Light curing non-transparent material for 3D printing and a preparation method threrof, a 3D printed product and a 3D printer

Abstract

The present disclosure provides a light curing non-transparent material for 3D printing and a preparation method thereof, a 3D printed product and a 3D printer. The light curing non-transparent material for 3D printing provided by the present disclosure can be used to print non-transparent 3D printed products without adding white pigments such as white pigments powder, and therefore has the characteristic of high stability, and also ensures fluency of the 3D printing process, good quality of the 3D printed products, as well as good performances of the 3D printer that containing light curing non-transparent material for 3D printing.

Claims

1. A light curing non-transparent material for 3D printing, comprising components as follows: 30 to 70 parts by weight of a first acrylate component, 20 to 60 parts by weight of a second acrylate component, 0.5 to 5 parts by weight of a photoinitiator, 0.5 to 8 parts by weight of an additive, and 0 to 4 parts by weight of a colorant; wherein the first acrylate component is a polar acrylate component, and the second acrylate component is selected from at least one of a weakly polar acrylate component and a non-polar acrylate component; wherein dielectric constant of the first acrylate component is greater than or equal to 3.6, dielectric constant of the second acrylate component is less than or equal to 3.

2. The light curing non-transparent material for 3D printing according to claim 1, wherein a weight ratio between the second acrylate component and the first acrylate component is less than 2:1.

3. The light curing non-transparent material for 3D printing according to claim 1, wherein the first acrylate component is selected from at least one of polar acrylate oligomers and polar acrylate monomers; the second acrylate component is selected from at least one of acrylate oligomers with dielectric constant less than or equal to 3 and acrylate monomers with dielectric constant less than or equal to 3.

4. The light curing non-transparent material for 3D printing according to claim 3, the polar acrylate oligomers are selected from at least one of aliphatic polyurethane acrylate oligomers and epoxy acrylate oligomers; the polar acrylate monomers are selected from at least one of hydroxyalkyl acrylate monomers, alkoxylated acrylate monomers and acrylate monomers with a heterocyclic structure.

5. The light curing non-transparent material for 3D printing according to claim 3, wherein the polar acrylate oligomers are aliphatic polyurethane acrylate oligomers and/or epoxy acrylate oligomers with at least one group selected from cyano, carboxyl, hydroxyl, acetylamino, amino and sulfydryl groups.

6. The light curing non-transparent material for 3D printing according to claim 4, wherein the hydroxyalkyl acrylate monomers are selected from at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate; the alkoxylated acrylate monomers are selected from at least one of 2-acrylic-2-methoxy ester, ethoxyethoxyethyl acrylate, methoxy (polyethylene glycol) monoacrylate, methoxy (polyethylene glycol) methacrylate and alkoxylated nonylphenol acrylate; the acrylate monomers with a heterocyclic structure are selected from at least one of tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1, 3-dioxolan-4-yl) acrylate and acryloyl morpholine.

7. The light curing non-transparent material for 3D printing according to claim 3, wherein the acrylate monomers with dielectric constant less than or equal to 3 are selected from at least one of bisphenol A acrylate monomers, alkyl (meth) acrylate monomers and cycloalkyl (meth) acrylate monomers; the acrylate oligomers with dielectric constant less than or equal to 3 are selected from at least one of bisphenol A acrylate oligomers, alkyl (meth) acrylate oligomers and cycloalkyl (meth) acrylate oligomers.

8. The light curing non-transparent material for 3D printing according to claim 7, wherein the bisphenol A acrylate oligomers are selected from acrylate oligomers with a diphenol propane structure; the alkyl (meth) acrylate oligomers are homopolymers or copolymers with the alkyl (meth) acrylate monomers as structural units; the cycloalkyl (meth) acrylate oligomers are homopolymers or copolymers with cycloalkyl (meth) acrylate monomers as structural units.

9. The light curing non-transparent material for 3D printing according to claim 7, wherein, the bisphenol A acrylate monomers are selected from acrylate monomers with a diphenol propane structure; the alkyl (meth) acrylate monomers are selected from at least one of butyl acrylate, n-octyl acrylate, isooctyl acrylate, isoctadecyl acrylate, isononyl acrylate, lauric acrylate, isodecyl acrylate, isodecyl methacrylate ester, stearic acrylate, dodecyl methacrylate and isotridecyl methacrylate; the cycloalkyl (meth) acrylate monomers are selected from at least one of isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 4-tert-butyl cyclohexyl acrylate and cyclohexyl methacrylate.

