CN112724605B - Photosensitive resin composition for photocuring rapid prototyping and preparation method and application thereof - Google Patents
Photosensitive resin composition for photocuring rapid prototyping and preparation method and application thereof Download PDFInfo
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- CN112724605B CN112724605B CN202011568229.7A CN202011568229A CN112724605B CN 112724605 B CN112724605 B CN 112724605B CN 202011568229 A CN202011568229 A CN 202011568229A CN 112724605 B CN112724605 B CN 112724605B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a photosensitive resin composition for photocuring rapid prototyping, and a preparation method and application thereof. The photosensitive resin composition comprises a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, modified nano spherical silicon dioxide, hyperbranched epoxy resin, an antioxidant and a cationic thermal initiator. The photosensitive resin composition provided by the invention has better mechanical property and Shore hardness, and the size stability and heat resistance of a later model are good.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a photosensitive resin composition 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 resins which are dominant in the market are mainly high-strength photosensitive resins, high-toughness photosensitive resins, high-temperature-resistant photosensitive resins, transparent photosensitive resins and the like, and at present, research reports on the high-toughness and high-temperature-resistant photosensitive resins for photocuring additive manufacturing are very lacking, and related products are basically blank. The DSM-promoted Somos PerFORM can resist high temperature, can be used for photosensitive resin of an injection mold, and is verified and produced for small-amount injection molding products, but the resin has poor toughness and limited application range. Therefore, aiming at the current situation that high-performance resin required by photocuring additive manufacturing is lack, a material which has independent intellectual property rights, high-toughness and high-temperature-resistant photosensitive resin and good dimensional stability of a formed part is developed and used as a forming material for additive manufacturing, so that the defects of the conventional photosensitive resin are overcome, and the application field of photocuring additive technology can be further developed.
Disclosure of Invention
The invention aims to overcome the defects of high-toughness and high-temperature-resistant photosensitive resin in the prior art and provide a photosensitive resin composition for photocuring rapid molding. The photosensitive resin composition provided by the invention introduces photoinitiator and cationic thermal initiator, adopts the principle of two-step curing, combines the photocuring reaction and the cationic thermocuring reaction, and utilizes thermal post-treatment to effectively improve the later conversion rate of a photosensitive resin molded part, thereby effectively solving the problems that the laser scanning speed is high, the conversion rate of the photosensitive resin in the initial molding process is low, the conversion rate cannot be effectively improved due to the weak ultraviolet penetration capability of the ultraviolet post-curing, and the printed part is deformed after being placed for a period of time, the dimensional accuracy is poor, the color is yellow and the like; in addition, the hyperbranched epoxy resin and the modified nano spherical silicon dioxide can effectively improve the heat resistance of the resin composition and effectively improve the toughness of a cured product on the premise of not increasing the viscosity of a resin system.
Another object of the present invention is to provide a method for preparing the above photosensitive resin composition.
Another object of the present invention is to provide use of the above photosensitive resin composition in 3D printing.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photosensitive resin composition for photocuring rapid prototyping comprises the following components in parts by weight:
the modified nanometer spherical silicon dioxide is obtained by modifying hyperbranched epoxy resin.
Compared with fumed silica or precipitated silica, the nano spherical silica has the advantages of small specific surface area, small influence on resin viscosity caused by addition, few spherical structural defects, and basically no stress midpoint formed in a cured product. However, the direct addition of the nano spherical silica into the resin system has the defects of poor compatibility, difficult dispersion and the like, and the surface treatment of the nano spherical silica can effectively improve the defects.
Repeated researches by the inventor of the invention find that the modified nano spherical silicon dioxide obtained by carrying out specific modification treatment on the nano spherical silicon dioxide by using the hyperbranched epoxy resin has excellent anti-settling and dispersing effects, and is easy to disperse and free of agglomeration when being used as a toughening agent and a heat resistance improving agent to be added into resin. The principle may be: the surface of the modified nano spherical silicon dioxide contains a certain amount of hyperbranched epoxy resin, so that the modified nano spherical silicon dioxide is very easy to disperse in a free radical-cation hybrid photocuring system and has no agglomeration phenomenon; the photosensitive resin system is kept still for 10 months, the modified nano spherical silicon dioxide dispersed in the photosensitive resin system does not have any sedimentation, the consistency of the front and back performances of a product printed by the photosensitive resin composition is effectively ensured, and the obvious change of the performance of a printed part caused by long standing time of the resin can not occur; epoxy groups on the surfaces of the nano-sphere-shaped silicon dioxide after surface modification participate in cationic photocuring reaction to form rigid particle toughening centers, 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 discovers 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 photosensitive resin composition; the resin condensate has excellent mechanical property, good toughness and good surface precision and dimensional stability of a printed piece, and provides guarantee for large-scale popularization of the resin.
