阅读说明：本技术 三维打印材料及其制备方法和应用 (Three-dimensional printing material and preparation method and application thereof ) 是由 王卉 黄蓓青 魏先福 张柳鑫 刘骏 于 2020-09-11 设计创作，主要内容包括：本申请提供了一种三维打印材料及其制备方法和应用。三维打印材料包括色浆15-25份(所述色浆,以重量份数计,包括：颜料5-7份,染料10-13份,单体45-75份,分散剂4-10份),自由基单体40-75份,自由基预聚物2-4份,自由基光引发剂8-12份,阳离子单体4-8份,阳离子预聚物0.2-3份,阳离子引发剂0.5-2份,活性胺1-4份,流平剂0.2-2份。制备方法：单体和分散剂混合均匀后加入色料,搅拌预分散然后研磨得到色浆；将各原料混合搅拌均匀过滤得到三维打印材料。另外,还提供了三维打印材料的应用,用于紫外光固化喷墨打印技术进行三维打印。使用本申请提供的三维打印材料,分散性好、平均粒径小,表面张力和黏度适中、体积收缩率小、色密度高、固化速度快、能更好应用于三维喷墨打印体系。(The application provides a three-dimensional printing material and a preparation method and application thereof. The three-dimensional printing material comprises 15-25 parts of color paste (the color paste comprises, by weight, 5-7 parts of pigment, 10-13 parts of dye, 45-75 parts of monomer, 4-10 parts of dispersing agent), 40-75 parts of free radical monomer, 2-4 parts of free radical prepolymer, 8-12 parts of free radical photoinitiator, 4-8 parts of cationic monomer, 0.2-3 parts of cationic prepolymer, 0.5-2 parts of cationic initiator, 1-4 parts of active amine and 0.2-2 parts of flatting agent. The preparation method comprises the following steps: uniformly mixing the monomer and the dispersing agent, adding the pigment, stirring for pre-dispersion, and grinding to obtain color paste; the three-dimensional printing material is obtained by mixing, stirring and filtering the raw materials uniformly. In addition, the application of the three-dimensional printing material is also provided, and the three-dimensional printing material is used for three-dimensional printing by using an ultraviolet curing ink-jet printing technology. The three-dimensional printing material provided by the application has the advantages of good dispersibility, small average particle size, moderate surface tension and viscosity, small volume shrinkage, high color density, high curing speed and capability of being better applied to a three-dimensional ink-jet printing system.)

1. A three-dimensional printing material is characterized by comprising the following components in parts by weight: 15-25 parts of color paste, 40-75 parts of free radical monomer, 2-4 parts of free radical prepolymer, 8-12 parts of free radical photoinitiator, 4-8 parts of cationic monomer, 0.2-3 parts of cationic prepolymer, 0.5-2 parts of cationic initiator, 1-4 parts of active amine and 0.2-2 parts of flatting agent;

the color paste comprises the following components in parts by weight: 15-24 parts of pigment, 45-75 parts of monomer and 4-10 parts of dispersing agent.

The pigment comprises the following components in parts by weight: 33-46 parts of pigment and 55-70 parts of dye.

2. The three-dimensional printed material according to claim 1, wherein the pigment is selected from one or more of quinacridone magenta, gold red (PR21), pigment Red G (PR37), pigment Red 171(PR171), DIC magenta pigment; the dye is selected from one or more of scarlet dye, brilliant red dye, 311 pink dye, peach red dye, 236 brilliant red dye and 237 scarlet dye; the monomer is one or more of monofunctional or difunctional monomers containing an active polymerizable carbon-carbon double bond, preferably ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine; the dispersing agent is selected from BYK9077, BYK9151 or BYK 9150.

3. Three-dimensional printed material according to claims 1-2, characterized in that the radical monomer is one or more of mono-or di-functional monomers containing an active polymerizable carbon-carbon double bond, preferably ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine.

