CN112679677A - Antistatic photosensitive resin for photocuring rapid forming and preparation method and application thereof - Google Patents
Antistatic photosensitive resin for photocuring rapid forming and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an antistatic photosensitive resin for photocuring rapid prototyping, and a preparation method and application thereof. The antistatic photosensitive resin comprises a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, a modified multi-walled carbon nanotube, hyperbranched epoxy resin and an antioxidant. The antistatic photosensitive resin provided by the invention has the advantages of good antistatic effect, low viscosity, extremely low addition of a conductive agent, good photocuring activity of a resin system, excellent mechanical property of a cured resin, good toughness and surface resistance value of the cured resin lower than 109Omega, and the resistance value is even, and printed material surface accuracy and dimensional stability are good.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to an antistatic photosensitive resin for photocuring rapid prototyping, and a preparation method and application thereof.
Background
The photocuring rapid prototyping (SLA) is the first rapid prototyping technology put into commercial use, and its specific working principle is as follows: and controlling the ultraviolet laser by using a computer program to scan and move the ultraviolet laser on the surface of the photosensitive resin, so that the photosensitive resin is cured to form a single layer of the model. After each layer of photosensitive resin is cured, the curing platform moves by a single layer thickness, and then the space formed by the resin is filled up through automatic flowing or passive coating, and curing is carried out again. Repeating the steps to obtain the formed part. The photocuring rapid prototyping technology can accurately control laser movement, has the advantages of low energy consumption, low cost, high prototyping precision and the like, and can print parts with any structures which cannot be manufactured by the traditional processing method. Therefore, the development of photocuring rapid prototyping equipment and materials has great development potential and application prospect.
The photosensitive resin which is the leading position in the market at present is mainly high-strength photosensitive resin, high-toughness photosensitive resin, high-temperature-resistant photosensitive resin, transparent photosensitive resin and the like, and the photosensitive resin composition is rarely developed specifically for special application occasions, such as the application field of electronic and electric appliances, and has higher requirements on static electricity resistance.
Patent CN 109517112 a discloses a conductive photosensitive resin composition for photo-curing rapid prototyping, which is developed for special application, but the conductive filler added in the conductive photosensitive resin composition reaches 30-78%, resulting in high viscosity of the photosensitive resin composition; in addition, the filler can affect the laser scanning process, such as reflecting or absorbing laser, which causes the laser scanning process to be obviously different from the scanning process of common resin, and the surface precision of the printed product can be affected to a certain extent.
Therefore, the development of photosensitive resin compositions for special applications has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects of photosensitive resin compositions aiming at special application occasions in the prior art and provide an antistatic photosensitive resin for photocuring rapid forming. The antistatic photosensitive resin provided by the invention has the advantages of good antistatic effect, low viscosity, extremely low addition of a conductive agent, good photocuring activity of a resin system, excellent mechanical property of a cured resin, good toughness and surface resistance value of the cured resin lower than 109Omega, and the resistance value is uniform, and the surface precision and the dimensional stability of a printed piece are good; the container-mounted electronic and electrical components printed by the antistatic photosensitive resin can effectively prevent the electronic components from generating destructive influence on electronic and electrical equipment due to static accumulation and failure in effectively conducting static in the carrying process.
Another object of the present invention is to provide a method for preparing the above antistatic photosensitive resin.
Another object of the present invention is to provide an application of the above antistatic photosensitive resin in 3D printing.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antistatic photosensitive resin for photocuring rapid prototyping comprises the following components in parts by weight:
the modified multi-walled carbon nanotube is obtained by modifying hyperbranched epoxy resin.
The conductivity of the multi-wall carbon nano tube is superior to that of carbon black, and the multi-wall carbon nano tube is one of ideal auxiliary agents for preparing conductive plastics, adhesives or coatings. However, when the multi-walled carbon nanotubes are added into the cylinder filling resin for 3D printing, the multi-walled carbon nanotubes are difficult to disperse and are easy to disperse unevenly, so that the surface resistance of a printed product is uneven; and the resin directly added with the multi-walled carbon nano-tube can be settled in the long-term use process, so that the resistance of a printed piece fluctuates, and the large-scale production is not facilitated.
