Organic-inorganic hybrid monomer, light-cured resin composition and application thereof

Abstract

The invention provides an organic-inorganic hybrid monomer, a light-cured resin composition and application thereof, and particularly relates to the technical field of 3D printing materials. The organic-inorganic hybrid monomer is prepared by the following steps: adding a silane coupling agent into an organic solvent dispersion liquid of silicon dioxide to carry out silane modification so as to obtain a silane modified silicon dioxide organic solvent dispersion liquid; continuously adding a high Tg monomer into the silane modified silicon dioxide organic solvent dispersion liquid, uniformly mixing, and finally removing the organic solvent to obtain an organic-inorganic hybrid monomer; wherein the Tg value of the high Tg monomer is greater than 100 DEG C. The organic-inorganic hybrid monomer provided by the invention effectively inhibits agglomeration and sedimentation phenomena of silicon dioxide nanoparticles, reduces the viscosity of the organic-inorganic hybrid monomer, has good fluidity, and facilitates flowing and spreading of the organic-inorganic hybrid monomer.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing materials, and in particular to an organic-inorganic hybrid monomer, a photocurable resin composition and applications thereof. Background Art

[0002] High temperature resistant 3D printing materials refer to materials that can maintain stable performance in high temperature environments and have good mechanical strength and chemical stability. In the aerospace field, such materials can be used to manufacture key components such as engine parts and rocket nozzles, thereby improving the performance and reliability of equipment; in the automotive manufacturing field, high temperature resistant materials can be used to manufacture engine peripheral components to improve the thermal efficiency and durability of the engine; in the industrial manufacturing field, they can be used to manufacture high temperature molds and furnace linings to improve production efficiency and product quality.

[0003] As a 3D printing material, the key to the high temperature resistance of high temperature resistant photocurable resin lies in the use of a large number of multifunctional monomers (functionality ≥ 3), and the mass ratio of these monomers in the formula is usually more than 40%. However, as the amount of multifunctional monomers added increases, the shrinkage of the resin during the curing process will also increase. In order to reduce the shrinkage after curing, powder materials are added to many photocurable resin formulas. However, this practice will cause powder agglomeration and sedimentation. At the same time, the addition of powder will increase the viscosity of the material, which is not conducive to the application of the material in photocuring printing equipment.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] One of the purposes of the present invention is to provide an organic-inorganic hybrid monomer, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0006] A second object of the present invention is to provide a photocurable resin composition.

[0007] A third object of the present invention is to provide an application of a photocurable resin composition.

[0008] In order to solve the above technical problems, the present invention particularly adopts the following technical solutions: The first aspect of the present invention provides an organic-inorganic hybrid monomer, wherein a silane coupling agent is added to an organic solvent dispersion of silicon dioxide for silane modification to obtain a silane-modified organic solvent dispersion of silicon dioxide.

[0009] Continue to add high Tg monomers to the silane-modified silica organic solvent dispersion and mix them evenly, and finally remove the organic solvent to obtain an organic-inorganic hybrid monomer.

[0010] Wherein, the Tg value of the high Tg monomer is greater than 100°C.

[0011] Further, the high Tg monomer includes at least one of DMAA, DCPDMA, DCPDA, TMCHA, IBOMA, IBOA, TMPTMA, 3EOTMPTA and 3POTMPTA.

[0012] The added amount of the high Tg monomer is 0.8 to 1.2 times the mass of silicon dioxide.

[0013] The organic solvent includes at least one of ethanol, isopropanol, undecanol, dodecanol, acetone, butanone, n-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, butyl acetate, ethyl valerate, butyl valerate and ethyl acetate.

[0014] In the organic solvent dispersion of silica, the mass content of silica is 30-80%.

[0015] Furthermore, the brand of the silane coupling agent includes at least one of KH-550, KH-560, KH-570, KH-792 and KH-900.

[0016] The added amount of the silane coupling agent is 10-30% of the mass of silicon dioxide.

[0017] The temperature of the silane modification is 40-80° C., and the time is 18-36 hours.

[0018] Furthermore, the organic solvent is removed by heating.