In addition, the photosensitive resin composition provided by the invention introduces a photoinitiator and a cationic thermal initiator, adopts a two-step curing principle, combines a photocuring reaction and a cationic thermal curing reaction, and utilizes thermal post-treatment to effectively improve the later conversion rate of a photosensitive resin molded part, thereby effectively solving the problems that the laser scanning speed is high, the conversion rate of the photosensitive resin in the initial molding process is low, and the conversion rate cannot be effectively improved due to the weak ultraviolet penetration capability of ultraviolet post-curing, so that a printed part is deformed after being placed for a period of time, the dimensional accuracy is poor, the color is yellow and the like.
By introducing the photoinitiator and the cationic thermal initiator and the synergistic cooperation of the modified nano spherical silicon dioxide and the hyperbranched epoxy resin, the photosensitive resin composition provided by the invention has better glass transition temperature and size stability under high-temperature and high-humidity conditions, and better mechanical property and Shore hardness.
Cationic photocurable components, free radical photosensitive resin components, cationic photoinitiators, free radical initiators, antioxidants and cationic thermal initiators, which are 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, novolac epoxy resin, OX of Toagosei corporation 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 HyPer E102, HyPer DE1050, HyPer FE1050, HyPer DE1045, HyPer ME1050 or HyPer ME 1045.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1176 or BHT.
Preferably, the cationic thermal initiator is one or more of SI-80L (Japan Sanxin chemistry), SI-100L (Japan Sanxin chemistry), Vicbase TC3633 (Shenzhen Kay chemistry), Vicbase TC3638 (Shenzhen Kay chemistry) or Vicbase TC3635 (Shenzhen Kay chemistry).
More preferably, the cationic thermal initiator is one or both of SI-100L or Vicbase TC3635 with an initiation temperature in excess of 90 ℃.
The nano spherical silica is commercially available, and the particle size of the nano spherical silica is generally 2 to 200nm, for example, nano spherical silica produced by chemical industry in Japan.
Preferably, the modified nano spherical silica is prepared by the following process:
s1: mixing and reacting a silane coupling agent with sulfydryl and the nano spherical silicon dioxide to obtain the nano spherical silicon dioxide with sulfydryl on the surface;
s2: and (4) mixing and modifying the nano spherical silicon dioxide with sulfydryl on the surface obtained in the step (S2) and hyperbranched epoxy resin to obtain the modified nano spherical silicon dioxide.
More preferably, the silane coupling agent with mercapto in S1 is one or more of 3-mercaptopropylmethyldimethoxysilane or 3-mercaptopropyltrimethoxysilane.
More preferably, the mass ratio of the nano spherical silica with sulfydryl on the surface in S2 to the hyperbranched epoxy resin is 1: 0.5-1: 10.
The preparation method of the photosensitive resin composition comprises the following steps: and mixing a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, modified nano spherical silica, an antioxidant and a cationic thermal initiator to obtain the photosensitive resin composition.
The application of the photosensitive resin composition in 3D printing is also within the protection scope of the present invention.
Preferably, the photosensitive resin composition is used for preparing a molding material for additive manufacturing.
Compared with the prior art, the invention has the following beneficial effects:
the photosensitive resin composition provided by the invention has the advantages of good heat resistance and mechanical property, high glass transition temperature, good toughness, high Shore hardness, high conversion rate, and good surface precision and dimensional stability of a printed product.
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 cation photocuring component No. 4, novolac epoxy resin, PNE177 of Changchun artificial resin factory, Inc.;
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 cationic thermal initiator 1# is Japanese Sanxin chemical SI-100L;
the hyperbranched epoxy resin No. 1 is HyPer E102;
the hyperbranched epoxy resin No. 2 is HyPer DE 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 nano spherical silicon dioxide is produced by chemical production in Japan, and the particle size is 2-200 nm;
the non-hyperbranched epoxy resin toughening agent is a core-shell structure toughening agent.
