CN113087859A - 3D printing light-cured resin model material for ornament casting and preparation method thereof - Google Patents

3D printing light-cured resin model material for ornament casting and preparation method thereof Download PDF

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Publication number
CN113087859A
CN113087859A CN202110443628.9A CN202110443628A CN113087859A CN 113087859 A CN113087859 A CN 113087859A CN 202110443628 A CN202110443628 A CN 202110443628A CN 113087859 A CN113087859 A CN 113087859A
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resin
model material
epoxy resin
modified
parts
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Chinese (zh)
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徐勇军
蔡卓弟
谭世芝
陈炎丰
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Dongguan University of Technology
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Dongguan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention relates to the technical field of photocuring 3D printing, in particular to a 3D printing photocuring resin model material for casting ornaments and a preparation method thereof, wherein the 3D printing photocuring resin model material comprises 25-45 parts of modified matrix resin, 20-32 parts of prepolymer matrix resin, 15-35 parts of reactive diluent, 2-7 parts of photoinitiator, 5-10 parts of wax emulsion and 0.1-1 part of auxiliary agent; according to the invention, epoxy resin is modified by GMA grafted carbon nanotubes, modified epoxy resin and methacrylic acid are synthesized to obtain modified epoxy acrylate, the matrix resin obtained by mixing modified matrix resin and prepolymer matrix resin has excellent comprehensive mechanical properties, and a photocuring resin model material with low viscosity, high toughness, high strength and excellent comprehensive properties is obtained by assisting with an active diluent, a photoinitiator and other auxiliaries, so that the photocuring resin model material has a relatively high market prospect.

Description

3D printing light-cured resin model material for ornament casting and preparation method thereof
Technical Field
The invention relates to the technical field of photocuring 3D printing, in particular to a 3D printing photocuring resin model material for casting ornaments and a preparation method thereof.
Background
The 3D printing technology has the advantages of directly generating parts in any shape from computer graphic data without machining or dies, greatly shortening the product development period, improving the production efficiency and the like, and is called as an important ring of the third industrial revolution. And the DLP type photocuring printing technology (Digital Light Processing) has the advantages of high forming speed and high precision, and is suitable for printing small-size precise casting components such as individuation and a small amount of jewelry and the like. The production method of the blank of the jewelry or the part thereof is called as casting or casting by heating and melting metal or alloy thereof, then casting the metal or the alloy into a casting mold cavity corresponding to the shape and the size of the jewelry or the part thereof, and cooling and solidifying the metal or the alloy. The method can cast a plurality of ornaments at one time, has extremely high production efficiency, can manufacture the ornaments with complex shapes, particularly the ornaments with complex inner cavities, and has almost no limit on the size of the castings. The model is printed by using a 3D printing technology, and the model is subjected to lost wax casting to obtain a casting, which is a technology increasingly widely used in the current ornament market.
And DLP type 3D printing technique and SLA type 3D printing technique are very similar, utilize liquid photosensitive resin reservoir to print the material to the mode that the layer by layer was printed the article and is printed the shaping, also can need add the support during printing, and holistic precision is high. The DLP type 3D printing technology is characterized in that a liquid photosensitive resin is photocured by a projector projection method to print a finished product. Firstly, the 3D model is transversely cut into layers by 3D printing software, then a projector projects the shape pattern of the first layer model onto liquid photosensitive resin, and then photocuring and molding are carried out. After the first layer is completed, the object is slightly raised, and then the shape pattern of the next layer of the pattern is projected onto the photosensitive resin, and the pattern is printed out in a laminated manner. Because DLP type 3D printing technique and SLA type 3D printing technique all use liquid photosensitive resin to make the material of printing, although print the fineness extremely high, print the cost more expensive, at present foreign country has basically monopolized 3D printer and photocuring resin raw materials market, leads to its manufacturing cost high. At present, domestic cured 3D printing photosensitive resin has poor forming effect, high viscosity, low printing precision and insufficient toughness. Therefore, in view of the above problems, a DLP type photocurable 3D printing photosensitive resin which has the same overall performance as that of the resin in the abroad but is relatively cheaper is developed, and has a high market potential in China.