[0019] In the silicon dioxide, the proportion of coarse-grained particles is 15-25wt%; the proportion of medium-grained particles is 15-25wt%; and the proportion of fine-grained particles is 50-70wt%.

[0020] The coarse particle size is greater than 4 μm, the medium particle size is 2-4 μm, and the fine particle size is less than 2 μm.

[0021] The second aspect of the present invention provides a photocurable resin composition, comprising a trifunctional (meth)acrylate monomer, a triallylcyanurate monomer, a (meth)acrylate diluent monomer, an organic-inorganic hybrid monomer, and a photoinitiator; Wherein, the organic-inorganic hybrid monomer is the organic-inorganic hybrid monomer described in the first aspect.

[0022] Furthermore, the trifunctional (meth)acrylate monomer includes at least one of tris(2-hydroxyethyl)isocyanurate triacrylate, triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, (3) propoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate.

[0023] The structural formula of the triallyl cyanurate monomer is shown in Formula I below:

[0024] Formula I Among them, R 1 , R 2 , R 3 is selected from hydrogen, methyl, ethyl or n-propyl.

[0025] Furthermore, the Tg value of the (meth)acrylate diluent monomer is greater than 100°C.

[0026] The (meth)acrylate diluent monomer includes a monofunctional (meth)acrylate monomer and / or a difunctional (meth)acrylate monomer.

[0027] Furthermore, the (meth)acrylate diluent monomer includes at least one of isobornyl acrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclohexane dimethanol diacrylate and tricyclohexane dimethanol dimethacrylate.

[0028] The photoinitiator includes at least one of ethyl 2,4,6-trimethylbenzoylphosphonate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether and methyl o-benzoylbenzoate.

[0029] Furthermore, the photocurable resin composition comprises, by weight, 15 to 20 parts of trifunctional (meth)acrylate monomer, 10 to 15 parts of triallyl cyanurate monomer, 8 to 10 parts of (meth)acrylate diluent monomer, 55 to 65 parts of organic-inorganic hybrid monomer and 0.5 to 2 parts of photoinitiator.

[0030] The third aspect of the present invention provides the use of the photocurable resin composition in 3D printing.

[0031] Compared with the prior art, the present invention has at least the following beneficial effects: The organic-inorganic hybrid monomer provided by the present invention forms a layer of organic functional groups on the surface of the silane-modified silica, which has better compatibility with organic solvents, thereby enhancing the dispersibility of silica in organic solvents, reducing the interaction between particles, and effectively inhibiting the agglomeration and sedimentation of silica nanoparticles. The high Tg monomer (Tg value>100°C) has good rheological properties, which helps to reduce the viscosity of the organic-inorganic hybrid monomer, maintain good fluidity, and facilitate the flow and spreading of the organic-inorganic hybrid monomer.

[0032] In the photocurable resin composition provided by the present invention, the introduction of trifunctional (meth) acrylate and cyanuric acid tryptophan significantly improves the crosslinking density of the resin, thereby enhancing the mechanical properties and thermal stability of the cured material. At the same time, the addition of organic-inorganic hybrid monomers effectively fills the gaps generated during the curing process and reduces the overall shrinkage of the material. In addition, the (meth) acrylate dilution monomer can not only reduce the viscosity of the composition, but also participate in the photocuring crosslinking reaction, further improving the crosslinking density of the material. There is good compatibility between the (meth) acrylate dilution monomer and the organic-inorganic hybrid monomer, so that the organic-inorganic hybrid monomer can be evenly dispersed in the resin composition. The resin composition not only has low viscosity and high temperature resistance, but also shows lower shrinkage after curing, which improves the precision of the cured material.

[0033] The application provided by the present invention, in view of the advantages of the above-mentioned photocurable resin composition, improves the accuracy, stability, toughness and thermomechanical properties of the printed parts obtained by 3D printing, while reducing the curing shrinkage rate and improving the printing efficiency, thereby meeting the needs of a wider range of industrial and engineering applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1 This is a photo of the organic-inorganic hybrid monomer obtained in Example 1; Figure 2 This is the infrared spectrum of the organic-inorganic hybrid monomer obtained in Example 1. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The components of the embodiments of the present invention described and shown herein can be arranged and designed in various different configurations.