In addition, the modified nano spherical silica is prepared by the following steps: adding nano spherical silicon dioxide (2g) into ethanol (2g of silane coupling agent added with 50 g of ethanol) solution of silane coupling agent with mercapto, stirring and refluxing for 12H at 40 ℃, filtering, reacting the silane coupling agent with mercapto with hydroxyl or carboxyl on the surface of the nano spherical silicon dioxide to obtain nano spherical silicon dioxide with mercapto on the surface, adding the treated nano spherical silicon dioxide (2g) into acetone (100g) solution, stirring, slowly adding hyperbranched epoxy resin (5g) containing 0.05 percent of DBU (calculated according to the amount of epoxy resin) into acetone solution (100g) of the nano spherical silicon dioxide (2g), after the addition is finished, increasing the reaction temperature to 60 ℃, stirring for reaction for 12H, filtering, firstly cleaning with alcohol, then cleaning with pure water until the cleaning solution is neutral, vacuum drying, and reacting the mercapto group on the surface of the nano spherical silicon dioxide with the epoxy group to obtain the nano spherical silicon dioxide with a certain amount of hyperbranched epoxy resin on the surface.
Wherein in the preparation process of the modified nano spherical silicon dioxide 1#, hyperbranched epoxy resin HyPer E102 is selected; in the preparation process of the modified nano spherical silicon dioxide 2#, hyperbranched epoxy resin HyPer DE1050 is selected.
The photosensitive resin compositions of the examples and comparative examples of the present invention were prepared by the following processes: and stirring and mixing the cationic photocuring component, the free radical photocuring component, the cationic photoinitiator, the free radical photoinitiator, the modified nano spherical silicon dioxide, the antioxidant and the cationic thermal initiator at 25 ℃ for 60min to obtain the modified nano spherical silicon dioxide.
The photosensitive resin compositions of the respective examples and comparative examples were subjected to critical exposure energy, curing depth, laser filling scan speed, bending strength, bending modulus, tensile strength, elongation at break, shore hardness, surface resistance and notched impact strength tests, and were subjected to comparative tests with conventional white materials purchased in the market. The method for testing each performance index comprises the following steps:
1) working fill scan rate: using SLA 3D printer at fixed power 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;
2) the tests for tensile strength and elongation at break were carried out according to the standard ASTM D638;
3) the flexural modulus and flexural strength are tested according to the standard ASTM D638;
4) the notched impact strength was tested according to the standard ASTM D256;
5) testing the Shore hardness D according to a standard ASTM D2240, and testing by using a Shore rubber durometer D type 0-100 HD;
6) 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.
7) The resin viscosity was measured using a rotational viscometer at 25 ℃ using a number 2 spindle at a spindle speed of 30 rpm/min.
8) Testing the dimensional stability under the condition that a model (the model is a cuboid with the length, the width and the thickness being 50cm, 5cm and 2 cm) is placed in an environment constant-temperature and constant-humidity testing box with the humidity of 100% and the temperature of 70 ℃ for testing for 7 days, testing the dimensional change conditions of the model, such as whether the model is warped, cracked, expanded, yellowed and the like, and testing the length change rate (the change rate is the change length/the original length 100%) before and after the model test, wherein the dimensional stability is defined when the change rate is less than 0.1%, and the dimensional stability is defined when the change rate is more than or equal to 0.1%;
9) before testing the mechanical property, Shore hardness, dimensional stability and glass transition temperature of the printed piece, the printed piece needs to be post-cured under the conditions of post-curing for 20min in an ultraviolet post-curing box (30W), 30min at 70 ℃ and 30min at 100 ℃.
Examples 1 to 7 and comparative examples 1 to 6
The present example and comparative example provide a series of photosensitive resin compositions, the formulations of which are shown in Table 1 below.
TABLE 2 formulations (parts) of examples 1 to 7 and comparative examples 1 to 5
In addition, a commercially available white material was used as comparative example 6.