The inventor of the invention repeatedly researches and discovers that the modified multi-walled carbon nanotube obtained by carrying out specific modification treatment on the multi-walled carbon nanotube by utilizing hyperbranched epoxy resin has excellent anti-settling and dispersing effects, can effectively avoid the remarkable reduction of the conductivity of a cured material caused by the settling or agglomeration of a conductive agent only by adding the modified multi-walled carbon nanotube into the resin in a very small amount when the modified multi-walled carbon nanotube is used as the conductive agent, does not need to improve the energy of a laser in the photocuring process, reduces the laser interval, reduces the scanning speed and other operations for improving the energy consumption or reducing the printing efficiency, can be completely operated according to the scanning process of common resin, and greatly improves the convenience of equipment operators. The principle may be: the surface of the modified multi-walled carbon nanotube contains a certain amount of hyperbranched epoxy resin, so that the modified multi-walled carbon nanotube is extremely easy to disperse in a free radical-cation hybrid photocuring system and has no agglomeration phenomenon, the photosensitive resin system is kept still for 12 months, the modified multi-walled carbon nanotube dispersed in the photosensitive resin system has no sedimentation, the surface resistance of a printing part of the photosensitive resin kept still for 12 months is uniform, and the resistivity of the surface resistance of the photosensitive resin prepared at the beginning is in the same order of magnitude; epoxy groups on the surface of the multi-walled carbon nano-tube after surface modification participate in cationic photocuring reaction to form a rigid particle toughening center, so that the toughness of the cured resin is improved to a certain extent, and the curing efficiency of a free radical-cationic resin system is not influenced.
In addition, the conventional epoxy resin is mainly rubber, elastomer with a core-shell structure and the like, and the addition of the series of epoxy resin into a resin system can obviously improve the viscosity of the resin system. The application unexpectedly finds that the hyperbranched epoxy resin has lower viscosity, has better toughening effect with the curing system of the application, and can have better toughness under the condition of not reducing the viscosity of the antistatic photosensitive resin; the resin condensate has excellent mechanical property, good toughness, uniform surface resistance and good surface precision and dimensional stability of printed parts, and provides guarantee for large-scale popularization of the resin.
The antistatic photosensitive resin provided by the invention is prepared by modifying multi-wall carbon nano-tubes and super-nano-tubesThe branched epoxy resin has good antistatic effect under the synergistic cooperation, low viscosity, extremely low addition of conductive agent, good photocuring activity of a resin system, excellent mechanical property of cured resin, good toughness and surface resistance value of the cured resin lower than 109And the resistance value is uniform, and the surface precision and the dimensional stability of the printed piece are good.
Cationic photocurable components, free radical photosensitive resin components, cationic photoinitiators, free radical initiators, and antioxidants conventional in the art may be used in the present invention.
Preferably, the cationic light-curing component is one or more of glycidyl ether type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, vinyl ether type monomer, aliphatic epoxy resin, novolac epoxy resin, vinyl ketal type monomer or oxetane type monomer.
More preferably, the cationic light-curing component is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, OX of Toagosei company or T-221.
Preferably, the radical photosensitive resin component is one or more of urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, silicone oligomer, hyperbranched oligomer, TPGDA, NPGDA, NPG (PO)2DA, DPGDA, TMPTA, PETA, PETTA, DPPA, or IBOA.
More preferably, the free radical photosensitive resin component is epoxy acrylate, polyester acrylate, hyperbranched oligomer, TPGDA, NPG (PO)2DA. PETA or PETTA.
Preferably, the cationic photoinitiator is one or more of diaryliodonium salts (such as didodecylbenziodonium salt, long-chain alkoxy diphenyliodonium salt, Omnicat 440 and Omnicat445 from IGM, 251 from Shanghai Bingzhi chemical engineering, and IK-1 from San-Apro), triarylsulfonium salts (6990 and 6976 from BSAF, Omnicat 320 and Omnicat430 from IGM, Omnicat432 and CPI-100P, CPI-101A, CPI-200K, CPI-210S from San-Apro) or ferrocenium salts (261 and 262 from Chivacure).