4. The three-dimensional printed material according to claims 1-3, characterized in that the free radical prepolymer is one or more of unsaturated oligomers containing polymerizable carbon-carbon double bonds, preferably epoxy acrylic resins, polyurethane acrylic resins, polyester acrylic resins, polyether acrylic resins, acrylated acrylic resins, vinyl resins or hyperbranched oligomers, preferably hyperbranched polyester acrylate V400, hyperbranched polyester acrylate V100, aliphatic polyurethane acrylic resins EB270, polyester acrylic resins EB870, hyperbranched polyester acrylate EB 150; the cationic prepolymer is one or more of oligomers capable of cationic polymerization, preferably epoxy resins, vinyl ether resins.

5. The three-dimensional printed material according to claims 1-4, wherein the radical photoinitiator is one or more of a cleavage type radical photoinitiator or a hydrogen abstraction type photoinitiator, preferably phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, thiophenyl-p-oxazacyclopropanone, photoinitiator 2773, photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, photoinitiator 389, photoinitiator 1508, isopropylthioxanthone, 2, 4-diethylthioxanthin-9-one; the cationic initiator is initiator PAG-2.

6. The three-dimensional printed material according to claim 5, wherein the cationic monomer is one or more of compounds which undergo ring-opening polymerization under the action of cationic radicals, preferably 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, 3-epoxyethyl 7-oxabicyclo [4.1.0] heptane, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-hydroxymethyloxetane, 3- [ oxybis-methylene ] bis [ 3-ethyl ] oxetane.

7. The three-dimensional printed material according to claim 6, wherein the leveling agent is TEGO410 or TEGO 432; the active amine is 2-benzyl phenyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.

8. A method for preparing the three-dimensional printed material according to any one of claims 1 to 7, comprising the steps of:

uniformly mixing the monomer and the dispersing agent, adding the pigment, stirring for pre-dispersion to obtain a pre-dispersed mixture, and then grinding to obtain the color paste;

and mixing the color paste, the free radical monomer, the free radical prepolymer, the free radical photoinitiator, the cationic monomer, the cationic prepolymer, the cationic initiator, the active amine and the leveling agent, uniformly stirring, and filtering to obtain the three-dimensional printing material.

9. The preparation method according to claim 8, wherein the stirring pre-dispersion time is 30-60min, and the grinding time is 90-180 min; before the grinding, adding pickaxe beads into the pre-dispersion mixture, wherein the adding amount of the pickaxe beads is 3-5 times of the total volume of the pre-dispersion mixture.

10. Use of the three-dimensional printing material according to any of claims 1 to 7 for three-dimensional printing by UV-curable ink-jet printing.

Technical Field

The application relates to the field of 3D printing, in particular to a three-dimensional printing material and a preparation method and application thereof.

Background

Three-dimensional printing technology has been developed rapidly in recent years as an additive manufacturing technology. The true-color three-dimensional printing technology is an important technology based on three-dimensional modeling data and color data, and can truly reproduce the color of a three-dimensional target object while three-dimensionally printing a model. The technology has wide application value and development space in the fields of medical industry, artistic creation, private customization, cultural relic replication, fast-moving industry, original model design, model teaching and the like.

In the existing color three-dimensional printing technology, the ultraviolet curing ink-jet printing technology is one of the modes which can really realize color three-dimensional printing. The principle is that based on photocuring reaction initiated by ultraviolet radiation, a photosensitive three-dimensional printing material is atomized by a nozzle to form liquid drops, and then the liquid drops are sprayed on the surface of a substrate or a bottom layer material, and then the liquid drops are cured to form a film under the irradiation of ultraviolet light, and a three-dimensional entity is formed in a layer-by-layer printing mode. The color ultraviolet curing ink-jet three-dimensional printing material mainly comprises a coloring component and a photocuring component, is cured and molded in an ultraviolet radiation mode, does not need heating, and does not need an organic solvent or a drier containing metal elements, so that the ultraviolet curing ink-jet printing technology is a green, environment-friendly and energy-saving printing and molding mode.

