CN109438632B - 3D printing photosensitive resin with ultralow volume shrinkage and preparation method thereof - Google Patents
3D printing photosensitive resin with ultralow volume shrinkage and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 152
- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 238000010146 3D printing Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000001723 curing Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims 2
- 229920006362 Teflon® Polymers 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 20
- 150000003254 radicals Chemical class 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 45
- -1 polytetrafluoroethylene Polymers 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 3
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013499 data model Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
Abstract
The method mainly adopts a 3D printing photosensitive resin material self-filling mode, and takes a cured product of the photosensitive resin as a filling material to reduce the volume shrinkage of the photosensitive resin. The method can effectively reduce the volume shrinkage of the free radical type photosensitive resin, increase the compatibility of the filler and the original system, and improve the dispersibility and stability of the filler in the system.
Description
Technical Field
The invention belongs to the field of functional organic high polymer materials, and particularly relates to 3D printing photosensitive resin.
Background
The 3D printing technology is also called additive manufacturing technology, and is a technology for constructing a three-dimensional object by using materials such as micron-sized metal powder, thermoplastic plastic, or liquid photosensitive resin and the like through layer-by-layer printing molding on the basis of a digital file. 3D printing technology has many prominent advantages: workpieces which cannot be manufactured by the traditional process with a complex structure can be directly obtained from the data model, and extra processing is not needed in the middle; the manufacturing period of the sample piece is short; the material waste is less, and no leftover material exists basically; unused materials may be reused, etc. It is because of these advantages that 3D printing is called "third industrial revolution", 21 is actually the most developmentally valuable technology, and so on.
At present, the mature 3D printing process mainly comprises 'fuse deposition rapid prototyping', 'selective laser sintering rapid prototyping' and 'stereolithography rapid prototyping'. The earliest and most widely used 3D printing technique in industry is stereolithography rapid prototyping, which is a computer stereolithography technique that divides a prepared product into a plurality of layers in a longitudinal space, controls laser to scan a single layer point by point, cures photosensitive resin, and finally obtains a complete three-dimensional entity. The quality of the prepared product mainly depends on the quality of the performance of the photosensitive resin, so that the photosensitive resin with excellent performance is a guarantee for the 3D printing technology to really enter practical application.
The radical type photosensitive resin is the most commercially available photosensitive resin at the earliest time, and the most widely used photosensitive resin in the field of 3D printing is also the radical type at present. The resin is obtained by polymerizing an acrylate prepolymer and a free radical photoinitiator. The photoinitiator decomposes free radicals under the action of ultraviolet light, and the free radicals initiate the double bonds of the acrylate to break, so that the double bonds are mutually polymerized to form the polymer with larger molecular weight. The main advantages of the radical type photosensitive resin are: the curing speed is high, the variety of the photosensitizer is high, but the problems of large volume shrinkage during polymerization, large internal stress of a product, easy buckling deformation and the like exist, and the application of the photosensitive resin in some fields with high requirements on the precision of workpieces is severely limited. Therefore, reducing the volume shrinkage of radical type photosensitive resins is a constant research focus in this field.
The volume shrinkage of photosensitive resins is reduced by adding inorganic powder, inert non-reactive resin or monomer with expansibility. Inorganic powders are more commonly used: nano silicon dioxide, titanium dioxide, aluminum silicate, barium sulfate, nano zinc oxide and the like. When the photosensitive resin is cured by the action of the radical initiator, the inorganic powder filled in the system occupies a part of the space because no reaction occurs, so that the volume shrinkage of the whole system can be obviously reduced, and other properties such as strength, modulus and the like of the original material can be additionally provided. However, the essential difference between the inorganic filler and the organic photosensitive resin leads the inorganic filler and the organic photosensitive resin not to be completely compatible, and most of the inorganic filler is suspended in a photosensitive resin system through high-speed dispersion, so that the inorganic filler has high requirements on equipment during dispersion, and is easy to agglomerate, precipitate and the like during use, thereby seriously affecting the stability of products. In some special application scenes, the inorganic filler cannot be used at all, for example, photosensitive resin for casting requires that the resin can be completely decomposed at high temperature without residues, and the inorganic filler cannot be decomposed and has a large amount of residues, so that the inorganic filler cannot be used.
Compared with inorganic fillers, the compatibility of the inert resins and photosensitive resins is greatly improved, the performance of the whole system is slightly influenced, the stability is good, but the compatibility of the inert resins is not as good as that of the inorganic fillers, so that the types of the inert resins which can be selected at present are not more, and the inert resins are not suitable for all photosensitive resin systems.