Disclosure of Invention
In order to solve the problems, the invention provides a 3D printing light-cured resin model material for ornament casting and a preparation method thereof, and the obtained light-cured resin model material has the characteristics of low viscosity, high toughness and high strength and has excellent comprehensive performance.
In order to achieve the purpose, the technical scheme adopted by the invention is that the 3D printing light-cured resin model material for casting the ornaments comprises the following components: 25-45 parts of modified matrix resin, 20-32 parts of prepolymer matrix resin, 15-35 parts of reactive diluent, 2-7 parts of photoinitiator, 5-10 parts of wax emulsion and 0.1-1 part of auxiliary agent; the modified matrix resin is obtained by modifying epoxy resin by GMA grafted carbon nano tubes and synthesizing methacrylic acid with the epoxy resin.
As a preferable scheme, the GMA grafted carbon nanotube is formed by reacting an acidified carbon nanotube with an N, N' -dimethylformamide solution and GMA through a catalyst and a polymerization inhibitor; the carbon nano tube has the outer diameter of 10nm-20nm and the specific surface area of 150m2(ii)/g; the catalyst comprises triethylamine and tetrabutylammonium bromide; the polymerization inhibitor is diethylhydroxylamine.
As a preferable scheme, the modified epoxy acrylate is synthesized by reacting epoxy resin, GMA grafted carbon nano tubes and methacrylic acid through a catalyst and a polymerization inhibitor; the catalyst is trimethyl benzyl ammonium chloride; the polymerization inhibitor is one of methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl-p-cresol.
Preferably, the epoxy resin is one of epoxy resin E51, epoxy resin E44, epoxy resin F51 or epoxy resin F44.
Preferably, the prepolymer matrix resin is one of bisphenol a epoxy acrylate, bisphenol F epoxy acrylate, urethane acrylate, polyester acrylate and polyether acrylate.
In a preferred embodiment, the reactive diluent is a combination of two or more of butyl acrylate, hydroxyethyl methacrylate, isobornyl methacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, and triethylene glycol diacrylate.
As a preferable scheme, the photoinitiator is one or two combinations of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 2-diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
Preferably, the wax emulsion is one of modified paraffin wax emulsion, palm wax emulsion, polyethylene wax emulsion, oxidized polyethylene wax emulsion and oxidized polypropylene wax emulsion.
As a preferable scheme, the auxiliary agent comprises a polymerization inhibitor, a leveling agent and a pigment; the polymerization inhibitor is one of methoxyphenol, diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the leveling agent is one of silicone leveling agents, organic silicon leveling agents, polysiloxane-polyether leveling agents and other organic silicon leveling agents; the pigment is one of indanthrone, chromium oxide green, quinacridone violet and lithol scarlet.
In order to obtain the 3D printing photosensitive resin model material, the invention also adopts the technical scheme that the preparation method of the 3D printing light-cured resin model material for casting the ornaments comprises the following steps:
preparing modified epoxy resin: adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, stirring and mixing uniformly, adding GMA, and reacting to obtain a GMA grafted carbon nano tube; adding the GMA grafted carbon nano tube into epoxy resin for ultrasonic blending to obtain modified epoxy resin;
preparing modified matrix resin: adding modified epoxy resin into a reaction kettle, heating, adding a polymerization inhibitor and a catalyst, dropwise adding methacrylic acid, and continuously stirring for reaction to obtain modified matrix resin;
preparing a light-cured resin model material: under the condition of room temperature, adding the modified matrix resin, the prepolymer matrix resin, the photoinitiator, the reactive diluent, the wax emulsion and the auxiliary agent into a reaction device in sequence, fully stirring until the mixture is uniformly mixed, placing the mixture into an ultrasonic cleaner, vibrating for a certain time, taking out the mixture, standing and defoaming to obtain the photocuring resin model material.