10. The light curing non-transparent material for 3D printing according to claim 1, wherein the photoinitiator is selected from free radical UV photoinitiators.

11. The light curing non-transparent material for 3D printing according to claim 1, wherein the additive is selected from at least one of toughening agents, defoamer agents, stabilizer agents and leveling agents.

12. The light curing non-transparent material for 3D printing according to claim 1, wherein the colorant is selected from at least one of dyes and pigments.

Description

BRIEF DESCRIPTION OF DRAWING(S)

(1) FIG. 1 is a structure schematic diagram of a 3D printer provided by example 6 of this disclosure.

DESCRIPTION OF REFERENCE NUMBERS

(2) 1: Material containers; 2: Inkjet print head; 3: Connecting device; 4: Controller; 5: UV light source; 6: Material layer.

DESCRIPTION OF EMBODIMENTS

(3) The technical solutions in the embodiment examples of present disclosure will be clearly and completely described in following with reference to the accompanying drawings of the embodiment examples of present disclosure such that the object, technical solution and advantage of the embodiment examples of present disclosure will be more clearly understood. Obviously, embodiment examples disclosed hereafter are merely a part of the embodiment examples of present disclosure and not all. Based on the embodiment examples of present disclosure, other embodiment examples obtained by the skilled in the art without making any inventive effort fall into the scope protected by the present disclosure.

Example 1

(4) The example provides a light curing non-transparent material for 3D printing, which has the following composition of table 1:

(5) TABLE-US-00001 TABLE 1 Components Compounds/trade name Weight First acrylate CN9021 NS (oligomer) 25.6 g component Acryloyl morpholine 20 g Second acrylate Isobornyl acrylate 30.6 g component Stearic acrylate 15 g Photoinitiator TPO (acyl phosphine oxide 2.78 g free radical photoinitiator) Additives GENORAD16 (stabilizer agent) 0.5 g BYK-377 (leveling agent) 0.02 g 305T (toughening agent) 5.5 g

(6) The preparation method of the light curing non-transparent material for 3D printing is as follows:

(7) (1) The components other than the photoinitiator are placed in a glass container and stirred by a stirrer, so as to obtain a well-mixed first mixture; the photoinitiator is then added to the first mixture and stirred until the photoinitiator is completely dissolved, so as to obtain a second mixture;

(8) (2) The second mixture was filtered with a 0.45 μm glass fiber membrane for a primary filtration and a 0.22 μm polypropylene membrane (PP membrane) for a secondary filtration to obtain a filtrate;

(9) (3) The filtrate is subjected to decompress filtration at a vacuum of 0.1 MPa for 1 hour to remove the air bubbles therein, then the light curing white material for 3D printing is obtained and it is translucent.

Example 2

(10) The example provides a light curing non-transparent material for 3D printing, which has the following composition of table 2:

(11) TABLE-US-00002 TABLE 2 Components Compounds/trade name Weight First acrylate Greatech GT-8270 (oligomer) 45 g component 2-hydroxyethyl acrylate 20 g Second acrylate BR-970BT (oligomer) 10 g component l-adamantyl methacrylate 22 g Photoinitiator TEPO (acyl phosphine oxide 2.4 g free radical photoinitiator) Additives BYK-088 (defoamer agent) 0.4 g ZJ-701 (stabilizer agent) 0.2 g

(12) In this example, the preparation method of the light curing non-transparent material for 3D printing is basically the same as that of Example 1, except that the components used are replaced accordingly. And step (3) uses heat degassing for degassing treatment, the filtrate obtained from step (2) is heated to 40° C. for degassing, and the degassing time is 50 min.

(13) In this example, a light curing white material for 3D printing is obtained, and it is completely opaque.