The color three-dimensional printing material suitable for ultraviolet curing ink-jet printing needs to meet the following conditions: (1) good dispersibility and proper particle size distribution, thereby ensuring that the material can be smoothly sprayed out from the spray head; otherwise, the molding quality is not good and the risk of blocking the spray head exists; (2) lower viscosity; (3) the material has smaller volume change rate before and after the photocuring reaction, thereby ensuring the molding quality; (4) the color printing ink has good color characteristics, so that a printed and molded product has higher color density; (5) has proper surface tension; (6) higher curing speed.

Patent CN107304318A discloses an ink composition for 3D inkjet printing, an ink set and a preparation method thereof, and the technology has the defects that: the monomers, prepolymers and initiators are based on free radical polymerization systems and tend to produce a large volume shrinkage; patent CN106700729A discloses a formula of an automatic leveling inkjet 3D printing material and a preparation method thereof, and the technical defects are as follows: the monomers, prepolymers and initiators are based on free radical polymerization systems and tend to produce a large volume shrinkage; further, it is difficult to obtain a high color density when the colorant is added in an amount of not more than 5%. Patent CN107109091A discloses an ink composition for 3D printing, a 3D printer and a method of controlling the same, the drawbacks of this technology are: (1) the monomers, prepolymers and initiators are based on free radical photopolymerization systems and tend to produce large volume shrinkage; (2) the organic solvent is used, Volatile Organic Compounds (VOCs) are discharged in the preparation and use processes, and the environmental protection and the personnel health are not facilitated; (3) the inorganic particles subjected to surface modification are contained in the formula, the modification steps are complicated, the high-content inorganic particles influence the viscosity and rheological behavior of the ink, the jetting performance is further influenced, and in addition, the particles easily block a nozzle. Patent CN 105949881 a discloses a UV curable ink for 3D printing, which has the following defects: (1) the preparation method needs to prepare the dry oil alkyd resin modified polyurethane acrylic resin, the preparation process is complicated, and organic tin compounds such as monobutyl tin oxide, dibutyl tin dilaurate, dibutyl tin diacetate or monobutyl tin trichloride are used as esterification catalysts, so that the dry oil alkyd resin modified polyurethane acrylic resin has great harm to the environment and human health; (2) the photo-curing system is a radical photo-polymerization system, which tends to generate a large volume shrinkage rate and reduce the molding quality. Patent CN 109517440 a discloses a 3D printing material for uv curing inkjet printing technology, which has the disadvantages that: (1) the color paste in the ink system is pigment type color paste, and the prepared ink has high average particle size and is easy to cause nozzle blockage; (2) the ink has high viscosity, which is not favorable for the atomization and the ejection of ink drops.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide a three-dimensional printing material which has small average particle size, good dispersibility, low viscosity, moderate surface tension, high color density, low volume shrinkage and high curing speed.

The second purpose of the invention is to provide a preparation method of the three-dimensional printing material, which is simple in process and environment-friendly.

The third purpose of the invention is to provide an application of the three-dimensional printing material, which is applied to the ultraviolet curing ink-jet printing technology for three-dimensional printing.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

a three-dimensional printing material comprises the following components in parts by weight: 15-25 parts of color paste, 40-75 parts of free radical monomer, 2-4 parts of free radical prepolymer, 8-12 parts of free radical photoinitiator, 4-8 parts of cationic monomer, 0.2-3 parts of cationic prepolymer, 0.5-2 parts of cationic initiator, 1-4 parts of active amine and 0.2-2 parts of flatting agent;

the color paste comprises the following components in parts by weight: 15-24 parts of pigment, 45-75 parts of monomer and 4-10 parts of dispersing agent.

The pigment comprises the following components in parts by weight: 33-46 parts of pigment and 55-70 parts of dye.

The color paste prepared by using the pigment and the dye as the pigment has small average particle size, good dispersibility and low viscosity compared with the pigment color paste. Compared with dye color paste, the color paste has smaller shrinkage, good color density and good printing effect. The optimal weight ratio of the pigment to the dye is 1: 2.

the use of the color paste, the free radical monomer, the free radical prepolymer, the free radical photoinitiator, the cationic monomer, the cationic prepolymer, the cationic initiator, the active amine and the leveling agent can well solve the problems of inappropriate surface tension and viscosity, large volume shrinkage, low curing speed, low color density and poor dispersibility caused by a single polymer, a monomer and an initiator. Compared with a simple free radical photopolymerization system, the free radical/cation hybrid photopolymerization system has the advantage of small volume shrinkage; compared with a pure cationic photopolymerization system, the curing speed is high.