As a preferred scheme, the specific steps for preparing the modified epoxy resin are as follows:
(1) adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, uniformly mixing, adding GMA, 0.2 wt% of diethylhydroxylamine, 2.5 wt% of triethylamine and 2.5 wt% of tetrabutylammonium bromide, and gradually heating to 75 ℃ for reacting for 24 hours;
(2) after the reaction is finished, precipitating a product in excessive distilled water, carrying out vacuum filtration, washing for 3-5 times by using absolute ethyl alcohol, carrying out Soxhlet extraction for 12 hours, and drying the product for 12 hours in a vacuum environment at the temperature of 60 ℃ to obtain a GMA grafted carbon nanotube;
(3) and adding the prepared modified carbon nano tube into epoxy resin, and performing ultrasonic blending treatment for 4 hours to obtain the modified epoxy resin.
As a preferred scheme, the specific steps for preparing the modified matrix resin are as follows: adding the obtained modified epoxy resin into a reaction kettle, heating to 85 ℃, adding 0.5-1 wt% of polymerization inhibitor and 0.5-2 wt% of trimethyl benzyl ammonium chloride, dropwise adding methacrylic acid with equal mass parts, stirring for 1 hour, heating to 110 ℃, and continuing to stir at high speed for 3 hours to obtain modified matrix resin; the polymerization inhibitor is one of methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl-p-cresol.
As a preferable scheme, the stirring reaction time for preparing the light-cured resin model material is 1 hour, and the ultrasonic oscillation time is 1.5 hours.
The invention has the beneficial effects that:
according to the invention, the modified epoxy resin is obtained by using GMA graft modified carbon nano tubes, the modified epoxy resin is synthesized with methacrylic acid to obtain a prepolymer matrix resin with excellent performance, and auxiliary agents such as an active diluent, a photoinitiator, wax emulsion and the like are added to obtain a photocuring resin model material with low viscosity, high toughness, high strength and excellent comprehensive performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a 3D printing light-cured resin model material for casting ornaments, which comprises the following components: 25-45 parts of modified matrix resin, 20-32 parts of prepolymer matrix resin, 15-35 parts of reactive diluent, 2-7 parts of photoinitiator, 5-10 parts of wax emulsion and 0.1-1 part of auxiliary agent; the modified matrix resin is obtained by modifying epoxy resin by GMA grafted carbon nano tubes and synthesizing methacrylic acid with the epoxy resin.
According to the invention, the modified epoxy resin is obtained by using GMA graft modified carbon nano tubes, the modified epoxy resin is synthesized with methacrylic acid to obtain a prepolymer matrix resin with excellent performance, and auxiliary agents such as an active diluent, a photoinitiator, wax emulsion and the like are added to obtain a photocuring resin model material with low viscosity, high toughness, high strength and excellent comprehensive performance.
GMA grafted carbon nanotubes
In one or more embodiments, the GMA grafted carbon nanotubes are formed by reacting acidified carbon nanotubes with N, N' -dimethylformamide solution and GMA through a catalyst and a polymerization inhibitor; preferably, the carbon nanotubes have an outer diameter of 10nm to 20nm and a specific surface area of 150m2(ii)/g; the catalyst comprises triethylamine and tetrabutylammonium bromide; the polymerization inhibitor is diethylhydroxylamine.
The carbon nano tube has the advantages of extremely large length-diameter ratio, large specific surface area and excellent mechanical properties (such as high strength, high rigidity and high modulus), and the mechanical properties of the material can be improved by adding a very small amount of the carbon nano tube. However, because the carbon nano tube is easy to form aggregates and is difficult to disperse, and the compatibility between the carbon nano tube and a high molecular organic matter is poor, the invention uses GMA (namely organic matter glycidyl methacrylate) to carry out surface treatment on the carbon nano tube, and esterifies the carbon nano tube through the ring-opening nucleophilic addition reaction of GMA and carboxyl on the carbon nano tube, thereby improving the dispersion problem of the carbon nano tube in an organic solution.