[0037] The first aspect of the present invention provides an organic-inorganic hybrid monomer, wherein a silane coupling agent is added to an organic solvent dispersion of silicon dioxide for silane modification to obtain a silane-modified organic solvent dispersion of silicon dioxide.

[0038] Then, high Tg monomer is added to the silane-modified silica organic solvent dispersion and mixed evenly, and finally, the organic solvent is removed to obtain an organic-inorganic hybrid monomer. Tg represents the glass transition temperature.

[0039] Wherein, the Tg value of the high Tg monomer is greater than 100°C.

[0040] The organic-inorganic hybrid monomer provided by the present invention forms a layer of organic functional groups on the surface of the silane-modified silica, which has better compatibility with organic solvents, thereby enhancing the dispersibility of silica in organic solvents, reducing the interaction between particles, and effectively inhibiting the agglomeration and sedimentation of silica nanoparticles. The high Tg monomer (Tg value>100°C) has good rheological properties, which helps to reduce the viscosity of the organic-inorganic hybrid monomer, maintain good fluidity, and facilitate the flow and spreading of the organic-inorganic hybrid monomer.

[0041] The organic solvent dispersion of silicon dioxide also includes a dispersant, and the specific type of the dispersant is not limited, and any dispersant that can disperse inorganic particles in an organic solvent can be used. The amount of the dispersant is 1-5% of the mass of the silicon dioxide.

[0042] Further, the high Tg monomer includes at least one of DMAA (dimethylacrylamide), DCPBA (3,5-dicarboxyphenylboronic acid), DCPDA (tricyclodecane dimethanol diacrylate), DCPA (dicyclopentenyl acrylate), TMCHA (3,3,5-trimethylcyclohexyl acrylate), IBOMA (isobornyl methacrylate), IBOA (isobornyl acrylate), TMPTMA (trimethylolpropane trimethacrylate), 3EOTMPTA (ethoxylated trimethylolpropane triacrylate) and 3POTMPTA (propoxylated trimethylolpropane triacrylate).

[0043] The organic solvent includes at least one of ethanol, isopropanol, undecanol, dodecanol, acetone, butanone, n-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, butyl acetate, ethyl valerate, butyl valerate and ethyl acetate.

[0044] In the organic solvent dispersion of silica, the mass content of silica is 30-80%, which ensures that the subsequently prepared organic-inorganic hybrid monomer has a high content of silica and a low viscosity.

[0045] Typically but not limitatively, in the organic solvent dispersion of silica, the mass content of silica can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, or any value within the range of 30% to 80%.

[0046] Furthermore, the brand of the silane coupling agent includes at least one of KH-550, KH-560, KH-570, KH-792 and KH-900.

[0047] The added amount of the silane coupling agent is 10-30% of the mass of silicon dioxide.

[0048] Typically but not limiting, the amount of the silane coupling agent added may be 10%, 15%, 20%, 25% or 30% of the mass of the silica, or any value within the range of 10% to 30%.

[0049] The temperature of the silane modification is 40-80° C., and the time is 18-36 hours.

[0050] Typically but not limiting, for the silane modification process, the temperature can be set to 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, or any temperature in the range of 40°C to 80°C; the time can be set to 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours or 36 hours, or any time in the range of 18 hours to 36 hours.

[0051] Furthermore, the organic solvent is removed by heating.

[0052] In the silicon dioxide, the proportion of coarse-grained particles is 15-25wt%; the proportion of medium-grained particles is 15-25wt%; and the proportion of fine-grained particles is 50-70wt%.

[0053] The coarse particle size is greater than 4 μm, the medium particle size is 2-4 μm, and the fine particle size is less than 2 μm.