More preferably, the cationic photoinitiator is one or more of triarylsulfonium salts or ferrocenium salts.
Further preferred is Chivacure 1190 or UVI-6976 from BASF.
Preferably, the free radical initiator is a cleavage type free radical photoinitiator.
More preferably, the radical initiator is one or more of 2-hydroxy-2-methyl-phenylacetone-1 (1173), 1-hydroxy-cyclohexanophenone (184), 2-hydroxy-2 methyl-p-hydroxyethyl ether phenylacetone-1 (2959), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), [ bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide ] (819), 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphine oxide (TEPO), Irgacure500 or Irgacure 1000.
Further preferably one or more of 1173, 184, 2959, TPO or 819.
Preferably, the hyperbranched epoxy resin is one or more of HyperE102, HyperDE1050, HyperFE1050, HyperDE1045, HyperME 1050 or HyperME 1045.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1176 or BHT.
Multi-walled carbon nanotubes are commercially available.
Preferably, the modified multi-walled carbon nanotube is prepared by the following process:
s1: carrying out acid washing treatment on the multi-walled carbon nano tube;
s2: mixing silane coupling agent with sulfydryl and multi-walled carbon nano-tubes treated by acid cleaning to react to obtain the multi-walled carbon nano-tubes with sulfydryl on the surfaces;
s3: and (3) mixing and modifying the multi-walled carbon nano tube with the surface provided with the sulfydryl obtained in the step (S2) with hyperbranched epoxy resin to obtain the modified multi-walled carbon nano tube.
More preferably, in S1, the multiwalled carbon nanotubes are acid-washed with a nitric acid solution (34% by mass).
Specifically, the multi-walled carbon nano-tube is added into a dilute nitric acid solution, refluxed, stirred, cleaned and filtered.
After the operation treatment, the surface of the multi-wall carbon nano tube is oxidized to a certain extent, and a certain amount of hydroxyl or carboxyl is generated on the surface.
More preferably, the silane coupling agent with mercapto in S2 is one or more of 3-mercaptopropyltetramethyldimethoxysilane or 3-mercaptopropyltrimethoxysilane.
More preferably, the mass ratio of the multi-walled carbon nanotubes with sulfydryl on the surface in S3 to the hyperbranched epoxy resin is 1: 0.5-1: 10.
The preparation method of the antistatic photosensitive resin comprises the following steps: and mixing a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, a modified multi-walled carbon nanotube and an antioxidant to obtain the antistatic photosensitive resin.
The application of the antistatic photosensitive resin in 3D printing is also within the protection scope of the invention.
Preferably, the antistatic photosensitive resin is applied to the preparation of electronic components.
Compared with the prior art, the invention has the following beneficial effects:
the antistatic photosensitive resin provided by the invention has the advantages of good antistatic effect, low viscosity, extremely low addition of a conductive agent, good photocuring activity of a resin system, excellent mechanical property of a cured resin, good toughness and surface resistance value of the cured resin lower than 109The resistance value is uniform, and the surface precision and the dimensional stability of a printed piece are good; the container-mounted electronic and electrical components printed by the antistatic photosensitive resin can effectively prevent the electronic components from generating destructive influence on electronic and electrical equipment due to static accumulation and failure in effectively conducting static in the carrying process.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
the cationic photocuring component 1#, bisphenol A epoxy resin, DER-331 of DOW chemical company;
the cationic photocuring component 2#, 3, 4-epoxycyclohexyl formic acid-3, 4-epoxycyclohexyl methyl ester is S-06E of New Nantong Xinnaxi Material Co., Ltd;
cationic photocurable component No. 3, an oxetane monomer, which is OXT-221 of Toagosei corporation;
the free radical photosensitive resin component No. 1 is TPGDA of MIWON company;
radical photosensitive resin component No. 2 is NPG (PO) of MIWON2DA；
The free radical photosensitive resin component No. 3 is TMPTA of MIMON company;
the free radical initiator No. 1 is 184 of Tianjin long time;
cationic initiator # 1 is UVI-6976 from BASF;
the hyperbranched epoxy resin No. 1 is HyPerE 102;
the hyperbranched epoxy resin No. 2 is HyPerDE 1050;
antioxidant No. 1 is antioxidant 168 from Dow chemical company;
antioxidant No. 1 is antioxidant 1010 from Dow chemical company;
the white material in the market is Geda 8118 of Zhongshan Dayi scientific and technological limited;
the multi-walled carbon nanotube is an industrial-grade multi-walled carbon nanotube which is synthesized by Shenzhen Nangang Limited company by a CVD method, and the purity of the multi-walled carbon nanotube is more than 95%.
