CN108976714B - Single-component epoxy resin modified photosensitive resin composition for 3D printing and preparation method thereof - Google Patents
Single-component epoxy resin modified photosensitive resin composition for 3D printing and preparation method thereof Download PDFInfo
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- CN108976714B CN108976714B CN201810839286.0A CN201810839286A CN108976714B CN 108976714 B CN108976714 B CN 108976714B CN 201810839286 A CN201810839286 A CN 201810839286A CN 108976714 B CN108976714 B CN 108976714B
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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
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to the technical field of photocuring 3D printing materials, and discloses a single-component epoxy resin modified photosensitive resin composition for 3D printing and a preparation method thereof. The resin composition comprises the following components in percentage by mass: 10-30% of single-component epoxy resin; 24-50% of bifunctional acrylate prepolymer; 10-30% of polyfunctional acrylate monomer; 11-30% of an active diluent; 1.5-4% of a photoinitiator; the single-component epoxy resin is composed of a liquid epoxy resin compound, a copolymer with an epoxy group on a side chain and a latent epoxy curing agent. The invention also provides a preparation method of the resin composition. The resin composition can be applied to SLA and DLP technologies of 3D printing, photocuring molded parts with good toughness, interlayer bonding force and heat resistance can be obtained after curing molding, and the defect of splitting among printing layers can not occur in the process of heating post-treatment.
Description
Technical Field
The invention belongs to the technical field of photocuring 3D printing materials, and particularly relates to a single-component epoxy resin modified photosensitive resin composition for 3D printing and a preparation method thereof.
Background
Photocuring molding is the earliest 3D printing molding technology and is also the mature 3D printing technology at present. The working process is under the control of a computer, and the ultraviolet laser beam scans the photosensitive resin in the raw material pool in sequence according to the profile data of each layered cross section. In the area where the ultraviolet light passes through, the photosensitive resin absorbs the light energy to perform photopolymerization and curing, and a thin cross-sectional layer is formed. And after one layer of curing is finished, controlling the workbench to move by one layer thickness height, uniformly laying a layer of liquid resin on the surface of the cured resin layer, repeating the ultraviolet curing process, and repeating the steps until the whole product model is formed.
However, the photosensitive resin material in the market at present mainly uses acrylate, and the acrylate oligomer with higher molecular weight and the low-molecular-weight acrylate diluent are matched to form the photocuring resin with lower viscosity and better forming performance, but the problems of higher brittleness and higher shrinkage of a formed product exist often, and the printing precision and the comprehensive performance of a 3D printing device are greatly influenced. The method is an effective method for improving the toughness of photosensitive resin, reducing the shrinkage rate of materials and effectively reducing the proportion of low-molecular-weight acrylate diluent in a photosensitive resin formula, but the method often causes that the viscosity of the photosensitive resin is high, the uncured liquid photosensitive resin is not beneficial to covering a cured and formed resin layer, the 3D printing forming performance of the photosensitive resin is poor, and the improvement of the bonding force between layers of a 3D printing product in the printing process is not beneficial.
The post-curing mode that uses after 3D printing shaping is ultraviolet illumination and heat radiation two kinds, because of the ultraviolet ray depth of penetration is limited, ultraviolet illumination post-curing easily causes the inhomogeneous problem of degree of solidification, consequently, post-curing is a comparatively common post-processing mode, but lower interbedded cohesion can lead to 3D printing shaping product can take place the interbedded separation at the in-process of follow-up post-curing that is heated, directly leads to the product to scrap. In a word, the 3D printing photosensitive resin composition with ideal material toughness, interlayer bonding force and heat resistance is difficult to obtain by only adopting the acrylate and the reactive diluent thereof.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a single-component epoxy resin modified photosensitive resin composition for 3D printing. According to the invention, the single-component epoxy resin with low molecular weight is added into the photosensitive resin system to modify the photosensitive resin system, so that the flowing property of acrylate is improved, the contact area between the later layer and the previous layer in the resin 3D printing process is increased, and the interlayer bonding force is improved, so that the single-component epoxy resin modified photosensitive resin composition for 3D printing is obtained, and the photocuring molding product with better interlayer bonding force, toughness and heat resistance for printing a 3D printing molding device is obtained. Meanwhile, the single-component epoxy resin is subjected to thermal curing reaction in the subsequent thermal curing process, so that the interlayer bonding force of the 3D printing product is further improved, and the specific expression is that the heat resistance is increased, and the defect of separation between printing layers is avoided.
The invention also aims to provide a preparation method of the single-component epoxy resin modified photosensitive resin composition for 3D printing.
The purpose of the invention is realized by the following scheme:
a single-component epoxy resin modified photosensitive resin composition for 3D printing comprises the following components in percentage by mass: 10-30% of single-component epoxy resin; 24-50% of bifunctional acrylate prepolymer; 10-30% of polyfunctional acrylate monomer; 11-30% of an active diluent; 1.5-4% of a photoinitiator.
Specifically, in the one-component epoxy resin modified photosensitive resin composition for 3D printing, the one-component epoxy resin is preferably composed of a liquid epoxy resin compound, a copolymer (BCP) having an epoxy group as a side chain, and a latent epoxy curing agent.