[0054] Typically but not limiting, the proportion of coarse-grained particles in the silica can be 15wt%, 18wt%, 20wt%, 22wt% or 25wt%, or any value in the range of 15wt% to 25wt%; the proportion of medium-sized particles can also be 15wt%, 18wt%, 20wt%, 22wt% or 25wt%, or any value in the range of 15wt% to 25wt%; the proportion of fine-sized particles can be, for example, 50wt%, 55wt%, 60wt%, 65wt% or 70wt%, or any value in the range of 50 to 70wt%.

[0055] The combination of coarse, medium and fine particles can increase the fluidity and dispersibility of organic-inorganic hybrid monomers. Coarse particles can serve as a "skeleton" to provide structural support, while medium and fine particles can fill the gaps and reduce agglomeration, thereby improving the uniformity and dispersibility of organic-inorganic hybrid monomers. The mixing of particles of different sizes can improve the thixotropy of the material, that is, forming a stable structure when stationary, while maintaining good fluidity under shear force, which helps prevent the sedimentation and agglomeration of particles. This gradation can maximize the use of space and improve filling efficiency, while reducing porosity and enhancing the mechanical properties of the material after curing.

[0056] The second aspect of the present invention provides a photocurable resin composition, comprising a trifunctional (meth)acrylate monomer, a triallylcyanurate monomer, a (meth)acrylate diluent monomer, an organic-inorganic hybrid monomer, and a photoinitiator; Wherein, the organic-inorganic hybrid monomer is the organic-inorganic hybrid monomer described in the first aspect.

[0057] In the photocurable resin composition provided by the present invention, the introduction of trifunctional (meth) acrylate and cyanuric acid tryptophan significantly improves the crosslinking density of the resin, thereby enhancing the mechanical properties and thermal stability of the cured material. At the same time, the addition of organic-inorganic hybrid monomers effectively fills the gaps generated during the curing process and reduces the overall shrinkage of the material. In addition, the (meth) acrylate dilution monomer can not only reduce the viscosity of the composition, but also participate in the photocuring crosslinking reaction, further improving the crosslinking density of the material. There is good compatibility between the (meth) acrylate dilution monomer and the organic-inorganic hybrid monomer, so that the organic-inorganic hybrid monomer can be evenly dispersed in the resin composition. The resin composition not only has low viscosity and high temperature resistance, but also shows lower shrinkage after curing, which improves the precision of the cured material.

[0058] Furthermore, the trifunctional (meth)acrylate monomer includes at least one of tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, (3) propoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate.

[0059] The structural formula of the triallyl cyanurate monomer is shown in Formula I below: Formula Ⅰ.

[0060] Among them, R 1 , R 2 , R 3 is selected from hydrogen, methyl, ethyl or n-propyl.

[0061] The structural formula of tris(2-hydroxyethyl)isocyanurate triacrylate is shown in Formula II below: Formula II.

[0062] The structural formula of trimethylolpropane triacrylate is shown in the following formula III: Formula III.

[0063] Trimethylolpropane trimethacrylate is shown in the following formula IV: Formula IV.

[0064] (3) Propoxylated trimethylolpropane triacrylate is represented by the following formula V: Formula V.

[0065] Pentaerythritol triacrylate is shown in the following formula VI: Formula VI.

[0066] Furthermore, the Tg value of the (meth)acrylate diluent monomer is greater than 100°C.

[0067] The (meth)acrylate diluent monomer includes a monofunctional (meth)acrylate monomer and / or a difunctional (meth)acrylate monomer.

[0068] Furthermore, the (meth)acrylate diluent monomer includes at least one of isobornyl acrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclohexane dimethanol diacrylate and tricyclohexane dimethanol dimethacrylate.

[0069] The photoinitiator includes at least one of ethyl 2,4,6-trimethylbenzoylphosphonate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether and methyl o-benzoylbenzoate.

[0070] Furthermore, the photocurable resin composition comprises, by weight, 15 to 20 parts of trifunctional (meth)acrylate monomer, 10 to 15 parts of triallyl cyanurate monomer, 8 to 10 parts of (meth)acrylate diluent monomer, 55 to 65 parts of organic-inorganic hybrid monomer and 0.5 to 2 parts of photoinitiator.