Example 3

(14) The example provides a light curing non-transparent material for 3D printing, which has the following composition of table 3:

(15) TABLE-US-00003 TABLE 3 Components Compounds/trade name Weight First acrylate Tetrahydrofuran acrylate 41 g component Ethoxyethoxyethyl acrylate 28 g Second acrylate Bisphenol A acrylate 3000A (oligomer) 20 g component Photoinitiator Isopropyl thioxanthone 3.6 g 6420 of Taiwan Eternal Materials Co., Ltd. l.2 g Additives Greatech GT8003 (toughening agent) 3.6 g TEGO Airex 920 (defoamer agent) 0.4 g ZJ-701 (stabilizer agent) 0.2 g Colorant Bronze red (PR21) red pigment 2 g

(16) In this embodiment, the preparation method of the light curing non-transparent material for 3D printing is basically the same as that of Example 1, except that the components used are replaced accordingly, and the specific time for decompress degassing in step (3) is adjusted to 2 hours.

(17) A light curing red opaque material for 3D printing is obtained in this example.

Example 4

(18) The example provides a light curing non-transparent material for 3D printing, which has the following composition of table 4:

(19) TABLE-US-00004 TABLE 4 Components Compounds/trade name Weight First acrylate 6101 (oligomer) of Taiwan Eternal 31.5 g component Materials Co., Ltd. Second acrylate BR-952 (oligomer) 20 g component lauric acrylate 36 g Photoinitiator 819 (acyl phosphine oxide 0.5 g free radical photoinitiator) Additives Greatech GT8003 (toughening agent) 7 g Modified polysiloxane polymer BYK-333 0.4 g GENORAD 20 (stabilizer agent) 0.6 g Colorant Phthalocyanine blue (PB15:3) 4 g blue pigment

(20) In this embodiment, the preparation method of the light curing non-transparent material for 3D printing is basically the same as that of Example 1, except that the components used are replaced accordingly, and step (3) uses atmospheric pressure static degassing for degassing treatment, the standing time is 3 h.

(21) A light curing blue opaque material for 3D printing is obtained in this example.

Example 5

(22) The example provides a light curing non-transparent material for 3D printing, which has the following composition of table 5:

(23) TABLE-US-00005 TABLE 5 Components Compounds/trade name Weight First acrylate 2-hydroxyethyl acrylate 31 g component Phenolic epoxy acrylate 20 g Second acrylate Isobornyl methacrylate 40 g component Photoinitiator TPO (acyl phosphine oxide 2.5 g free radical photoinitiator) 184 (α-hydroxyketone 2.5 g free radical photoinitiator) Additives TEGO Airex 921 (defoamer agent) 0.3 g PM2010 (stabilizer agent) 0.2 g Colorant Pigment Yellow 185 (PY185) 3.5 g yellow pigment

(24) In this embodiment, the preparation method of the light curing non-transparent material for 3D printing is basically the same as that of Example 1, except that the components used are replaced accordingly, and step (3) uses heat degassing for degassing treatment, the filtrate obtained from step (2) is heated to 50° C. for degassing, and the degassing time is 30 min.

(25) A light curing yellow opaque material for 3D printing is obtained in this example.

Comparative Example 1

(26) This Comparative example provides a light curing material for 3D printing, which has the following composition of table 6:

(27) TABLE-US-00006 TABLE 6 Components Compounds/trade name Weight First acrylate CN9021 NS (oligomer) 25.6 g component 6101 (oligomer) of Taiwan 31.6 g Eternal Materials Co., Ltd. Acryloyl morpholine 40 g Photoinitiator TPO (acyl phosphine oxide 2.78 g free radical photoinitiator) Additives GENORAD16 (stabilizer agent) 0.5 g BYK-377 (surfactant agent) 0.02 g 305T (toughening agent) 5.5 g

(28) In this Comparative example 1, the preparation method of the light curing material for 3D printing is basically the same as that of Example 1, except that the components used are replaced accordingly.

(29) Polar acrylate monomer and polar acrylate oligomer are used as the acrylate component in Comparative example 1, and a light curing transparent materials for 3D printing is obtained.