More preferably, the epoxy resin composition comprises a liquid epoxy resin compound having a viscosity of less than 3000 mPas, a copolymer (BCP) having an epoxy group as a side chain, and a latent epoxy curing agent.
Specifically, the epoxy resin is obtained by mixing and ball-milling a liquid epoxy resin compound, a copolymer with a side chain being an epoxy group and a latent epoxy curing agent. More preferably, a planetary ball mill is adopted for ball milling for 0.5-2 h.
Further, the copolymer (BCP) with the side chain being the epoxy group can be prepared by a method comprising the following steps: mixing 1, 2-epoxy-4-vinylcyclohexane and glycidyl methacrylate, preheating, dissolving a dibenzoyl peroxide initiator in the glycidyl methacrylate, dropwise adding the mixture into the mixed system, and heating for reaction to obtain the copolymer.
The total molar ratio of 1, 2-epoxy-4-vinylcyclohexane (molecular weight of 124.18) and glycidyl methacrylate (molecular weight of 142.15) is 1: 3-6: 5.
The mass of the initiator is preferably 4-9% of the sum of the two monomers.
The preheating is preferably carried out to 45-65 ℃, and more preferably to 60 ℃.
The heating reaction is preferably carried out for 2-4 h by heating to 70-85 ℃, and more preferably carried out for 2h by heating to 80 ℃ at the speed of 2 ℃/min and carrying out heat preservation reaction.
The molar weight ratio of the glycidyl methacrylate G1 to G2 used twice before and after is preferably 2:3 to 3:2, and more preferably 1: 1.
The dripping is preferably finished within 30-60 min.
The above reaction is preferably carried out under an inert gas atmosphere.
The copolymer (BCP) with the side chain being the epoxy group contains vinyl double bonds and the epoxy group in the chemical structure, so that the interface compatibility of the single-component epoxy resin and the 3D printing photosensitive resin can be effectively improved.
Further, the liquid epoxy resin compound includes any one of glycidyl ether type epoxy resin and glycidyl ester type epoxy resin. The following can be selected but not limited to: 1, 6-trimethylolpropane triglycidyl ether, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, adipic acid bis (3, 4-epoxycyclohexyl) methyl ester, ethylene glycol diglycidyl ether, and 1, 2-cyclohexanediol diglycidyl ether. More preferably, the viscosity is less than 3000 mPaS.
Further, the latent epoxy curing agent is preferably an epoxy curing agent which is stable to an epoxy group at room temperature and can not open a ring of the epoxy group to perform an epoxy curing reaction when heated to a temperature of 80 ℃ or higher, and may include at least one of a hexafluoroantimonate thermally-initiated cationic curing agent (e.g., ICAM-8409), an organoborane compound curing agent (e.g., 594 curing agent), and a modified amine latent curing agent (e.g., Aradur 9506).
In the composition, the difunctional acrylate prepolymer is preferably at least one of epoxy modified acrylate prepolymer and polyurethane modified acrylate prepolymer with the viscosity of 6000-30000 mPa & S at room temperature (25 ℃).
The epoxy modified acrylate prepolymer may be selected from, but is not limited to, at least one of epoxy acrylate (e.g., RJ313), epoxy acrylate (e.g., JZ-101), bisphenol A epoxy acrylate (e.g., BC-8001), ethoxylated bisphenol A diacrylate (e.g., SR349 NS).
The urethane-modified acrylate prepolymer may be selected from, but is not limited to, at least one of urethane acrylate, urethane acrylate mixture, aliphatic urethane acrylate (e.g., RJ429), aliphatic urethane acrylate (e.g., JZ-302), aliphatic urethane acrylate (e.g., lucire 8240), and aromatic urethane acrylate (e.g., JZ-304).
In the composition, in order to increase the heat resistance of the photosensitive resin, the multifunctional acrylate monomer effectively considers the balance relationship between the resin viscosity and the heat resistance. Preferably, the multifunctional acrylate monomer includes at least one of pentaerythritol triacrylate, dipentaerythritol hexaacrylate (e.g., easipi 7300), ditrimethylolpropane tetraacrylate, low viscosity dipentaerythritol pentaacrylate (e.g., SR399LVNS), bisphenol a glycerol dimethacrylate, tripropylene glycol diacrylate (e.g., TPGDA).
In the composition, in order to reduce the viscosity of the light-cured resin and improve the flow property of the resin in the printing process, the reactive diluent is added into a photosensitive resin system, and the reactive diluent participates in the light-curing process through double bonds and is crosslinked into a material. Preferably, the reactive diluent is at least one of glycidyl methacrylate, lauryl acrylate, isobornyl acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate/bisphenol A diacrylate, tetraethylene glycol triacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclic trimethylolpropane formal acrylate, 4-hydroxybutyl vinyl ether, 4-vinyl epoxycyclohexane, vinylpyrrolidone, diethylene glycol divinyl ether, and 4-vinyl epoxycyclohexane.
In the composition of the present invention, the photoinitiator may be at least one of azobisisobutyronitrile, Irgacure 754, Irgacure369, Irgacure819, Irgacure651, Irgacure184D, easebi 820, easebi 6992, Darocur1173D, Rjoji907 and trigonox k 90.