The properties of the photosensitive resin compositions of the respective examples and comparative examples were measured according to 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 photosensitive resin composition provided in each embodiment of the present invention has no influence on the viscosity of the resin system, no delamination or sedimentation occurs after 12 months of storage, and has better mechanical properties and shore hardness, and the size stability and heat resistance of the model at the later stage are good, and the properties thereof are significantly better than those of some products currently on the market (e.g., comparative example 6). The viscosity of the resin composition (for example, comparative example 3) to which the surface-untreated nanospherical silica was added was slightly higher than that of the resin composition to which the surface-treated nanospherical silica was added in an equivalent weight (example 1), and the resin system was allowed to stand for 12 times, and was remarkably delaminated and settled, on the one hand, because the dispersion of the unmodified nanospherical silica in the resin was remarkably deteriorated and agglomeration was easily occurred; on the other hand, the interaction force between the unmodified nano spherical silica and the resin is weak, and a winding structure cannot be formed on the surface of the nano spherical silica; the two aspects cause that the unmodified nano spherical silicon dioxide is easy to have a sedimentation phenomenon; and the surface of the nano spherical silicon dioxide which is not subjected to surface treatment has no reactive group, and the nano spherical silicon dioxide can not react with other resins of the system in the illumination process to form a rigid toughening center which is tightly combined, so that the impact strength of the resin system is poor. The resin system without the addition of modified nanospherical silica (as in comparative example 2) has a different reduction in mechanical properties, shore hardness and heat resistance than example 1. The core-shell structure toughening agent (such as comparative example 4) is added, so that the impact strength of the material is obviously improved, but the viscosity is obviously increased, so that the leveling time of the coating liquid is obviously increased, the heat resistance, the bending strength/modulus, the tensile strength and the Shore hardness of a printed part are obviously reduced compared with those of example 1, and the tensile elongation at break is improved to a certain extent; compared with the resin composition of example 1, the resin composition (comparative example 1) without the hyperbranched epoxy resin is obviously reduced in impact strength and tensile elongation at break; comparative example 5, which is a resin composition to which a cationic thermal initiator was added, was found to have poor dimensional stability and to have some reduction in heat resistance, shore hardness, flexural strength, flexural modulus and tensile strength, but the notched impact strength and elongation at break were slightly improved as compared to comparative example 1.
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 (9)
1. The photosensitive resin composition for photocuring rapid prototyping is characterized by comprising the following components in parts by weight:
the modified nano spherical silicon dioxide is prepared by the following steps:
s1: mixing and reacting a silane coupling agent with sulfydryl and the nano spherical silicon dioxide to obtain the nano spherical silicon dioxide with sulfydryl on the surface;
s2: and (4) mixing and modifying the nano spherical silicon dioxide with sulfydryl on the surface obtained in the step (S1) and hyperbranched epoxy resin to obtain the modified nano spherical silicon dioxide.
2. The photosensitive resin composition of 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 photocuring component is polyurethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, pure acrylic resin, organic silicon oligomer, TPGDA, NPGDA, NPG (PO)2DA. One or more of DPGDA, TMPTA, PETA, PETTA, DPHA or IBOA.
3. The photosensitive resin composition of 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;
the cationic thermal initiator is one or more of SI-80L, SI-100L, Vicbase TC3633, Vicbase TC3638 or Vicbase TC 3635.
4. The photosensitive resin composition 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 photosensitive resin composition of claim 1, wherein the mercapto group-containing silane coupling agent in S1 is one or both of 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
6. The photosensitive resin composition according to claim 1, wherein the mass ratio of the nanospherical silica having mercapto groups on the surface to the hyperbranched epoxy resin in S2 is 1:0.5 to 1: 10.
7. The photosensitive resin composition of claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1176, or BHT.
8. A method for preparing the photosensitive resin composition according to any one of claims 1 to 7, comprising the steps of: and mixing a cationic photocuring component, a free radical photocuring component, a cationic photoinitiator, a free radical photoinitiator, modified nano spherical silicon dioxide, hyperbranched epoxy resin, an antioxidant and a cationic thermal initiator to obtain the photosensitive resin composition.
9. Use of the photosensitive resin composition according to any one of claims 1 to 7 for 3D printing.
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| CN111925759A (en) * | 2020-08-10 | 2020-11-13 | 青岛爱尔家佳新材料股份有限公司 | Solvent-free adhesive and preparation method and application thereof |
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