Adding a monomer with expansion performance to compensate for curing shrinkage of the photosensitive resin is another method for reducing volume shrinkage of the photosensitive resin at present, but the monomer with expansion performance has few types, high price and limited application in large quantity.
In summary, the existing methods for reducing the volume shrinkage rate of photosensitive resin have respective defects, and it is of great significance to research a new method for effectively solving the problem of volume shrinkage of photosensitive resin and overcoming the defects.
Disclosure of Invention
The invention aims to provide a 3D printing photosensitive resin with ultralow volume shrinkage and a preparation method thereof, which can effectively reduce the volume shrinkage of a free radical type photosensitive resin, increase the compatibility of a filler and an original system, and improve the dispersibility and stability of the filler in the system.
The method mainly adopts a 3D printing photosensitive resin material self-filling mode, and takes a cured product of the photosensitive resin as a filling material to reduce the volume shrinkage of the photosensitive resin.
The invention provides a preparation method of a 3D printing photosensitive resin with ultralow volume shrinkage, which comprises the following steps:
synthesizing 3D printing photosensitive resin according to the conventional method, or taking the conventional 3D printing photosensitive resin sold in the market as a raw material, solidifying the photosensitive resin, crushing, grinding into resin powder, and adding the nanoscale resin powder serving as a filling material into a corresponding 3D printing photosensitive resin (the 3D printing photosensitive resin same as the resin powder) formula system to prepare a 3D printing photosensitive resin product.
Further, the filling proportion of the resin powder in the 3D printing photosensitive resin is 1% to 50% (percentage of the filling material in the total mass of the photosensitive resin after filling, i.e. content), preferably 20% to 30%. Because the addition of the nano powder filler can cause the viscosity of the system fluid to increase, the specific addition proportion can be specifically controlled according to the requirements of different devices on the viscosity of the 3D printing resin and the volume shrinkage of the product in practical application.
Further, the method of curing the photosensitive resin is to perform complete curing under the curing conditions under the irradiation of ultraviolet rays corresponding to the kind of the resin.
Preferably, the curing method is to coat the photosensitive resin on a polytetrafluoroethylene plate, cure under a high-pressure mercury lamp, and then peel off the polytetrafluoroethylene plate to obtain a solid resin, and then crush and grind the solid resin.
Further, the powder and grinding are to crush and grind the cured resin into nano-scale powder;
further, the resin includes various systems of 3D printing photosensitive resins, such as epoxy acrylates, polyester acrylates, urethane acrylates, cationic epoxies, or a mixture of multiple types.
Further, the 3D printing photosensitive resin is selected from one or more of polyester acrylate resin, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, epoxy acrylate resin, trimethylolpropane triacrylate, tripropylene glycol diacrylate and hexanediol diacrylate.
Further, a resin powder filler is added to a 3D printing photosensitive resin (the same 3D printing photosensitive resin as the resin powder) formulation system by a high speed dispersion method.
Preferably, the high-speed dispersion is carried out for 15-25 minutes at the speed of 2500-.
Compared with the prior art, the method of the invention takes the self-filling of the nano particles of the original formula system as the filler and has the following advantages:
1. in the method, as the performance of the filling material is completely consistent with that of the original formula system, any performance of the original resin system is not influenced, the volume shrinkage of the free radical type photosensitive resin is effectively reduced, and the volume shrinkage after filling is reduced by more than 50%.
2. In the method, the 3D printing photosensitive resin is used as a filling material, and the filling material is completely consistent with the original formula system, so that the compatibility is good, the dispersibility is good, the product performance is stable, and the situations of precipitation and the like are not easy to occur in the using process.
3. In the method, 3D printing photosensitive resin is used as a filling material, no residue is sufficient, and some special application scenes are met, for example, the photosensitive resin for casting requires that the resin can be completely decomposed at high temperature;
4. in the method, the 3D printing photosensitive resin is used as a filling material, the compatibility is good, the dispersibility is good, any performance of the original resin system is not influenced, and the adding amount of the filling material in the preparation process can be far greater than that of the inorganic filling material and the inert resin, so that the volume shrinkage reducing effect is obvious.
5. In the method, the 3D printing photosensitive resin is used as a filling material, so that the cost of the original formula system is slightly influenced.