The photosensitive resin for 3D printing provided by the invention can also comprise a defoaming agent, a polymerization inhibitor and a leveling agent, preferably; 0.7-1.5 wt% of defoaming agent; 0.6-0.9 wt% of polymerization inhibitor; 0.6 to 1.1wt% of a leveling agent.
Preferably, the defoaming agent is at least one of hydrophobic stearate EL-2600, dimethyl polysiloxane BK-C058, AFE-3168, polypropylene glycol defoaming agent DQ-Q019, polyether AFE0800 defoaming agent and polyether modified siloxane defoaming agent B-0518.
In order to ensure that the photosensitive resin does not self-polymerize in the effective period and reaches a certain quality guarantee period, a polymerization inhibitor can be added. The polymerization inhibitor comprises hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and other conventional polymerization inhibitors.
The viscosity of the photosensitive resin for 3D printing is generally 300-800 mPa & S, and in order to improve the surface quality of a 3D printing device and reduce traces between printing layers, a leveling agent, such as an acrylate leveling agent, can be added to increase the popularity of a resin layer. The leveling agent can comprise at least one of a Camett KMT-5510, a KMT-5519, a BETTERSOL3896, a BETTERSOL3897, an acrylate leveling agent SP-956N and a radiation curing leveling agent Glide 450.
The invention also provides a preparation method of the single-component epoxy resin modified photosensitive resin composition for 3D printing, which comprises the following steps: stirring the bifunctional acrylate prepolymer, the polyfunctional acrylate monomer and the reactive diluent at the temperature of 30-60 ℃ and at the speed of 200-300 rpm for 30-50 minutes; cooling to room temperature, adding the single-component epoxy resin, and stirring at the speed of 300-500 rpm for 30-60 minutes; and adding a photoinitiator, and stirring at the speed of 300-500 rpm for 20-30 minutes to obtain the single-component epoxy resin modified photosensitive resin composition for 3D printing.
The single-component epoxy resin modified photosensitive resin composition for 3D printing has good mechanical strength, heat resistance and toughness after photocuring, and solves the problem that the photocuring resin is easy to split between printing layers in the curing process after heating after 3D printing and forming. The method can be applied to SLA and DLP technologies of 3D printing, photocuring molded parts with good toughness, interlayer bonding force and heat resistance can be obtained after curing molding, and the defect of interlayer cracks can not occur in the heating post-treatment process. According to the composition, the single-component epoxy resin is added into the photosensitive resin, the single-component epoxy resin is not completely cured in the printing process of the photosensitive resin, the product is placed in a heating environment after the product is printed, a heating reaction occurs, the photosensitive resin cured product forms stronger interlayer bonding force and higher free radical curing degree under the action of the epoxy resin, and the improvement of interlayer bonding force, toughness and heat resistance of a photosensitive resin 3D printing formed part is facilitated.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1
(1) Preparation of copolymer BCP:
according to the total molar preferred ratio of 1, 2-epoxy-4-vinylcyclohexane (UVR, the avastin reagent, the same below) to glycidyl methacrylate (GMA, the avastin reagent, the same below) of 1:3 two monomers are metered in. Adding all UVR into a reaction kettle, dividing GMA monomers into a G1 part and a G2 part according to the molar weight ratio of 1:1, adding the G1 part and the G2 part into the reaction kettle, dissolving 9% of total mass of the two monomers of an initiator dibenzoyl peroxide initiator into G2 to obtain a mixed solution M, introducing nitrogen, stirring, dropwise adding the mixed solution M into the reaction kettle at the temperature of 45 ℃, completing dropwise adding within 30-60 minutes, heating to 80 ℃ at the speed of 2 ℃/minute, and preserving heat for 2 hours to obtain a copolymer BCP 1.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 40 parts by mass of latent epoxy curing agent ICAM-8409 (Shenzhen, pioneer applied materials science and technology Co., Ltd.) and 600 parts by mass of liquid epoxy resin compound bis [ (3, 4-epoxy cyclohexyl) methyl ] adipate (Hubei Xinjing new materials Co., Ltd.) and 400 parts by mass of BCP are subjected to ball milling for 2 hours at the rotating speed of 600rpm (zirconia beads are used as ball milling carriers), and the zirconia beads are filtered and removed to obtain the single-component epoxy resin A1.