In addition, the modified multi-walled carbon nanotube is prepared by the following steps: adding multi-wall carbon nano-tubes (2g) into nitric acid (100g) with the concentration of 37%, ultrasonically cleaning for 30min at room temperature, and filtering. Adding acid-treated multi-walled carbon nanotubes (2g) into an ethanol (2g of silane coupling agent added with 100g of ethanol) solution of 3-mercaptopropyltetramethyldimethoxysilane serving as a silane coupling agent with mercapto groups, ultrasonically stirring and refluxing for 12h at 40 ℃, filtering, adding the treated multi-walled carbon nanotubes (2g) into an acetone (100g) solution, stirring, adding 0.05 percent of DBU (calculated according to the amount of epoxy resin) into hyperbranched epoxy resin (5g) dropwise adding the acetone solution (100g) of the multi-walled carbon nanotubes (2g), increasing the reaction temperature to 60 ℃, stirring and reacting for 12h, filtering and cleaning with acetone and water after the reaction is finished until cleaning solution is neutral, and drying in vacuum to obtain the multi-walled carbon nanotubes with organically treated surfaces.
Wherein, in the preparation process of the modified multi-walled carbon nanotube 1#, hyperbranched epoxy resin HyPerE102 is selected; in the preparation process of the modified multi-walled carbon nanotube 2#, hyperbranched epoxy resin HyPerDE1050 is selected.
The antistatic photosensitive resin of each example and comparative example of the present invention was prepared by the following process: and (3) stirring and mixing the cationic photocuring component, the free radical photocuring component, the cationic photoinitiator, the free radical photoinitiator, the modified multi-walled carbon nanotube and the antioxidant for 60min at 25 ℃ to obtain the modified multi-walled carbon nanotube.
The test method of each performance index of each example and comparative example is as follows:
1) critical exposure energy EcAnd a curing depth DpThe test of (2): using SLA 3D printer, at a known laser power PLLaser scanning interval hsIn the case of different laser scanning rates VsPerforming single-layer scanning curing to obtain different thicknesses CdAccording to formula Cd＝Dp Ln[PL/(Vs*hs)]—DpLnEcFrom a series of known PL、VsAnd HsValue by measured CdCan find EcAnd DpThe value is obtained.
2) Working fill scan rate: using SLA 3D printer, at constant workRate PLIn the case of 300mW, scan curing is performed, taking the maximum fill scan rate at which the liquid material can be cured and shaped, and can be removed for cleaning, as the working fill scan rate of the material. The index directly reflects the curing rate of the photosensitive resin composition, wherein the higher the working filling scan rate of the material, the higher the molding efficiency of the material;
3) the tests for tensile strength and elongation at break were carried out according to the standard ASTM D638;
4) the flexural modulus and flexural strength are tested according to the standard ASTM D638;
5) the notched impact strength was tested according to the standard ASTM D256;
6) testing the Shore hardness D according to a standard ASTM D2240, and testing by using a Shore rubber durometer D type 0-100 HD;
7) testing the surface resistance by using a surface resistance meter; the surface needs to be smooth during testing;
8) the glass transition temperature of the cured resin was measured by DMA equipment, and the temperature was raised from room temperature to 200 ℃ at a rate of 2 ℃/min at a frequency of 1 HZ.
9) The resin viscosity was measured using a rotational viscometer at 25 ℃ using a number 2 spindle at a spindle speed of 30 rpm/min.
Examples 1 to 7 and comparative examples 1 to 5
The present example and comparative example provide a series of antistatic photosensitive resins having the following formulation in table 1 below.
