色着色剂＞蓝色着色剂＞黄色着色剂＞黑色着色剂。
  14. 权利要求1至12任一所述3D喷墨打印用墨水组合物的制备方法，其特征在于，包括如下步骤：
    1)将45～75份丙烯酸低聚物、20～45份丙烯酸单体和0.2～10份助剂混合均匀，生成第一混合物；随后向所述第一混合物中加入1～9份光引发剂直至所述光引发剂溶解完全，生成第二混合物；向所述第二混合物中加入0～4份着色剂并混合均匀，生成第三混合物；
    2)过滤所述第三混合物，收集滤液，得到所述墨水组合物。
  15. 根据权利要求14所述的制备方法，其特征在于，所述过滤为采用微孔滤膜对所述第三混合物进行二级过滤；其中，第一级过滤采用孔径为0.6μm的玻璃纤维膜，第二级过滤采用孔径为0.2μm的聚丙烯膜。
  16. 根据权利要求14-15中任一所述的制备方法，其特征在于，还包括对所收集的滤液进行脱气处理。
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