(3) Preparation of photosensitive resin composition
290 parts by mass of epoxy acrylate RJ313 (German good chemical (China) Co., Ltd.), 210 parts by mass of dipentaerythritol hexaacrylate Easepi7300 (Shanghai light chemical Co., Ltd.), 140 parts by mass of lauryl acrylate and isobornyl acrylate (volume ratio 2/1), 8 parts by mass of defoaming agent hydrophobe stearate EL-2600 (Yilianhua chemical Co., Ltd., Dongguan), 6 parts by mass of polymerization inhibitor hydroquinone and 9 parts by mass of leveling agent Camet KMT-5510 (Kyuda plastics Ministry of Shenzhen, Bao's province), and the like are stirred at 40 ℃ at a speed of 200rpm for 30 minutes; reducing the temperature of the system to room temperature, adding 300 parts by mass of the single-component epoxy resin, and stirring at the speed of 300-500 rpm for 30-60 minutes; and adding 37 parts by mass of free radical initiators Irgacure819 and Irgacure651 (in a weight ratio of 3/1) and mechanically stirring at the speed of 300-500 rpm for 20-30 minutes to obtain the one-component epoxy resin modified photosensitive resin composition A2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" a3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 1 photosensitive resin composition Property parameters
| Properties | Test standard | A2 | A3 |
| Density (liquid state) | / | 1.14 | 1.13 |
| Density (solid state) | / | 1.18 | 1.21 |
| Curing shrinkage (%) | Density method | 3.39 | 6.61 |
| Tensile Strength (MPa) | D638 | 45 | 32 |
| Tensile modulus (MPa) | D638 | 1890 | 1430 |
| Elongation at Break (%) | D638 | 13 | 14 |
| Flexural Strength (MPa) | D790 | 67 | 52 |
| Impact Strength (J/m) | D256 | 48 | 41 |
| Heat distortion temperature (. degree.C.) of 0.45MPa | D648 | 76 | 59 |
| Heat distortion temperature (. degree.C.) of 1.82MPa | D649 | 65 | 51 |
| Glass transition (Tg) | DMA | 73 | 54 |
| Temperature of post-treatment layer separation (. degree. C.) | Vacuum | 81 | 66 |
Note: the post-treatment layering temperature test method comprises the following steps: after washing the printed product with ethanol to remove the surface liquid resin, placing the printed product in a vacuum oven to bake for 2 hours, wherein the samples are cylinders with the diameter of 20mm x 10mm, testing two samples at each temperature, naturally cooling the samples, and observing whether cracks exist by using a magnifying glass with the magnification of 10 times. If no crack exists, the samples in the same batch of the same formula are selected again, the original temperature is increased by 3 ℃, and the steps are repeated for testing until the temperature which enables the samples to crack for the first time is found as the post-treatment layering temperature. The same applies below.
Example 2
(1) Preparation of copolymer BCP:
according to the total mole preferred ratio of 1, 2-epoxy-4-vinylcyclohexane (UVR molecular weight 124.18) and glycidyl methacrylate (GMA molecular weight 142.15) of 4: 5 two monomers are metered in. Adding all UVR into a reaction kettle, dividing GMA monomers into a G1 part and a G2 part according to the molar weight ratio of 3:2, adding an initiator dibenzoyl peroxide initiator with 6% of the total mass of the two monomers into G2 to obtain a mixed solution M, introducing nitrogen, stirring, dropwise adding the mixed solution M into the reaction kettle at 60 ℃, completing dropwise adding within 30-60 minutes, heating to 70 ℃, and reacting for 4 hours to obtain a copolymer BCP 2.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 70 parts by mass of 594 curing agent (Huayue viscose chemical Co., Ltd., Guangzhou city), 300 parts by mass of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester (Shandong Baihong new material Co., Ltd.), 400 parts by mass of 1, 6-trimethylolpropane triglycidyl ether (Guangdong Shanghe chemical reagent Co., Ltd.) and 300 parts by mass of BCP were ball-milled at 500rpm for 0.5 hour (zirconia beads were used as ball-milling carriers) by using a planetary ball mill, and the zirconia beads were removed by filtration to obtain a one-component epoxy resin B1.
(3) Preparation of photosensitive resin composition
480 parts by mass of epoxy acrylate JZ-101 (Nanjing Jia chemical technology Co., Ltd.), 120 parts by mass of pentaerythritol triacrylate (Guangzhou Tejing chemical technology Co., Ltd.), 230 parts by mass of isobornyl acrylate and 1, 6-hexanediol diacrylate (in a volume ratio of 3/5), 13 parts by mass of defoaming agent dimethylpolysiloxane BK-C058 (Duomadolo), 6 parts by mass of polymerization inhibitor p-hydroxyanisole, 11 parts by mass of leveling agent SP-956N (Dongguan Bocheng chemical technology Co., Ltd.) and the like are stirred at a speed of 300rpm at 40 ℃ for 50 minutes; reducing the temperature of the system to room temperature, adding 100 parts by mass of single-component epoxy resin, and stirring at the speed of 300-500 rpm for 30-60 minutes; adding 18 parts by mass of azobisisobutyronitrile and 22 parts by mass of Irgacure 754, and mechanically stirring at the speed of 300-500 rpm for 20-30 minutes to obtain the one-component epoxy resin modified photosensitive resin composition B2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" B3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 2 photosensitive resin composition Property parameters
Example 3
(1) Preparation of copolymer BCP:
according to the total molar preferred ratio of 1, 2-epoxy-4-vinylcyclohexane (UVR molecular weight 124.18) and glycidyl methacrylate (GMA molecular weight 142.15) of 6:5 two monomers are metered in. The UVR is added in its entirety to the reaction kettle, dividing the GMA monomers into 6:5, firstly adding the G1 part of the reaction kettle and the G2 part of the dissolved initiator, dissolving the dibenzoyl peroxide initiator 9% of the total mass of the two monomers in the G2 to obtain a mixed solution M, introducing nitrogen, dropwise adding the mixed solution M into the reaction kettle under the condition of stirring at 65 ℃, completing dropwise adding in 30-60 minutes, and heating to 85 ℃ to react for 2 hours to obtain the copolymer BCP 3.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 70 parts by mass of 594 curing agent (Huayue viscose chemical company, Inc. in Guangzhou city), 500 parts by mass of bis (3, 4-epoxycyclohexylmethyl) adipate (New Material, Inc. in Hubei), 180 parts by mass of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester (New Material, Inc. in Shandong Bai hong) and 120 parts by mass of bis (3, 4-epoxycyclohexylmethyl) adipate (New Material, Inc. in Hubei) and 200 parts by mass of BCP are subjected to ball milling for 0.5 hour at the rotating speed of 500rpm (zirconium oxide beads are used as ball milling carriers), and the zirconium oxide beads are filtered and removed to obtain epoxy resin C1.