6. The method of the invention has simple operation and low cost.
Detailed Description
The present invention is further illustrated by the following specific embodiments. The following examples are only some embodiments of the present invention, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
The following examplesAnd the volume shrinkage rate is the ratio of the product volume printed by actual 3D to the product volume printed by set 3D, wherein the product value accounts for the product volume printed by actual 3D. For example, a 5 cm by 5 cm cube model is designed by software, introduced into an existing 3D printing device, the cube model is printed using the prepared photosensitive resin as a printing material, and the length of each side of the cube is measured after printing. The design cube side length is 5 cm x 5 cm, and if the actual printed cube physical model side length is 4.9 cm x 4.9 cm, then the cube is used
Example 1
Unfilled 3D printing photosensitive resin:
600 g of epoxy acrylate resin, 100 g of trimethylolpropane triacrylate, 250 g of tripropylene glycol diacrylate and 50 g of photoinitiator 1173 are uniformly mixed to prepare the 3D printing photosensitive resin A. The resin volume shrinkage was 10.6%.
Filled 3D printing photosensitive resin:
coating 300 g of the mixed photosensitive resin on a polytetrafluoroethylene plate, curing for 5 minutes under a 3KW high-pressure mercury lamp at a lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing in a crusher, and grinding in a ball mill to nano level. And then adding 20 g of crushed resin powder into 80 g of photosensitive resin A, and dispersing at a high speed of 3000 rpm for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
After the test filling, the volume shrinkage of the resin after curing (after 3D printing) is 5.1%, the volume shrinkage after filling is reduced by 51.9%, and the product is stored for 3 months without filler precipitation and uneven dispersion.
Example 2
Unfilled 3D printing photosensitive resin:
600 g of epoxy acrylate resin, 100 g of trimethylolpropane triacrylate, 250 g of tripropylene glycol diacrylate and 50 g of photoinitiator 1173 are uniformly mixed to prepare the 3D printing photosensitive resin A. The resin volume shrinkage was 10.6%.
Filled 3D printing photosensitive resin:
coating 300 g of the mixed photosensitive resin on a polytetrafluoroethylene plate, curing for 5 minutes under a 3KW high-pressure mercury lamp at a lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing in a crusher, and grinding in a ball mill to nano level. And then adding 30 g of crushed nano powder into 70 g of resin A, and dispersing at a high speed of 3000 r/min for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
After filling was tested, the volume shrinkage of the product after resin curing (after 3D printing) could be reduced by 57.6%. The product is stored for 3 months without filler precipitation and uneven dispersion.
Example 3
Unfilled 3D printing photosensitive resin:
and uniformly mixing 700 g of urethane acrylate resin, 100 g of trimethylolpropane triacrylate, 200 g of 1, 6-hexanediol diacrylate and 50 g of photoinitiator 184 to obtain the 3D printing photosensitive resin A. The resin was found to shrink by 8.5% in volume.
Filled 3D printing photosensitive resin:
coating 300 g of mixed photosensitive resin A on a polytetrafluoroethylene plate with the thickness of 5mm, curing for 5 minutes under a 3KW high-pressure mercury lamp with the lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing the product in a crusher, and then grinding the crushed product in a ball mill to a nanometer level. And then adding 20 g of the crushed powder into 80 g of photosensitive resin A, and dispersing at a high speed of 3000 rpm for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
After the test filling, the volume shrinkage of the resin after curing (after 3D printing) is 3.8%, the volume shrinkage after filling is reduced by 55.3%, and the product is stored for 3 months without filler precipitation and uneven dispersion.
Example 4
Unfilled 3D printing photosensitive resin:
and uniformly mixing 700 g of urethane acrylate resin, 100 g of trimethylolpropane triacrylate, 200 g of 1, 6-hexanediol diacrylate and 50 g of photoinitiator 184 to obtain the 3D printing photosensitive resin A. The resin was found to shrink by 8.5% in volume.
Filled 3D printing photosensitive resin:
coating 300 g of mixed photosensitive resin A on a polytetrafluoroethylene plate with the thickness of 5mm, curing for 5 minutes under a 3KW high-pressure mercury lamp with the lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing the product in a crusher, and then grinding the crushed product in a ball mill to a nanometer level. And adding 30 g of crushed nano powder into 70 g of resin A, and dispersing at a high speed of 3000 r/min for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
The filled resin was tested to reduce the volume shrinkage after curing (after 3D printing) by 60.2%. The product is stored for 3 months without filler precipitation and uneven dispersion.