The three-dimensional printing material provided by the application is a hybrid photocuring system comprising a free radical polymerization system and a cationic polymerization system; the free radical polymerization system comprises a free radical photoinitiator, a free radical monomer, a free radical prepolymer and a reactive amine; the cationic polymerization system includes a cationic photoinitiator, a cationic monomer, and a cationic prepolymer. The proportion of the free radical polymerization system and the cationic polymerization system has a remarkable influence on the printing and forming performance indexes of the three-dimensional printing material, and the optimal weight proportion is 9: 1.

Preferably, the pigment is selected from one or more of quinacridone magenta, gold bright red, pigment red G, pigment red 171; the dye is selected from one or more of scarlet dye, brilliant red dye, 311 pink dye, peach red dye, 236 brilliant red dye and 237 scarlet dye; the monomer is one or more of monofunctional or difunctional monomers containing an active polymerizable carbon-carbon double bond, preferably ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine; the dispersing agent is selected from BYK9077, BYK9151 or BYK 9150.

In order to obtain a magenta three-dimensional printing material having a good performance, a coloring material is preferable. The monomer is matched with the pigment and the dispersing agent, so that color paste with good dispersibility and uniform particle size distribution can be prepared, which is the basis for obtaining the color three-dimensional printing material with excellent performance.

Preferably, the free radical monomer is one or more of a mono-or di-functional monomer containing an activated polymerizable carbon-carbon double bond, preferably ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine.

More preferably, the free radical prepolymer is one or more of unsaturated oligomers containing polymerizable carbon-carbon double bonds, preferably epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic resin, polyether acrylic resin, acrylated acrylic resin, vinyl resin, or hyperbranched oligomers, preferably hyperbranched polyester acrylate V400, hyperbranched polyester acrylate V100, aliphatic polyurethane acrylic resin EB270, polyester acrylic resin EB870, hyperbranched polyester acrylate EB 150; the cationic prepolymer is one or more of oligomers capable of cationic polymerization, preferably epoxy resins, vinyl ether resins.

Further preferably, the free radical photoinitiator is one or more of a cleavage type free radical photoinitiator or a hydrogen abstraction type photoinitiator, preferably phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, thiophenyl-p-oxazacycloacetone, photoinitiator 2773, photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, photoinitiator 389, photoinitiator 1508, isopropylthioxanthone, 2, 4-diethylthioxanth-9-one; the cationic initiator is initiator PAG-2.

More preferably, the cationic monomer is one or more of compounds which undergo ring-opening polymerization by the action of cationic radicals, preferably 3, 4-epoxycyclohexylmethylmethacrylate, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate, 3-oxiranyl 7-oxabicyclo [4.1.0] heptane, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-hydroxymethyloxetane, 3- [ oxybis-methylene ] bis [ 3-ethyl ] oxetane.

The optimization of the free radical monomer, the free radical prepolymer, the cationic prepolymer, the free radical photoinitiator, the cationic initiator and the cationic monomer ensures that the three-dimensional printing material can obtain better performance.

Still further preferably, the leveling agent is TEGO410 or TEGO 432; the active amine is 2-benzyl phenyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.

The use of the leveling agent and the active amine enables the three-dimensional printing material to have better surface tension and viscosity, and simultaneously optimizes the matching of the components. In addition, the combination of the active amine and the hydrogen abstraction type free radical photoinitiator can improve the curing speed, reduce the influence of oxygen inhibition and improve the curing effect.

The preparation method of the three-dimensional printing material comprises the following steps:

uniformly mixing the monomer and the dispersing agent, adding the pigment, stirring for pre-dispersion to obtain a pre-dispersed mixture, and then grinding to obtain the color paste;

and mixing the color paste, the free radical monomer, the free radical prepolymer, the free radical photoinitiator, the cationic monomer, the cationic prepolymer, the cationic initiator, the active amine and the leveling agent, uniformly stirring, and filtering to obtain the three-dimensional printing material.