(3) Preparation of photosensitive resin composition
Stirring 500 parts by mass of acrylate prepolymer ethoxylated bisphenol A diacrylate SR349NS (Shadoma Guangzhou chemical Co., Ltd.), 100 parts by mass of low-viscosity dipentaerythritol pentaacrylate SR399LVNS (Shadoma Guangzhou chemical Co., Ltd.), 50 parts by mass of dipropylene glycol diacrylate as an active diluent, 70 parts by mass of hydroxyethyl methacrylate, 15 parts by mass of AFE defoamer-3168 (Dow Corning), 9 parts by mass of hydroquinone as a polymerization inhibitor, 8 parts by mass of BETTERSOL3897 (Shanghai Binghong Kogyo Co., Ltd.) and the like for 50 minutes at a speed of 200rpm under a nitrogen atmosphere at 60 ℃; reducing the temperature of the system to room temperature, adding 220 mass parts of single-component epoxy resin C1, and stirring at the speed of 300rpm for 60 minutes; adding 11 parts by mass of free radical initiator Darocur1173D and 17 parts by mass of free radical initiator Rjoji907, and mechanically stirring at the speed of 400rpm for 30 minutes to obtain the one-component epoxy resin modified photosensitive resin composition C2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" C3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 3 photosensitive resin composition Property parameters
| Properties | Test standard | C2 | C3 |
| Density (liquid state) | / | 1.12 | 1.13 |
| Density (solid state) | / | 1.19 | 1.24 |
| Curing shrinkage (%) | Density method | 5.88 | 8.87 |
| Tensile Strength (MPa) | D638 | 41 | 39 |
| Tensile modulus (MPa) | D638 | 1620 | 1480 |
| Elongation at Break (%) | D638 | 17 | 14 |
| Flexural Strength (MPa) | D790 | 59 | 52 |
| Impact Strength (J/m) | D256 | 51 | 49 |
| Heat distortion temperature of 0.45MPa(℃) | D648 | 68 | 58 |
| Heat distortion temperature (. degree.C.) of 1.82MPa | D649 | 63 | 50 |
| Glass transition (Tg) | DMA | 60 | 52 |
| Temperature of post-treatment layer separation (. degree. C.) | Vacuum heating | 84 | 63 |
Example 4
(1) Preparation of copolymer BCP:
according to the total mole preferred ratio of 1, 2-epoxy-4-vinylcyclohexane (UVR molecular weight 124.18) and glycidyl methacrylate (GMA molecular weight 142.15) being 2:3 two monomers are metered in. The UVR is added in its entirety to the reaction kettle, dividing the GMA monomers into 3: and 4, firstly adding the G1 part of the reaction kettle and the G2 part of the dissolved initiator, dissolving the dibenzoyl peroxide initiator 9% of the total mass of the two monomers in G2 to obtain a mixed solution M, introducing nitrogen, stirring, dropwise adding the mixed solution M into the reaction kettle at 45 ℃, completing dropwise adding in 30-60 minutes, heating to 80 ℃ at the speed of 2 ℃/minute, and preserving the temperature for 2 hours to obtain the copolymer BCP 4.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 80 parts by mass of latent epoxy curing agent Aradur 9506 (Hensman) and 700 parts by mass of liquid epoxy resin compound 1, 2-cyclohexanediol diglycidyl ether (New technology Co., Ltd., Anhui) and 300 parts by mass of BCP were ball-milled at 500rpm for 0.5 hour (zirconia beads are used as ball-milling carriers) by a planetary ball mill, and the zirconia beads were removed by filtration to obtain one-component epoxy resin D1.