TABLE 2 formulations (parts) of examples 1 to 7 and comparative examples 1 to 4
In addition, a commercially available white material was used as comparative example 5.
The antistatic photosensitive resins of the respective examples and comparative examples were measured for their properties in accordance with the above-mentioned methods, and the results are shown in Table 2.
TABLE 2 results of the performance test of each example and comparative example
As can be seen from Table 2, the antistatic photosensitive resin provided by the embodiments of the present invention has a good antistatic effect with an extremely low conductive agent, and the surface resistance of the cured product is much lower than 109Omega, low viscosity, excellent mechanical property and good toughness, and the performance of the product is far better than that of some products sold on the market at present (such as comparative example 5). The impact strength and elongation at break of the photosensitive resin (as comparative example 1) without the hyperbranched epoxy resin are seriously reduced; the photosensitive resin without the modified multi-walled carbon nanotube (as in comparative example 2) has no antistatic effect, and the glass transition temperature is slightly lowered; after the photosensitive resin (such as comparative example 3) added with the unmodified multi-wall carbon nano tube is placed for 12 months, the carbon nano tube is seriously settled, the surface resistance of a printed piece is obviously increased, the antistatic effect of the printed piece cannot be ensured, and the impact strength of the printed piece is obviously reduced due to the uneven dispersion of the carbon nano tube; the glass transition temperature and the impact strength of the cured product of the photosensitive resin added with the non-hyperbranched epoxy resin (such as the comparative example 5) are obviously reduced.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. An antistatic photosensitive resin for photocuring rapid prototyping is characterized by comprising the following components in parts by weight:
the modified multi-walled carbon nanotube is obtained by modifying hyperbranched epoxy resin.
2. The antistatic photosensitive resin according to claim 1, wherein the cationic photocurable component is one or more of glycidyl ether type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, vinyl ether type monomer, aliphatic epoxy resin, novolac epoxy resin, vinyl ketal type monomer or oxetane type monomer;
the free radical photosensitive resin component is one or more of polyurethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, organic silicon oligomer, hyperbranched oligomer, TPGDA, NPGDA, NPG (PO)2DA, DPGDA, TMPTA, PETA, PETTA, DPPA or IBOA.
3. The antistatic photosensitive resin according to claim 1, wherein the cationic photoinitiator is one or more of diaryliodonium salts, triarylsulfonium salts, or ferrocenium salts;
the free radical initiator is a cracking type free radical photoinitiator.
4. The antistatic photosensitive resin of claim 1, wherein the hyperbranched epoxy resin is one or more of Hyper e102, Hyper de1050, Hyper fe1050, Hyper de1045, Hyper ME1050, or Hyper ME 1045.
5. The antistatic photosensitive resin of claim 1, wherein the modified multi-walled carbon nanotubes are prepared by the following process:
s1: carrying out acid washing treatment on the multi-walled carbon nano tube;
s2: mixing silane coupling agent with sulfydryl and multi-walled carbon nano-tubes treated by acid cleaning to react to obtain the multi-walled carbon nano-tubes with sulfydryl on the surfaces;
s3: and (3) mixing and modifying the multi-walled carbon nano tube with the surface provided with the sulfydryl obtained in the step (S2) with hyperbranched epoxy resin to obtain the modified multi-walled carbon nano tube.
6. The antistatic photosensitive resin according to claim 5, wherein S1 is acid-washed with a nitric acid solution.
7. The antistatic photosensitive resin as claimed in claim 5, wherein the mercapto group-containing silane coupling agent in S2 is one or more selected from 3-mercaptopropyltetramethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
8. The antistatic photosensitive resin of claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1176, or BHT.
9. The method for preparing the antistatic photosensitive resin according to any one of claims 1 to 8, comprising the steps of: and mixing a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, a modified multi-walled carbon nanotube, hyperbranched epoxy resin and an antioxidant to obtain the antistatic photosensitive resin.
10. Use of the antistatic photosensitive resin according to any one of claims 1 to 8 in 3D printing.
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| CN114213810A (en) * | 2021-12-28 | 2022-03-22 | 宁波美佳速创智能科技有限公司 | High-strength 3D printing photosensitive resin material |
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