The method is simple, and the three-dimensional printing material does not use an organic tin catalyst and any organic solvent in the preparation process, thereby having the advantage of environmental protection. Firstly, pigment-based magenta paste needs to be prepared, the paste is used as a colorant component to prepare a color three-dimensional printing material, and compared with the prior art in which pigment is selected as a colorant, the color three-dimensional printing material can realize smaller average particle size and lower viscosity, and is not easy to block a spray head. Higher color density can be achieved compared to the prior art, which selects dyes as colorants. The preparation process of the color paste can be realized by adopting commercial raw materials and physically grinding, and the preparation process of the three-dimensional printing material can be realized by adopting commercial raw materials and simply and electromagnetically stirring or mechanically stirring, does not need complicated chemical modification and synthesis processes, and has the advantage of simple and convenient operation.

Preferably, the stirring pre-dispersion time is 30-60min, and the grinding time is 90-180 min; before the grinding, adding pickaxe beads into the pre-dispersion mixture, wherein the adding amount of the pickaxe beads is 3-5 times of the total volume of the pre-dispersion mixture.

The parameters of stirring and grinding are controlled, and pickaxe beads are added for grinding, so that a product with more excellent particle size distribution can be obtained.

The application of the three-dimensional printing material is used for three-dimensional printing by an ultraviolet curing ink-jet printing technology.

Compared with the prior art, the invention has the beneficial effects that:

(1) the three-dimensional printing material is applied to three-dimensional printing, has small particle size and low viscosity, is favorable for ink droplet ejection, and reduces the risk of nozzle blockage.

(2) The three-dimensional printing material has moderate surface tension, small volume shrinkage, high curing speed, high color density and good dispersibility;

(3) the preparation method is simple, simple and convenient to operate, and green and environment-friendly;

(4) the three-dimensional printing material is applied to three-dimensional printing, has good performance, and can obtain good three-dimensional printing products.

Detailed Description

Firstly, the conditions to be satisfied by the color three-dimensional printing material suitable for ultraviolet curing ink-jet printing are explained:

(1) good dispersibility and proper particle size distribution, thereby ensuring that the material can be smoothly atomized and sprayed from the spray head; otherwise, the molding quality is not good, and the risk of blocking the spray head exists.

(2) Lower viscosity. If the viscosity of the material is too high, the nozzle is blocked and cannot normally spray liquid drops; if the viscosity of the material is too low, the material can directly flow out from the spray head, the outflow quantity of the material cannot be controlled, and the forming precision is seriously damaged, so that the viscosity is generally in a range of between 10 and 25 mPa.s.

(3) Appropriate surface tension. Too big surface tension can lead to the material directly to flow out, and too low surface tension can cause the unable blowout of shower nozzle, blocks up the shower nozzle, can't reach the injection requirement. The appropriate surface tension ensures that the three-dimensional printing material is ejected from the nozzle with sufficient power to form droplets with uniform volume and to form an appropriate contact angle when the droplets contact the substrate, generally between 20 and 22 mN/m.

(4) The color printing ink has good color characteristics, so that a printed and molded product has higher color density.

(5) The three-dimensional printing material has a small volume change rate before and after the photocuring reaction, so that the forming quality is ensured. When the photo-curing material is changed into a solid film layer from liquid molecules during cross-linking and curing, the acting distance of van der Waals force between the liquid molecules is larger than the acting distance of covalent bonds of the solid molecules, so that the photo-curing material generates a certain volume shrinkage effect when being changed from the liquid state to the solid state. The size of the molded part is caused to generate errors even warping deformation due to the volume shrinkage of the photocuring material, so that the selection of the photocuring material system with low shrinkage rate in the formula design has very important significance for reducing the curing shrinkage effect of the material and improving the molding precision of the molded part.