Modified epoxy acrylate
In one or more embodiments, the modified epoxy acrylate is synthesized by reacting epoxy resin, GMA grafted carbon nanotubes and methacrylic acid with a catalyst and a polymerization inhibitor; preferably, the catalyst is trimethyl benzyl ammonium chloride, and the polymerization inhibitor is one of methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl-p-cresol; the epoxy resin is one of epoxy resin E51, epoxy resin E44, epoxy resin F51 or epoxy resin F44.
The nano-particle carbon nano-tube is introduced into the epoxy resin, so that the mechanical properties such as toughness, strength and the like of the matrix resin are obviously improved; and then the prepolymer is compounded with the prepolymer matrix resin on the market, so that the prepolymer matrix resin has lower viscosity and high mechanical property.
Prepolymer matrix resins
In one or more embodiments, the prepolymer base resin is one of bisphenol a type epoxy acrylate, bisphenol F type epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate.
Reactive diluent
In one or more embodiments, the reactive diluent is a combination of two or more of butyl acrylate, hydroxyethyl methacrylate, isobornyl methacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate.
Photoinitiator
In one or more embodiments, the photoinitiator is one or a combination of two of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone.
Wax emulsion
In one or more embodiments, the wax emulsion is one of a modified paraffin wax emulsion, a palm wax emulsion, a polyethylene wax emulsion, an oxidized polypropylene wax emulsion.
By adding the wax emulsion, the surface of the 3D printing light-cured resin model material is fine and smooth, the gloss is uniform, the transparency is good, the light-cured effect is not influenced, the surface quality and the scratch resistance of the model material are improved, the subsequent casting process of the ornament can be carried out without processing and repairing the model material, the process is simplified, and the time and the cost are saved.
Auxiliary agent
In one or more embodiments, the additives include polymerization inhibitors, leveling agents, and pigments; the polymerization inhibitor is one of methoxyphenol, diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the leveling agent is one of silicone leveling agents, organic silicon leveling agents, polysiloxane-polyether leveling agents and other organic silicon leveling agents; the pigment is one of indanthrone, chromium oxide green, quinacridone violet and lithol scarlet.
Preferably, the silicone leveling agent is VOK-Levaslip-410 leveling agent; the organic silicon flatting agent is a BYK378 flatting agent; the organic silicon flatting agent such as polysiloxane-polyether is BYK331 polyether flatting agent.
In order to obtain the 3D printing photosensitive resin, the invention also provides a related preparation method, which comprises the following steps:
preparing modified epoxy resin: adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, stirring and mixing uniformly, adding GMA, and reacting to obtain a GMA grafted carbon nano tube; adding the GMA grafted carbon nano tube into epoxy resin for ultrasonic blending to obtain modified epoxy resin;
preparing modified matrix resin: adding modified epoxy resin into a reaction kettle, heating, adding a polymerization inhibitor and a catalyst, dropwise adding methacrylic acid, and continuously stirring for reaction to obtain modified matrix resin;
preparing a light-cured resin model material: under the condition of room temperature, adding the modified matrix resin, the prepolymer matrix resin, the photoinitiator, the reactive diluent, the wax emulsion and the auxiliary agent into a reaction device in sequence, fully stirring until the mixture is uniformly mixed, placing the mixture into an ultrasonic cleaner, vibrating for a certain time, taking out the mixture, standing and defoaming to obtain the photocuring resin model material.
In one or more embodiments, the specific steps for preparing the modified epoxy resin are:
(1) adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, uniformly mixing, adding GMA, 0.2 wt% of diethylhydroxylamine, 2.5 wt% of triethylamine and 2.5 wt% of tetrabutylammonium bromide, and gradually heating to 75 ℃ for reacting for 24 hours;
(2) after the reaction is finished, precipitating a product in excessive distilled water, carrying out vacuum filtration, washing for 3-5 times by using absolute ethyl alcohol, carrying out Soxhlet extraction for 12 hours, and drying the product for 12 hours in a vacuum environment at the temperature of 60 ℃ to obtain a GMA grafted carbon nanotube;
(3) and adding the prepared modified carbon nano tube into epoxy resin, and performing ultrasonic blending treatment for 4 hours to obtain the modified epoxy resin.