[0071] In the above-mentioned photocurable resin composition, the optimization of high temperature resistance and the effective reduction of material shrinkage are achieved by the coordinated use of low weight parts of trifunctional (meth) acrylate monomers and low viscosity organic-inorganic hybrid monomers. Although trifunctional (meth) acrylate monomers can improve the heat resistance of materials, the increase in their dosage will lead to increased material shrinkage, thereby affecting the dimensional accuracy of the model. In this case, the introduction of silica powder not only enhances the high temperature resistance of the material, but also helps to alleviate the shrinkage problem, thereby ensuring the stability of the material in high temperature applications and the accuracy of the model.

[0072] As a trifunctional monomer, cyanuric acid triene ester monomer plays an important role in the preparation of the composition. It can not only act as a curing crosslinking agent to increase the crosslinking density of the composition, but also because its molecular structure contains a six-membered heterocyclic ring, which further enhances the heat resistance of the composition. Therefore, the application of cyanuric acid triene ester monomer can effectively improve the heat resistance of the polymer and maintain stable performance in a high temperature environment.

[0073] Typically but not limiting, in the photocurable resin composition, the trifunctional (meth)acrylate monomer can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, or any value between 15 parts and 20 parts; the cyanuric acid trialenyl ester monomer can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, or any value between 10 parts and 15 parts; the (meth)acrylate diluent monomer can be 8 parts, 9 parts or 10 parts, or any value between 8 parts and 10 parts. any value; the organic-inorganic hybrid monomer can be 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts or 65 parts, or any value between 55 parts and 65 parts; the photoinitiator can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts or 2 parts, or any value between 0.5 parts and 2 parts.

[0074] The third aspect of the present invention provides the use of the photocurable resin composition in 3D printing.

[0075] The application provided by the present invention, in view of the advantages of the above-mentioned photocurable resin composition, improves the accuracy, stability, toughness and thermomechanical properties of the printed parts obtained by 3D printing, while reducing the curing shrinkage rate and improving the printing efficiency, thereby meeting the needs of a wider range of industrial and engineering applications.

[0076] In the following, some embodiments of the present invention are described in detail in conjunction with the embodiments. In the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. The raw materials used in the present invention can be obtained by commercial purchase unless otherwise specified.

[0077] Example 1 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. First weigh 2g of dispersant ANTI-TERRA-210 (BYK) and add it to 100g of acetone solvent. After stirring evenly, weigh 20g of silica powder with an average particle size of 5μm, 20g of silica powder with an average particle size of 3μm, and 60g of silica powder with an average particle size of 1μm in order, stir and disperse them in acetone solvent, then place them in an ultrasonic cell crusher for homogenization for 2h, set the homogenized liquid temperature to 40℃, and obtain an acetone dispersion with a silica content of 50%.

[0078] 2. Add 20 g of silane coupling agent KH-550 to the silica acetone dispersion obtained in step 1, stir evenly and seal, then place in an ultrasonic disperser at 50°C and continue to react for 24 hours to obtain a silane-modified silica dispersion.

[0079] 3. Add 100 g of DMAA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent under vacuum at 40° C. to obtain an organic-inorganic hybrid monomer with a viscosity of 1000 mPa·s.

[0080] The photo of the organic-inorganic hybrid monomer is shown in Figure 1 Its infrared spectrum is shown as Figure 2 shown.

[0081] Example 2 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0082] 2. Same as the step in Example 1.

[0083] 3. Add 100 g of DCPDA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 1200 mPa·s.

[0084] Example 3 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0085] 2. Same as the step in Example 1.

[0086] 3. Add 120 g of DCPDMA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 800 mPa·s.

[0087] Example 4 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0088] 2. Same as the step in Example 1.

[0089] 3. Add 120 g of 3EOTMPTMA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 900 mPa·s.

[0090] Example 5 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0091] 2. Same as the step in Example 1.

[0092] 3. Add 80 g of TMCHA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 1200 mPa·s.

[0093] Example 6 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0094] 2. Same as the step in Example 1.

[0095] 3. Add 100 g of IBOMA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 1000 mPa·s.