(6) Higher curing speed. After the material liquid drops are sprayed out, the material liquid drops are instantly solidified under the radiation of an ultraviolet light source, so that the liquid state is converted into the solid state, and a three-dimensional entity is formed in a layer-by-layer superposition mode; if the curing speed of the material is insufficient, the material can flow in the forming process, and the like, so that the manufacturing precision of the product is seriously affected, and even the product cannot be formed.

Based on the cognition, the application provides a three-dimensional printing material and a preparation method and application thereof.

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

For the sake of clarity of the protocol of the present application, the sources of reagents used in the examples are set forth below:

pigment: quinacridone magenta (gaede chemical), chrysene red (PR21) (suzhou taipu rui fine chemicals, ltd.), pigment red G (PR37) (shenzhen rainbow packaging material, ltd.), pigment red 171(PR171) (shanghai baiyan industries, ltd.), and DIC magenta pigment (shenzhen dingtai chemical, ltd);

dye: scarlet dyes (Shandong Hongyi chemical Co., Ltd.), brilliant red dyes (Aurtella chemical Co., Ltd.), 311 pink dyes (Aurtella chemical Co., Ltd. in Wenzhou), pink dyes (Zhongshan Hentai technical materials Co., Ltd.), 236 brilliant red dyes (Shanghai Huayuan practical Co., Ltd.), 237 brilliant red dyes (Kun shan Wanfukai chemical Co., Ltd.);

free radical monomer: ethoxyethoxyethyl acrylate EOEOEA, 1, 6-hexanediol diacrylate HDDA, tripropylene glycol diacrylate TPGDA, neopentyl glycol diacrylate NPGDA, dipropylene glycol diacrylate DPGDA, acryloylmorpholine ACMO and the like are all available from Tianjin Tianjiao radiation-cured materials Co., Ltd;

free radical prepolymer: hyperbranched polyester acrylates EB150, V400 and V100, aliphatic polyurethane acrylic resin EB270, polyester acrylic resin EB870 and the like are purchased from Zhan Xin resins (Shanghai) Co., Ltd;

free radical photoinitiator: phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), thiophenyl-p-oxacycloacetone (907), photoinitiator 2773, photoinitiator 2776, photoinitiator 2778, photoinitiator 2777, photoinitiator 2671, photoinitiator 898, photoinitiator 910, photoinitiator 389, photoinitiator 1508 and the like are all available from Tianjin Jieshi materials, Inc.; isopropyl Thioxanthone (ITX), 2, 4-diethyl thioxanthone-9-one (DETX) were purchased from Beijing Engli scientific development Inc.;

cationic monomer: 3, 4-epoxycyclohexylmethylmethacrylate (TTA-15), 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (TTA-21), 3-oxiranyl 7-oxabicyclo [4.1.0] heptane (TTA-22), bis ((3, 4-epoxycyclohexyl) methyl) adipate (TTA-26) was purchased from Jiangsutton's chemical industry, 3-ethyl-3-hydroxymethyloxetane (OXT-1), 3- [ oxybis-methylene ] bis [ 3-ethyl ] oxetane (OXT-3) was purchased from Kurthe scientific Co., Ltd.;

cationic initiator: (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile (PAG-2) was purchased from Kunbei Kogyun science, Inc.; other cationic initiators which may be used are based on absorption at the wavelength 385-;

leveling agents TEGO410, 432, available from Texaco;

activated amine 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone (EHA) was purchased from Beijing Engli scientific development Co., Ltd.

Example 1

(1) Preparation of color paste

Magenta pigment quinacridone Magenta RTS6 parts, 311 pink dye 12 parts, 72 parts of tripropylene glycol diacrylate (TPGDA) and 7710 parts of dispersant BYK 907710 parts are taken.

First, the monomers and the dispersant were mixed uniformly using a constant temperature magnetic stirrer. Then, the magenta pigment was added thereto, and pre-dispersed for 30 minutes using a mechanical stirrer. And finally, placing the pre-dispersed mixture into a grinding machine, adding pickaxe beads with the volume 4 times of the total volume of the pre-dispersed mixture, and grinding for 180 minutes at the rotating speed of 220r/min to obtain the fuchsin color paste.