(3) Preparation of photosensitive resin composition
Stirring 240 parts by mass of urethane acrylate BH-3309A (Bohai fine chemical Co., Ltd., Zhongshan), 300 parts by mass of di-trimethylolpropane tetraacrylate SR355 (Sandoma Guangzhou chemical Co., Ltd.), 110 parts by mass of dipropylene glycol diacrylate, 7 parts by mass of an antifoaming agent polypropylene glycol antifoaming agent DQ-Q019 (centurie macrographic chemical science and technology Co., Ltd., Dongguan), 8 parts by mass of polymerization inhibitor p-hydroxyanisole, 6 parts by mass of a leveling agent Moneng-1077 (Dongguan Mooney chemical Co., Ltd.) and the like for 40 minutes at a speed of 250rpm under a nitrogen atmosphere at 60 ℃; reducing the temperature of the system to room temperature, adding the single-component epoxy resin D1, and stirring at the speed of 500rpm for 30 minutes; 5 parts by mass of azobisisobutyronitrile initiator and 24 parts by mass of Trigonox K90 initiator are added, and mechanical stirring is carried out for 30 minutes at the speed of 300rpm, so as to obtain the one-component epoxy resin modified photosensitive resin composition D2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" D3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 4 photosensitive resin composition Property parameters
| Properties | Test standard | D2 | D3 |
| Density (liquid state) | / | 1.14 | 1.16 |
| Density (solid state) | / | 1.2 | 1.25 |
| Curing shrinkage (%) | Density method | 5.00 | 7.20 |
| Tensile Strength (MPa) | D638 | 43 | 32 |
| Tensile modulus (MPa) | D638 | 1865 | 1730 |
| Elongation at Break (%) | D638 | 17 | 16 |
| Flexural Strength (MPa) | D790 | 61 | 56 |
| Impact Strength (J/m) | D256 | 54 | 48 |
| Heat distortion temperature (. degree.C.) of 0.45MPa | D648 | 70 | 62 |
| Heat distortion temperature (. degree.C.) of 1.82MPa | D649 | 64 | 56 |
| Glass transition (Tg) | DMA | 68 | 57 |
| Temperature of post-treatment layer separation (. degree. C.) | Vacuum heating | 78 | 57 |
Example 5
(1) Preparation of copolymer BCP:
according to the total molar preferred ratio of 1, 2-epoxy-4-vinylcyclohexane (UVR molecular weight 124.18) and glycidyl methacrylate (GMA molecular weight 142.15) being 3: 5 two monomers are metered in. Adding all UVR into a reaction kettle, dividing GMA monomers into a G1 part and a G2 part according to the molar weight ratio of 3:4, firstly adding the G1 part and the G2 part of a dissolved initiator into the reaction kettle, dissolving a dibenzoyl peroxide initiator which is 4% of the total mass of the two monomers into G2 to obtain a mixed solution M, introducing nitrogen, stirring, dropwise adding the mixed solution M into the reaction kettle at 65 ℃, completing dropwise adding within 30-60 minutes, heating to 75 ℃ at the speed of 2 ℃/minute, and preserving heat for 3 hours to obtain a copolymer BCP 5.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 90 parts by mass of latent epoxy curing agent ICAM-8409 (Shenzhen, pioneer applied materials science and technology Co., Ltd.) and 100 parts by mass of liquid epoxy resin compound bis [ (3, 4-epoxycyclohexyl) methyl ] adipate (Hubei Xinjing new materials Co., Ltd.), 600 parts by mass of bis ((3, 4-epoxycyclohexyl) methyl) adipate (Hubei Xinjing new materials Co., Ltd.) and 300 parts by mass of BCP are subjected to ball milling for 2 hours at the rotating speed of 600rpm (zirconium oxide beads are used as ball milling carriers) by adopting a planetary ball mill, and the zirconium oxide beads are removed by filtration to obtain the mono-component epoxy resin E1.
(3) Preparation of photosensitive resin composition
Stirring 360 parts by mass of polyurethane acrylate RJ429 (Germany chemical), 190 parts by mass of bisphenol A glycerol dimethacrylate (an avadin reagent), 140 parts by mass of 1, 6-hexanediol diacrylate as an active diluent/150 parts by mass of 4-hydroxybutyl vinyl ether, 7 parts by mass of a defoaming agent polyether modified siloxane defoaming agent B-0518 (Federal Fine chemical Co., Ltd. in Guangdong), 8 parts by mass of hydroquinone as a polymerization inhibitor, 6 parts by mass of a leveling agent KMT-5519 (Ministry of America plastics, department of America, Baonan, Shenzhen) and the like for 30 minutes under the conditions of nitrogen atmosphere and 50 ℃ at a speed of 300 rpm; reducing the temperature of the system to room temperature, adding the single-component epoxy resin E1, and stirring at the speed of 500rpm for 30 minutes; adding 15 parts by mass of free radical initiator Irgacure184D, and mechanically stirring at 500rpm for 20 minutes to obtain the one-component epoxy resin modified photosensitive resin composition E2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" E3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 5 photosensitive resin composition Property parameters
| Properties | Test standard | E2 | E3 |
| Density (liquid state) | / | 1.13 | 1.15 |
| Density (solid state) | / | 1.19 | 1.23 |
| Curing shrinkage (%) | Density method | 5.04 | 6.50 |
| Tensile Strength (MPa) | D638 | 48 | 42 |
| Tensile modulus (MPa) | D638 | 1720 | 1600 |
| Elongation at Break (%) | D638 | 18 | 15 |
| Flexural Strength (MPa) | D790 | 54 | 53 |
| Impact Strength (J/m) | D256 | 56 | 50 |
| Heat distortion temperature (. degree.C.) of 0.45MPa | D648 | 67 | 59 |
| Heat distortion temperature (. degree.C.) of 1.82MPa | D649 | 58 | 48 |
| Glass transition (Tg) | DMA | 68 | 58 |
| Temperature of post-treatment layer separation (. degree. C.) | Vacuum heating | 87 | 72 |
Example 6
(1) Preparation of copolymer BCP:
the two monomers are metered in a total molar preferred ratio of 2:3 of 1, 2-epoxy-4-vinylcyclohexane (UVR molecular weight 124.18) and glycidyl methacrylate (GMA molecular weight 142.15). Adding all UVR into a reaction kettle, dividing GMA monomers into a G1 part and a G2 part according to the molar weight of 2:3, adding an initiator dibenzoyl peroxide initiator with 6% of the total mass of the two monomers into G2 to obtain a mixed solution M, introducing nitrogen, stirring, dropwise adding the mixed solution M into the reaction kettle at 60 ℃, completing dropwise adding within 30-60 minutes, heating to 80 ℃ at the speed of 2 ℃/minute, and preserving heat for 2 hours to obtain a copolymer BCP 6.