[0096] Example 7 This embodiment provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0097] 2. Same as the step in Example 1.

[0098] 3. Add 120 g of TMPTMA to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 1100 mPa·s.

[0099] Comparative Example 1 This comparative example provides a silane-modified silicon dioxide dispersion, and the preparation process is as follows: 1. First weigh 2g of dispersant ANTI-TERRA-210 (BYK) and add it to 100g of acetone solvent. After stirring evenly, weigh 20g of silica powder with an average particle size of 5μm, 20g of silica powder with an average particle size of 3μm, and 60g of silica powder with an average particle size of 1μm in order, stir and disperse them in acetone solvent, then place them in an ultrasonic cell crusher for homogenization for 2h, set the homogenized liquid temperature to 40℃, and obtain an acetone dispersion with a silica content of 50%.

[0100] 2. Add 20 g of silane coupling agent KH-550 to the silica acetone dispersion obtained in step 1, stir evenly and seal, then place in an ultrasonic disperser at 50°C and continue to react for 24 hours to obtain a silane-modified silica dispersion.

[0101] Comparative Example 2 This comparative example provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0102] 2. Same as the step in Example 1.

[0103] 3. Add 100 g of methyl acrylate to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 1000 mPa·s.

[0104] Comparative Example 3 This comparative example provides an organic-inorganic hybrid monomer, and the preparation process is as follows: 1. Same as the step in Example 1.

[0105] 2. Same as the step in Example 1.

[0106] 3. Add 120 g of ethyl methacrylate (EMA) to the silane-modified silica dispersion obtained in step 2, stir evenly, and then remove the solvent at 40° C. under vacuum conditions to obtain an organic-inorganic hybrid monomer with a viscosity of 800 mPa·s.

[0107] Examples 8-14 and Comparative Examples 4-6 These embodiments and comparative examples provide a photocurable resin composition consisting of the following components: 20 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 15 parts of triallyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 55 parts of organic-inorganic hybrid monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0108] The organic-inorganic hybrid monomers in Examples 8-14 and Comparative Examples 4-6 are provided by Examples 1-7 and Comparative Examples 1-3, respectively.

[0109] Comparative Example 4 uses the silane-modified silica dispersion prepared in Comparative Example 1 to replace the above organic-inorganic hybrid monomer.

[0110] Embodiment 15 This embodiment provides a photocurable resin composition, which is composed of the following components: 10 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 10 parts of trimethylolpropane trimethacrylate, 15 parts of butyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 55 parts of organic-inorganic hybrid monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0111] The organic-inorganic hybrid monomer is provided by Example 1.

[0112] Example 16 This embodiment provides a photocurable resin composition, which is composed of the following components: 15 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 15 parts of triallyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 60 parts of organic-inorganic hybrid monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0113] The organic-inorganic hybrid monomer is provided by Example 1.

[0114] Embodiment 17 This embodiment provides a photocurable resin composition, which is composed of the following components: 20 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 10 parts of 2-methyltrienylbutyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 60 parts of organic-inorganic hybrid monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0115] The organic-inorganic hybrid monomer is provided by Example 1.

[0116] Embodiment 18 This embodiment provides a photocurable resin composition, which is composed of the following components: 20 parts of triallyl isocyanurate, 15 parts of triallyl cyanurate monomer, 8 parts of tricyclohexane dimethanol diacrylate, 55 parts of organic-inorganic hybrid monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0117] The organic-inorganic hybrid monomer is provided by Example 1.

[0118] Comparative Example 7 This comparative example provides a photocurable resin composition, which is composed of the following components: 20 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 15 parts of triallyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 55 parts of dimethyl acrylamide monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0119] Comparative Example 8 This comparative example provides a photocurable resin composition, which is composed of the following components: 10 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 10 parts of trimethylolpropane trimethacrylate, 15 parts of triallyl cyanurate monomer, 8 parts of tricyclodecane dimethanol diacrylate, 55 parts of dimethylacrylamide monomer, 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0120] Comparative Example 9 This comparative example provides a photocurable resin composition, which is composed of the following components: 45 parts of tris(2-hydroxyethyl)isocyanurate triacrylate, 8 parts of tricyclodecane dimethanol diacrylate, 45 parts of dimethyl acrylamide monomer, and 2 parts of ethyl 2,4,6-trimethylbenzoylphosphonate. The above components are fully mixed and stirred at 25°C for 60 minutes to obtain a uniform liquid, which is a photocurable resin composition.