(2) Preparation of three-dimensional printing material

20 parts of fuchsin color paste, 43 parts of tripropylene glycol diacrylate, 43 parts of neopentyl glycol diacrylate, 5 parts of bis ((3, 4-epoxycyclohexyl) methyl) adipate, 3-ethyl-3-hydroxymethyl oxetane, 5 parts of 3, 3- [ oxybis methylene ] bis [ 3-ethyl ] oxetane, 5 parts of polyester acrylic resin and polyether acrylic resin, 3 parts of epoxy resin E51, 12 parts of thiophenyl-p-oxacycloacetone and isopropyl thioxanthone, 2 parts of initiator PAG-2, 4 parts of active amine 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone (EHA) and 0.2 part of flatting agent TEGO 432.

Mixing the raw materials, placing the mixture on a mechanical stirrer, stirring the mixture for 30 minutes until the mixture is uniform, and filtering the mixture to obtain the three-dimensional printing material.

Example 2

(1) Preparation of color paste

Taking 5 parts of magenta pigment golden light red (PR21), 10 parts of 236 brilliant red dye, 75 parts of monomer tripropylene glycol diacrylate (TPGDA) and neopentyl glycol diacrylate (NPGDA) and 10 parts of dispersant BYK 9150.

First, the monomers and the dispersant were mixed uniformly using a constant temperature magnetic stirrer. Then, the magenta pigment was added thereto, and pre-dispersed for 60 minutes using a mechanical stirrer. And finally, placing the pre-dispersed mixture into a grinding machine, adding pickaxe beads of which the volume is 3 times that of the pre-dispersed mixture, and grinding for 90 minutes at the rotating speed of 250r/min to obtain the fuchsin color paste.

(2) Preparation of three-dimensional printing material

15 parts of fuchsin color paste, 26.48 parts of dipropylene glycol diacrylate (DPGDA), 19.77 parts of acryloyl morpholine (ACMO), 13.83 parts of ethoxy ethyl acrylate (EOEOEA), 6.68 parts of 3-ethylene oxide 7-oxabicyclo [4.1.0] heptane (TTA-22), 1.44 parts of aliphatic polyurethane acrylic resin EB270, 1.44 parts of hyperbranched polyester acrylate V400, 0.32 part of epoxy resin E44, 3.02 parts of photoinitiator 2777, 5.04 parts of photoinitiator 2671, 2.02 parts of photoinitiator 898, 0.96 part of initiator PAG-2, 3.60 parts of active amine 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone (EHA) and 0.4 part of leveling agent TEGO 432.

Mixing the raw materials, placing the mixture on a mechanical stirrer, stirring the mixture for 30 minutes until the mixture is uniform, and filtering the mixture to obtain the three-dimensional printing material.

Example 3

(1) Preparation of color paste

Pigment red G (PR37)8 parts, scarlet dye and 237 scarlet dye 16 parts in total, monomer 1, 6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), acryloyl morpholine (ACMO) 70 parts in total, and dispersant BYK9151 6 parts in total.

First, the monomers and the dispersant were mixed uniformly using a constant temperature magnetic stirrer. Then, the magenta pigment was added thereto, and pre-dispersed for 50 minutes using a mechanical stirrer. And finally, placing the pre-dispersed mixture into a grinding machine, adding pickaxe beads which are 5 times of the total volume of the pre-dispersed mixture, and grinding for 120 minutes at the rotating speed of 200r/min to obtain the fuchsin color paste.

(2) Preparation of three-dimensional printing material

25 parts of fuchsin color paste, 65 parts of 1, 6-hexanediol diacrylate, 8 parts of 3, 4-epoxy cyclohexyl methyl methacrylate and 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate, 2 parts of epoxy acrylic resin, 0.2 part of vinyl ether resin, 8 parts of phenyl bis (2,4, 6-trimethyl benzoyl) phosphine oxide, 0.5 part of initiator PAG-2, 1 part of active amine 2-phenyl benzyl-2-dimethyl amine-1- (4-morpholine benzyl phenyl) butanone (EHA) and 2 parts of a TEGO410 leveling agent.