In one or more embodiments, the specific steps for preparing the modified base resin are: adding the obtained modified epoxy resin into a reaction kettle, heating to 85 ℃, adding 0.5-1 wt% of polymerization inhibitor and 0.5-2 wt% of trimethyl benzyl ammonium chloride, dropwise adding methacrylic acid with equal mass parts, stirring for 1 hour, heating to 110 ℃, and continuing to stir at high speed for 3 hours to obtain modified matrix resin; the polymerization inhibitor is one of methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl-p-cresol.
In one or more embodiments, the stirring reaction time for preparing the photocurable resin molding material is 1 hour, and the ultrasonic oscillation time is 1.5 hours.
The following embodiments are provided to illustrate the present invention in detail, and it should be noted that the invention is not limited to the embodiments.
Example 1
The preparation process of the 3D printing light-cured resin model material for ornament casting in the embodiment is as follows:
weighing 25 parts of modified matrix resin, 32 parts of bisphenol A epoxy acrylate, 15 parts of hydroxyethyl methacrylate, 20 parts of 1, 6-hexanediol diacrylate, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 5 parts of oxidized polypropylene wax emulsion, 0.85 part of p-hydroxyanisole, 0.1 part of VOK-Levaslip-410 silicone flatting agent and 0.05 part of lithol scarlet in sequence at room temperature, stirring for 1 hour by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, placing the container in an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, and standing for defoaming to obtain the photocuring resin model material.
Example 2
The preparation process of the 3D printing light-cured resin model material for ornament casting in the embodiment is as follows:
under the condition of room temperature, weighing 30 parts of modified matrix resin, 30.7 parts of urethane acrylate, 15 parts of hydroxyethyl methacrylate, 15 parts of dipropylene glycol diacrylate, 3 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 6 parts of oxidized polyethylene wax emulsion, 0.65 part of p-hydroxyanisole, 0.1 part of VOK-Levaslip-410 flatting agent and 0.05 part of indanthrone according to the mass ratio, sequentially adding the materials into a round-bottom flask, stirring for 1 hour by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, standing and defoaming to obtain the light-cured resin model material.
Example 3
The preparation process of the 3D printing light-cured resin model material for ornament casting in the embodiment is as follows:
weighing 35 parts of modified matrix resin, 28.4 parts of polyurethane acrylate, 10 parts of isobornyl methacrylate, 15 parts of 1, 6-hexanediol diacrylate, 4 parts of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 7 parts of modified paraffin emulsion, 0.5 part of hydroquinone, 0.05 part of BYK378 flatting agent and 0.05 part of indanthrone in sequence at room temperature, stirring for 1 hour by using an electric stirrer, pouring into a container, sealing, placing into an ultrasonic cleaning instrument, vibrating for 1.5 hours, taking out, standing and defoaming to obtain the photocuring resin model material.
Example 4
The preparation process of the 3D printing light-cured resin model material for ornament casting in the embodiment is as follows:
weighing 35 parts of modified matrix resin, 26.6 parts of bisphenol A epoxy acrylate, 10 parts of isobornyl methacrylate, 15 parts of neopentyl glycol diacrylate, 3 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2 parts of 2, 2-diethoxyacetophenone, 8 parts of polypropylene oxide wax emulsion, 0.3 part of hydroquinone, 0.05 part of BYK378 flatting agent and 0.05 part of quinacridone violet in sequence at room temperature, adding the mixture into a round-bottom flask, stirring the mixture for 1 hour by using an electric stirrer until the mixture is uniform, pouring the mixture into a container for sealing, placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the mixture, and standing and defoaming to obtain the photocuring resin model material.