Comparative Example 2

(30) This Comparative example provides a light curing material for 3D printing, which has the following composition of table 7:

(31) TABLE-US-00007 TABLE 7 Components Compounds/trade name Weight Second acrylate BR-952 (oligomer) 25 g component 3000A (oligomer) 10 g Lauric acrylate 26 g Isobornyl methacrylate 27 g Photoinitiator 819 (acyl phosphine oxide 0.5 g radical photoinitiator) Additives Greatech GT8003 (toughening agent) 7 g BYK-377 (leveling agent) 0.4 g GENORAD 20 (stabilizer agent) 0.6 g Colorant Phthalocyanine blue 3.5 g (PB15:3)blue pigment

(32) In this Comparative example 2, the preparation method of the light curing material for 3D printing is basically the same as that of Example 4, except that the components used are replaced accordingly.

(33) Weakly/non-polar acrylate monomers or oligomers are used as the acrylate component in Comparative example 2, and a light curing transparent blue materials for 3D printing is obtained.

(34) Performance testing of the light curing materials for 3D printing in the above examples and the Comparative examples are carried out:

(35) 1. The viscosity and surface tension of the ink composition in the example were tested at room temperature and operating temperature by using a DV-I digital viscometer and a BZY-1 automatic surface tension meter.

(36) 2. The ink composition of the example is applied to a 3D light curing inkjet printer with an industrial jet nozzle, and the wavelength of the UV light source is set as 395 nm, and the ink fluency test and the accuracy test of the molded parts are carried out at the appropriate injection temperature, respectively, the accuracy test is mainly reflected by the volume shrinkage, the testing method is:

(37) The density ρ1 before curing and ρ2 after complete curing of the photosensitive resin was determined at 25° C. using the specific gravity bottle method with water as a reference, the volumetric shrinkage is calculated with the following equation:
volumetric shrinkage %=(ρ.sub.2−ρ.sub.1)÷ρ.sub.2×100%

(38) 3. Testing of the Light Transmittance

(39) The ink composition of this example is applied to a 3D light curing inkjet printer with an industrial jet nozzle, and the wavelength of the UV light source is set as 395 nm, and a 50 mm×50 mm block with a thickness of 2 mm is printed at the injection temperature.

(40) The light transmittance is measured by a UV spectrophotometry, the light transmittance is the ratio of the light flux through the specimen to the light flux irradiated on the specimen, expressed as a percentage. For specific testing methods, refer to GB/T 2410-2008, Measurement of light transmittance and haze of transparent plastics.

(41) 4. Testing of Shore Hardness

(42) The ink composition of this example is applied to a 3D light curing inkjet printer with an industrial jet nozzle, and the wavelength of the UV light source is set as 395 nm, a 50 mm×50 mm block with a thickness of 6.4 mm is printed at the injection temperature, the Shore hardness of the block is measured. For the specific testing methods, refer to GB/T2411-2008, Indentation hardness (Shore hardness) of plastics and hard rubber is measured by using a hardness tester.

(43) 5. Testing of Bending Performance

(44) Bending properties are used to indicate the ability of a material to resist flexural deflection or the rigidity of a tested material. The ink composition of this example is applied to a 3D light curing inkjet printer with an industrial jet nozzle and the wavelength of the UV light source is set as 395 nm, and a long block with length×width×thickness of 80 mm×10 mm×4 mm is printed at the injection temperature, its bending performance is tested. For the specific testing methods, refer to GB/T 9341-2008, Determination of the bending performance of plastics.

(45) 6. Testing of the Impact Strength

(46) Impact strength is a measure for a material's toughness, usually defined as the energy absorbed by per unit of the cross-sectional area when a specimen is broken or fractured under an impact load. For the specific testing method, refer to GB/T1043.1-2008, Part 1 of the Impact performance determination of a plastic simple supported beam: non-instrumental impact testing.

(47) The testing results of each performance are shown in table 8 below:

(48) TABLE-US-00008 TABLE 8 Testing results of the performances Parameters Examples of the Comparative Comparative performances Example 1 Example 2 Example 3 Example 4 Example 5 example 1 example 2 Viscosity at 45.6 62.1 35.8 60.1 32.5 50.4 40.2 room Surface 23.9 30.6 29.8 23.5 29.2 24.5 23.4 tension at room Injection 50 60 45 55 40 55 50 temperature Viscosity at 12.4 12.1 12.6 12.8 11.8 10.9 11.2 the Injection temperature Surface 23.7 29.8 29.4 22.7 28.9 24.2 22.9 tension at the injection temperature Shrinkage 3.75 3.14 4.25 3.25 4.57 3.54 4.15 Fluency OK OK OK OK OK OK OK Light 51.47 5.6 4.2 76.8 39.8 91 87 transmittanc Shore 92 96 91 95 90 92 89 Bending 82 89 80 85 75 83 72 strength Bending 2421 2651 2254 2500 2124 2412 2105 modulus Impact 30 38 40 24 35 15 17 strength