(2) Preparing single-component epoxy resin:
under the condition of room temperature, 40 parts by mass of latent epoxy curing agent ICAM-8409 (Shenzhen, pioneer applied materials science and technology Limited) and 300 parts by mass of liquid epoxy resin compound bis [ (3, 4-epoxy cyclohexyl) methyl ] adipate (400-750, Hubei New Zengjing materials Limited) and 1, 2-cyclohexanediol diglycidyl ether (35-65, Anhui New Yunqi technology Limited) are subjected to ball milling for 2 hours at the rotating speed of 600rpm (zirconium oxide beads are used as ball milling carriers), and the zirconium oxide beads are filtered and removed to obtain the single-component epoxy resin F1.
(3) Preparation of photosensitive resin composition
Stirring 300 parts by mass of aliphatic urethane acrylate LuCure8240 (Runkou chemical materials Co., Ltd., Guangzhou), 240 parts by mass of tripropylene glycol diacrylate TPGDA (Taiwan Changxing chemical), 170 parts by mass of tripropylene glycol diacrylate as an active diluent, 12 parts by mass of an antifoaming agent polyether AFE0800 antifoaming agent (Dookuning), 8 parts by mass of 2-tert-butylhydroquinone as an inhibitor, 9 parts by mass of a leveling agent Moneng-1077 (Dongguan Mooney chemical Co., Ltd.) and the like for 60 minutes at a speed of 200rpm under the condition of 60 ℃ and in a nitrogen atmosphere; reducing the temperature of the system to room temperature, adding 240 mass parts of single-component epoxy resin, and stirring at the speed of 500rpm for 50 minutes; adding 21 parts by mass of a free radical initiator Irgacure651, and mechanically stirring at 300rpm for 30 minutes to obtain the one-component epoxy resin modified photosensitive resin composition F2 special for 3D printing.
The "3D printing photosensitive resin composition without added one-component epoxy resin" F3 prepared according to the same formulation and preparation process as described above was used as a reference formulation. The performance test results are shown in the table below.
TABLE 6 photosensitive resin composition Property parameters
| Properties | Test standard | F2 | F3 |
| Density (liquid state) | / | 1.16 | 1.15 |
| Density (solid state) | / | 1.22 | 1.26 |
| Curing shrinkage (%) | Density method | 4.92 | 8.73 |
| Tensile Strength (MPa) | D638 | 47 | 41 |
| Tensile modulus (MPa) | D638 | 1680 | 1510 |
| Elongation at Break (%) | D638 | 17 | 17 |
| Flexural Strength (MPa) | D790 | 58 | 54 |
| Impact Strength (J/m) | D256 | 46 | 42 |
| Heat distortion temperature (. degree.C.) of 0.45MPa | D648 | 66 | 58 |
| Heat distortion temperature (. degree.C.) of 1.82MPa | D649 | 53 | 47 |
| Glass transition (Tg) | DMA | 66 | 59 |
| Temperature of post-treatment layer separation (. degree. C.) | Vacuum heating | 81 | 63 |
The embodiment shows that the single-component epoxy resin modified photosensitive resin composition for 3D printing has good mechanical strength, heat resistance and toughness after photocuring, and solves the problem that the photocuring resin is easy to split between printing layers after being subjected to post-curing treatment at 60-75 ℃ after 3D printing and forming.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The single-component epoxy resin modified photosensitive resin composition for 3D printing is characterized by comprising the following components in percentage by mass: 10-30% of single-component epoxy resin; 24-50% of bifunctional acrylate prepolymer; 10-30% of polyfunctional acrylate monomer; 11-30% of an active diluent; 1.5-4% of a photoinitiator; the single-component epoxy resin consists of a liquid epoxy resin compound, a copolymer with an epoxy group on a side chain and a latent epoxy curing agent; the copolymer with the side chain being an epoxy group is prepared by the following steps: mixing 1, 2-epoxy-4-vinylcyclohexane and glycidyl methacrylate, preheating, dissolving a dibenzoyl peroxide initiator in the glycidyl methacrylate, dropwise adding the mixture into the mixed system, and heating for reaction to obtain a copolymer; the total molar ratio of the 1, 2-epoxy-4-vinylcyclohexane to the glycidyl methacrylate is 1: 3-6: 5; the preheating is heating to 45-65 ℃; the heating reaction is heating to 70-85 ℃ and reacting for 2-4 h; the molar weight ratio of glycidyl methacrylate used in the two previous times to glycidyl methacrylate used in the two previous times is 2: 3-3: 2;
the difunctional acrylate prepolymer is at least one of epoxy modified acrylate prepolymer and polyurethane modified acrylate prepolymer, the viscosity of which is 6000-30000 mPa & S at room temperature;
the single-component epoxy resin modified photosensitive resin composition for 3D printing is prepared by the following method: stirring the bifunctional acrylate prepolymer, the polyfunctional acrylate monomer and the reactive diluent at the temperature of 30-60 ℃ and at the speed of 200-300 rpm for 30-50 minutes; cooling to room temperature, adding the single-component epoxy resin, and stirring at the speed of 300-500 rpm for 30-60 minutes; and adding a photoinitiator, and stirring at the speed of 300-500 rpm for 20-30 minutes to obtain the single-component epoxy resin modified photosensitive resin composition for 3D printing.
2. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 1, wherein: the liquid epoxy resin compound comprises any one of glycidyl ether epoxy resin and glycidyl ester epoxy resin; the latent epoxy curing agent is an epoxy curing agent which is stable to epoxy groups at room temperature and generates epoxy curing reaction when heated to the ring-opening epoxy groups of more than 80 ℃.
3. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 1, wherein: the liquid epoxy resin compound includes at least one of 1, 6-trimethylolpropane triglycidyl ether, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, adipic acid bis (3, 4-epoxycyclohexyl) methyl ester, ethylene glycol diglycidyl ether, and 1, 2-cyclohexanediol diglycidyl ether;
the latent epoxy curing agent comprises at least one of a hexafluoroantimonate thermal initiation cation curing agent, an organic boron amine compound curing agent and a modified amine latent curing agent.
4. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 1, wherein:
the multifunctional acrylate monomer comprises at least one of pentaerythritol triacrylate, dipentaerythritol hexaacrylate, di-trimethylolpropane tetraacrylate, low-viscosity dipentaerythritol pentaacrylate, bisphenol A glycerol dimethacrylate and tripropylene glycol diacrylate;
the active diluent is at least one of glycidyl methacrylate, lauryl acrylate, isobornyl acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate/bisphenol A diacrylate, tetraglycol triacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclotrimethylolpropane formal acrylate, 4-hydroxybutyl vinyl ether, 4-vinyl epoxycyclohexane, vinyl pyrrolidone and diethylene glycol divinyl ether;
the photoinitiator comprises at least one of azobisisobutyronitrile, Irgacure 754, Irgacure369, Irgacure819, Irgacure651, Irgacure184D, Easepi820, Easepi6992, Darocur1173D and TrigonoxK 90.
5. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 1, wherein: also comprises a defoaming agent, a polymerization inhibitor and a flatting agent.
6. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 1, wherein: also comprises 0.7 to 1.5 weight percent of defoaming agent; 0.6-0.9 wt% of polymerization inhibitor; 0.6 to 1.1wt% of a leveling agent.
7. The one-component epoxy resin modified photosensitive resin composition for 3D printing according to claim 5 or 6, wherein: the defoaming agent is at least one of hydrophobic stearate EL-2600, AFE-3168, polypropylene glycol defoaming agent DQ-Q019, polyether AFE0800 defoaming agent and polyether modified siloxane defoaming agent B-0518;
the polymerization inhibitor comprises at least one of hydroquinone, p-hydroxyanisole and 2-tert-butylhydroquinone;
the leveling agent comprises at least one of a Camett KMT-5510, a KMT-5519, a BETTERSOL3896, a BETTERSOL3897, an acrylate leveling agent SP-956N and a radiation curing leveling agent Glide 450.
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| CN109955480B (en) * | 2019-04-16 | 2021-06-15 | 南京航空航天大学 | Method for improving interlayer binding force of fused deposition 3D printing polymer device |
| CN110437382A (en) * | 2019-07-25 | 2019-11-12 | 华南协同创新研究院 | A kind of low smell rapid curing advertisement character panel potting resin and the preparation method and application thereof |
| CN111234513A (en) * | 2020-03-24 | 2020-06-05 | 李飞 | High-modulus 3D printing epoxy resin and preparation method thereof |
| CN111690096A (en) * | 2020-05-20 | 2020-09-22 | 广西春景环保科技有限公司 | Preparation method of 3D printing photosensitive resin material |
| CN113278108A (en) * | 2021-06-10 | 2021-08-20 | 淄博华天橡塑科技有限公司 | Interpenetrating network reinforced flexible photocuring 3D printing resin composition and photocuring 3D printing method |
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| CN104945968A (en) * | 2015-05-16 | 2015-09-30 | 刘彦君 | Light-cured three-dimensional printing resin composition and preparation method thereof |
| JP2016166262A (en) * | 2015-03-09 | 2016-09-15 | 東洋インキＳｃホールディングス株式会社 | Unsaturated ester group-containing epoxy resin |
| CN106773532A (en) * | 2015-11-19 | 2017-05-31 | 芜湖启泽信息技术有限公司 | It is a kind of to be applied to photosensitive resin of 3D printing and preparation method thereof |
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| JP2016166262A (en) * | 2015-03-09 | 2016-09-15 | 東洋インキＳｃホールディングス株式会社 | Unsaturated ester group-containing epoxy resin |
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| CN106773532A (en) * | 2015-11-19 | 2017-05-31 | 芜湖启泽信息技术有限公司 | It is a kind of to be applied to photosensitive resin of 3D printing and preparation method thereof |
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