Example 5
The preparation process of the 3D printing light-cured resin model material for ornament casting in the embodiment is as follows:
under the condition of room temperature, weighing 40 parts of modified matrix resin, 24.7 parts of polyester acrylate, 10 parts of butyl acrylate, 10 parts of neopentyl glycol diacrylate, 3 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 3 parts of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 9 parts of wax emulsion, 0.2 part of p-tert-butyl catechol, 0.05 part of BYK331 polyether flatting agent and 0.05 part of lithol scarlet in according to the mass ratio, sequentially adding the materials into a round-bottom flask, stirring the materials for 1 hour by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container, sealing the container, placing the container into an ultrasonic cleaning instrument, oscillating the materials for 1.5 hours, taking the materials out, and standing and defoaming the photocuring resin model material is obtained.
Example 6
Weighing 45 parts of modified matrix resin, 22.9 parts of polyester acrylate, 5 parts of butyl acrylate, 10 parts of triethylene glycol diacrylate, 4 parts of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 3 parts of 1-hydroxycyclohexyl phenyl ketone, 10 parts of oxidized polypropylene wax emulsion, 0.05 part of p-tert-butyl catechol, 0.05 part of BYK331 polyether flatting agent and 0.05 part of chromium oxide green in sequence at room temperature, stirring for 1 hour by using an electric stirrer, pouring into a container for sealing, placing into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out, standing and defoaming to obtain the light-cured resin model material.
Comparative example 1
The preparation process of the photo-curing 3D printing photosensitive resin of the comparative example is as follows:
under the condition of room temperature, weighing 61.6 parts of bisphenol A epoxy acrylate, 10 parts of isobornyl methacrylate, 15 parts of neopentyl glycol diacrylate, 3 parts of 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2 parts of 2, 2-diethoxyacetophenone, 8 parts of oxidized polypropylene wax emulsion, 0.3 part of hydroquinone, 0.05 part of BYK378 flatting agent and 0.05 part of quinacridone violet in sequence according to the mass ratio, stirring for 1 hour by using an electric stirrer until the mixture is uniform, pouring the mixture into a container for sealing, then placing the container in an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the mixture, standing and defoaming to obtain the photocuring resin model material.
The results of the performance tests conducted on examples 1 to 6 of the present invention and comparative example 1 are shown in table 1.
Table 1: performance parameters for examples 1-6 and comparative example 1
Figure BDA0003035941110000111
As can be seen from the performance test results in Table 1, the modified epoxy acrylate has a certain improvement on various performance parameter indexes of the 3D printing photocuring resin model material, so that the material has the characteristics of low viscosity, high toughness and high strength, has excellent comprehensive performance, can well meet the requirements of actual production, and has high market competitiveness.
The above embodiments are merely illustrative of the preferred embodiments of the present invention, and not restrictive, and various changes and modifications to the technical solutions of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are intended to fall within the scope of the present invention defined by the appended claims.

Claims (10)

1. A3D printing light-cured resin model material for casting ornaments is characterized by comprising the following components: 25-45 parts of modified matrix resin, 20-32 parts of prepolymer matrix resin, 15-35 parts of reactive diluent, 2-7 parts of photoinitiator, 5-10 parts of wax emulsion and 0.1-1 part of auxiliary agent;
the modified matrix resin is obtained by modifying epoxy resin by GMA grafted carbon nano tubes and synthesizing methacrylic acid with the epoxy resin.
2. The 3D printing light-cured resin model material for jewelry casting according to claim 1, wherein: the GMA grafted carbon nanotube is prepared by mixing an acidified carbon nanotube with N, N' -dimethyl formamide solution and GMA are reacted by catalyst and polymerization inhibitor; the carbon nano tube has the outer diameter of 10nm-20nm and the specific surface area of 150m2(ii)/g; the catalyst comprises triethylamine and tetrabutylammonium bromide; the polymerization inhibitor is diethylhydroxylamine.