(49) It can be seen from the results of the above testing:

(50) 1. Using the light curing non-transparent materials for 3D printing provided by the present disclosure, the light transmittance values of the test blocks are all below 80%. Furthermore, by adjusting the ratio of the first acrylate component to the second acrylate component and the polarity of the two components, it is possible to obtain non-transparent objects with different light transmittance. If the first acrylate component and the second acrylate component are not both included, e.g. only the polar acrylate component or the weakly polar/non-polar acrylate component is included, the light transmittance values of the test blocks are all greater than 80%, i.e. the light curing materials are transparent materials.

(51) 2. For the test blocks printed by using the light curing non-transparent materials for 3D printing provided by the present disclosure, the Shore hardness values are all above 90%, the bending strength values are above 75 Mpa, the bending modulus values are above 2100 Mpa, the impact strength values are above 20 KJ/m.sup.2, indicating that the objects printed by using the materials have high hardness, good bending properties, especially outstanding impact strength and toughness, that is, the 3D printed products have good mechanical properties to meet practical needs.

(52) 3. The light curing non-transparent material for 3D printing provided by the present disclosure has good printing smoothness, no clog of the nozzle hole of the print head or disconnection of the printing process, and the shrinkage rate of the printed object is less than 5%, thus the accuracy of the printed object is high.

(53) 4. The light curing non-transparent material for 3D printing provided by the present disclosure has low viscosity at room temperature and operating temperature (40˜60° C.), and low injection temperature, which is not only suitable for 3D printing, but also able to extend the service life of 3D printer.

Example 6

(54) This example provides a 3D printer, specifically a 3D inkjet printer. The structure schematic diagram of the 3D printer is shown in FIG. 1, which comprises a material container 1, an inkjet print head 2 and a connecting device 3, where:

(55) The light curing non-transparent material for 3D printing provided by any one of examples 1˜5 is stored in the material container 1;

(56) The connecting device 3 is used to connect the material container 1 and the inkjet print head 2, the light curing non-transparent material for 3D printing stored in material container 3 is supplied to the inkjet print head 2 via the connecting device 3;

(57) The light curing non-transparent material for 3D printing injected from the inkjet print head 2 is cured to form a light curing layer on a bearing platform (not shown).

(58) The number of the material containers 1 is not specifically limited in this example, and the number of material containers 1 can be set according to the types of light curing non-transparent materials. The inkjet print head 2 can be a single-channel print head or a multi-channel print head, or it can be a combination of a single-channel print head and a multi-channel print head.

(59) Further referring to FIG. 1, the 3D printer provided by this example may further comprise: a controller 4 and a UV light source 5, wherein the controller 4 is capable of controlling the supply of the light curing non-transparent material for 3D printing from the material container 1 to the inkjet print head 2, and controlling the UV radiation curing of the material layer 6 injected on the bearing platform by the UV light source 5 so as to form a light curing layer; the specific UV light source 5 may be a UV light emitting diode.

Example 7

(60) This example provides a 3D product, which is printed by using the light curing non-transparent material for 3D printing provided by any one of examples 1˜5.

(61) Specifically, 3D printed products with different colors can be printed according to the requirements, for example, by supplying the materials in examples 1-5 above to the printer J501 of Seine or the 3D printer provided in example 6 above, white objects, red non-transparent objects, blue non-transparent objects and yellow non-transparent objects can be printed respectively. Of course, it is also possible to mix the materials in the above examples in a certain proportion to obtain non-transparent 3D printed products with other colors.

(62) What shall be clarified is that the above-described embodiments are merely illustrative of several implementing schemes of the disclosure, but should not be construed as limiting the scope of the present disclosure. It should be noted that variations and modifications may be made by those skilled in the art without departing from the concept of the present disclosure. Therese variations and modifications all fall into the protection scope of the present disclosure. Therefore, the scope of the present disclosure should be subject to the appended claims.