Mixing the raw materials, placing the mixture on a mechanical stirrer, stirring the mixture for 30 minutes until the mixture is uniform, and filtering the mixture to obtain the three-dimensional printing material.

The three-dimensional printing material obtained in example 1 was subjected to a performance test, and the results thereof were as follows:

(1) surface tension: the test was carried out using a K100 full-automatic surface tensiometer (KRUSS, Germany) in mN/m units.

And (3) testing results: the surface tension was 23.32 mN/m.

(2) Viscosity: the viscosity at a shear rate of 1s-1 was measured using an AR2000ex type rheometer (TA, USA) at a constant temperature of 25 ℃ using an aluminium rotor with a diameter of 60 mm.

And (3) testing results: the viscosity was 11.99 mPas.

(3) Volume Shrinkage (Shrinkage Ratio, SR): the test was carried out according to the relevant provisions in international standard ISO3521, the value of SR being calculated from formula (1):

in the formula, ρ₁And ρ₂The densities of the liquid sample and the solidified solid material, respectively, were measured by a 10mL pycnometer.

And (3) testing results: the volume shrinkage was 1.30%.

(4) Curing speed: the prepared liquid sample is uniformly coated on a PET film by a No. 0 silk rod at room temperature, and is placed on an ultraviolet curing machine (Eita precision photoelectric Co., Ltd.) for curing, and then the curing condition is observed by adopting a finger touch method. The ultraviolet light source is 385nm and 395nm double-wavelength light source.

And (3) testing results: the radiation energy density of the ultraviolet light source is 1.2W/cm²The curing speed was 880 cm/min.

(5) Color density: the color density of the cured film was measured using an X-rite X-528 type spectrodensitometer (Achrome technologies, Inc.), five different positions were selected for the measurement, and the average value was used as the color density measurement result.

And (3) testing results: the color density was 0.68.

(6) Dispersibility: the equivalent diameter of the largest particles at a cumulative distribution of 95% in the particle size distribution curve was measured using a Microtrac S3500 laser particle size analyzer (Microtrac, USA) with ethanol as the solvent.

And (3) testing results: the particle size measurement was 0.78 microns.

The three-dimensional printing materials obtained in examples 1 to 3 were injected into an ultraviolet curing ink-jet three-dimensional printer (Beijing color rhyme digital technologies, Ltd.), and a magenta three-dimensional entity could be printed. The wavelength of a radiation light source of the ultraviolet curing ink-jet three-dimensional printer is 395 nm.

To more clearly express the effects of the three-dimensional printed material provided herein, a control test was performed, as follows:

comparative example 1

Compared with example 1, the difference is that the coloring materials used in step (1) are all 311 parts of pink dye.

Namely, only a dye type color paste system is adopted.

Comparative example 2

Compared with example 1, the difference is that the colorant used in step (1) is Magenta pigment quinacridone Magenta RTS 18 parts.

Namely only adopting a pigment type color paste system.

Comparative example 3

The difference is only that the colorant used in step (1) is Magenta pigment quinacridone Magenta RTS9 parts and 311 pink dye 9 parts compared to example 1.

Namely, the ratio of the pigment to the dye in the color paste is changed to be 1: 1.

comparative example 4

Compared with example 1, the difference is only that step (1) takes quinacridone Magenta RTS5 parts of Magenta pigment, 10 parts of 311 pink dye, 75 parts of monomer ethoxyethoxyethyl acrylate (EOEOEA) and BYK 915010 parts of dispersant.

Namely, the proportion of the pigment in the color paste is reduced.

The performance tests were performed according to the method described above, and the performance data are shown in table 1 below:

TABLE 1 Performance data

As can be seen from table 1 above, the three-dimensional printing material provided by the application, which includes the dye and the pigment as the colorant together, has the advantages of moderate surface tension, low viscosity, small volume shrinkage, high curing speed, high color density, good dispersibility, and excellent printing forming performance, and is very suitable for being used in an ultraviolet curing inkjet three-dimensional printer for three-dimensional printing.

While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.