3. The 3D printing light-cured resin model material for jewelry casting according to claim 2, wherein: the modified epoxy acrylate is synthesized by reacting epoxy resin, GMA grafted carbon nano tube and methacrylic acid through a catalyst and a polymerization inhibitor; the catalyst is trimethyl benzyl ammonium chloride; the polymerization inhibitor is one of methoxyphenol, hydroquinone, 2, 5-dimethyl hydroquinone and 2, 6-di-tert-butyl-p-cresol.
4. The 3D printing light-cured resin model material for jewelry casting according to claim 3, wherein: the epoxy resin is one of epoxy resin E51, epoxy resin E44, epoxy resin F51 or epoxy resin F44.
5. The 3D printing light-cured resin model material for jewelry casting according to claim 1, wherein: the prepolymer matrix resin is one of bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, polyurethane acrylate, polyester acrylate and polyether acrylate.
6. The 3D printing light-cured resin model material for jewelry casting according to claim 1, wherein: the active diluent is a combination of more than two of butyl acrylate, hydroxyethyl methacrylate, isobornyl methacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate and triethylene glycol diacrylate; the photoinitiator is one or two combinations of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, 2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
7. The 3D printing light-cured resin model material for jewelry casting according to claim 1, wherein: the wax emulsion is one of modified paraffin wax emulsion, palm wax emulsion, polyethylene wax emulsion, oxidized polyethylene wax emulsion and oxidized polypropylene wax emulsion.
8. The 3D printing light-cured resin model material for jewelry casting according to claim 1, wherein: the auxiliary agent comprises a polymerization inhibitor, a flatting agent and a pigment; the polymerization inhibitor is one of methoxyphenol, diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the leveling agent is one of silicone leveling agents, organic silicon leveling agents, polysiloxane-polyether leveling agents and other organic silicon leveling agents; the pigment is one of indanthrone, chromium oxide green, quinacridone violet and lithol scarlet.
9. A preparation method of a 3D printing light-cured resin model material for casting ornaments is characterized by comprising the following steps:
preparing modified epoxy resin: adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, stirring and mixing uniformly, adding GMA, and reacting to obtain a GMA grafted carbon nano tube; adding the GMA grafted carbon nano tube into epoxy resin for ultrasonic blending to obtain modified epoxy resin;
preparing modified matrix resin: adding modified epoxy resin into a reaction kettle, heating, adding a polymerization inhibitor and a catalyst, dropwise adding methacrylic acid, and continuously stirring for reaction to obtain modified matrix resin;
preparing a light-cured resin model material: under the condition of room temperature, adding the modified matrix resin, the prepolymer matrix resin, the photoinitiator, the reactive diluent, the wax emulsion and the auxiliary agent into a reaction device in sequence, fully stirring until the mixture is uniformly mixed, placing the mixture into an ultrasonic cleaner, vibrating for a certain time, taking out the mixture, standing and defoaming to obtain the photocuring resin model material.
10. The preparation method of the 3D printing light-cured resin model material for ornament casting according to claim 9, wherein the specific steps of preparing the modified epoxy resin are as follows:
(1) adding the acidified carbon nano tube into an N, N' -dimethylformamide solution, uniformly mixing, adding GMA, 0.2 wt% of diethylhydroxylamine, 2.5 wt% of triethylamine and 2.5 wt% of tetrabutylammonium bromide, and gradually heating to 75 ℃ for reacting for 24 hours;
(2) after the reaction is finished, precipitating a product in excessive distilled water, carrying out vacuum filtration, washing for 3-5 times by using absolute ethyl alcohol, carrying out Soxhlet extraction for 12 hours, and drying the product for 12 hours in a vacuum environment at the temperature of 60 ℃ to obtain a GMA grafted carbon nanotube;
(3) and adding the prepared modified carbon nano tube into epoxy resin, and performing ultrasonic blending treatment for 4 hours to obtain the modified epoxy resin.
CN202110443628.9A 2021-04-23 2021-04-23 3D printing light-cured resin model material for ornament casting and preparation method thereof Pending CN113087859A (en)

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Application publication date: 20210709