Example 5
Unfilled 3D printing photosensitive resin:
650 g of polyester acrylate resin, 50 g of trimethylolpropane triacrylate, 110 g of ethoxylated pentaerythritol tetraacrylate, 140 g of ethoxylated bisphenol A diacrylate and 50 g of photoinitiator 184 are uniformly mixed to prepare the 3D printing photosensitive resin A, and the volume shrinkage of the resin is 8.2%.
Filled 3D printing photosensitive resin:
coating 300 g of mixed photosensitive resin A on a polytetrafluoroethylene plate with the thickness of 5mm, curing for 5 minutes under a 3KW high-pressure mercury lamp with the lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing the product in a crusher, and then grinding the crushed product in a ball mill to a nanometer level. And adding 20 g of the crushed powder into 80 g of photosensitive resin, and dispersing at a high speed of 3000 rpm for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
After testing, after the filled resin is cured (after 3D printing), the curing shrinkage after filling is tested to be 4.3%, the volume shrinkage after filling is reduced by 47.6%, and the situation of filler precipitation and uneven dispersion does not occur after the product is stored for 3 months.
Example 6
Unfilled 3D printing photosensitive resin:
650 g of polyester acrylate resin, 50 g of trimethylolpropane triacrylate, 110 g of ethoxylated pentaerythritol tetraacrylate, 140 g of ethoxylated bisphenol A diacrylate and 50 g of photoinitiator 184 are uniformly mixed to prepare the 3D printing photosensitive resin A, and the volume shrinkage of the resin is 8.2%.
Filled 3D printing photosensitive resin:
coating 300 g of mixed photosensitive resin A on a polytetrafluoroethylene plate with the thickness of 5mm, curing for 5 minutes under a 3KW high-pressure mercury lamp with the lamp distance of 10 cm from the product, peeling the cured product from the polytetrafluoroethylene plate, crushing the product in a crusher, and then grinding the crushed product in a ball mill to a nanometer level. And adding 30 g of the crushed powder into 70 g of photosensitive resin, and dispersing at a high speed of 3000 rpm for 20 minutes to obtain the finished product of the 3D printing photosensitive resin.
The volume shrinkage of the filled resin after curing (after 3D printing) was tested to be reduced by 53.9%. The product is stored for 3 months without filler precipitation and uneven dispersion.
Claims (7)
1. The preparation method of the 3D printing photosensitive resin with ultralow volume shrinkage comprises the following steps:
synthesizing 3D printing photosensitive resin according to the conventional method, solidifying the photosensitive resin, crushing, grinding into nanoscale resin powder, adding the nanoscale resin powder serving as a filler into the corresponding same 3D printing photosensitive resin formula system, and preparing the 3D printing photosensitive resin product with ultralow volume shrinkage;
the mass fraction of the nanoscale resin powder in the ultralow-volume-shrinkage 3D printing photosensitive resin is 20-30%.
2. The method for preparing the photosensitive resin for ultra-low volume shrinkage 3D printing according to claim 1, wherein the photosensitive resin is cured by fully curing under ultraviolet irradiation curing conditions corresponding to the resin species.
3. The method for preparing the photosensitive resin for 3D printing with ultra-low volume shrinkage of claim 1, wherein the curing method comprises coating the photosensitive resin on a teflon plate, curing under a high-pressure mercury lamp, peeling off the teflon plate to obtain a solid resin, and then pulverizing and grinding the solid resin.
4. The preparation method of the photosensitive resin for 3D printing with ultralow volume shrinkage according to claim 1, wherein the photosensitive resin for 3D printing comprises one or more of epoxy acrylates, polyester acrylates, polyurethane acrylates and cationic epoxy resins.
5. The method for preparing the photosensitive resin for 3D printing with ultra-low volume shrinkage of claim 1, wherein the nano-scale resin powder filler is added into the 3D printing photosensitive resin formulation system by a high-speed dispersion method.
6. The method for preparing the 3D printing photosensitive resin with the ultralow volume shrinkage as claimed in claim 5, wherein the high-speed dispersion is carried out at 3500 rpm of 2500 for 15-25 minutes to obtain the 3D printing photosensitive resin with the ultralow volume shrinkage.
7. The ultra-low volume shrinkage 3D printing photosensitive resin prepared by the method of any one of claims 1 to 6.
Priority Applications (1)
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