[0121] Test Case The photocurable resin compositions obtained in Examples 8-18 and Comparative Examples 4-9 were subjected to the following tests: Resin viscosity: The testing equipment is a rheometer.

[0122] Tensile properties: The test equipment is a test tensile machine; the test standard: ASTM-D638, Type V, 1mm / min.

[0123] Heat deformation temperature at 0.45MPa: The test equipment is a heat deformation temperature tester, and the test standard is ASTM-D648.

[0124] Shrinkage test: The test equipment is a line confocal sensor.

[0125] .

[0126] The obtained data are shown in Table 1 below.

[0127] Table 1

[0128] As can be seen from Table 1, the viscosity of the resin is in a relatively low range, which can be well applied to light-curing 3D printing equipment. At the same time, the thermal deformation temperature of the material is high, and it has good high temperature resistance. The light-curing resin contains a high content of multifunctional monomers, but the addition of organic-inorganic hybrid monomers ensures low shrinkage of the material.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An organic-inorganic hybrid monomer, characterized in that: Adding a silane coupling agent to an organic solvent dispersion of silicon dioxide for silane modification to obtain a silane-modified organic solvent dispersion of silicon dioxide; Continue to add high Tg monomer to the silane-modified silica organic solvent dispersion and mix evenly, and finally remove the organic solvent to obtain an organic-inorganic hybrid monomer; Wherein, the Tg value of the high Tg monomer is greater than 100°C.

2. The organic-inorganic hybrid monomer according to claim 1, characterized in that: The high Tg monomer includes at least one of DMAA, DCPDMA, DCPDA, TMCHA, IBOMA, IBOA, TMPTMA, 3EOTMPTA and 3POTMPTA; The amount of the high Tg monomer added is 0.8 to 1.2 times the mass of silica; The organic solvent comprises at least one of ethanol, isopropanol, undecanol, dodecanol, acetone, butanone, n-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, butyl acetate, ethyl valerate, butyl valerate and ethyl acetate; In the organic solvent dispersion of silica, the mass content of silica is 30-80%.

3. The organic-inorganic hybrid monomer according to claim 1, characterized in that: The brand of the silane coupling agent includes at least one of KH-550, KH-560, KH-570, KH-792 and KH-900; The amount of the silane coupling agent added is 10-30% of the mass of silicon dioxide; The temperature of the silane modification is 40-80° C., and the time is 18-36 hours.

4. The organic-inorganic hybrid monomer according to any one of claims 1 to 3, characterized in that: Removal of organic solvents by heating; In the silicon dioxide, the proportion of coarse particles is 15-25wt%; the proportion of medium particles is 15-25wt%; the proportion of fine particles is 50-70wt%; The coarse particle size is greater than 4 μm, the medium particle size is 2-4 μm, and the fine particle size is less than 2 μm.

5. A photocurable resin composition, characterized in that: It includes trifunctional (meth)acrylate monomers, triallylcyanurate monomers, (meth)acrylate diluent monomers, organic-inorganic hybrid monomers and photoinitiators; Wherein, the organic-inorganic hybrid monomer is the organic-inorganic hybrid monomer according to any one of claims 1 to 4.

6. The photocurable resin composition according to claim 5, characterized in that: The trifunctional (meth)acrylate monomer includes at least one of tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, (3) propoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate; The structural formula of the triallyl cyanurate monomer is shown in Formula I below: Formula I Wherein, R1, R2, R3 are selected from hydrogen, methyl, ethyl or n-propyl.

7. The photocurable resin composition according to claim 5, characterized in that: The Tg value of the (meth)acrylate diluent monomer is greater than 100°C; The (meth)acrylate diluent monomer includes a monofunctional (meth)acrylate monomer and / or a difunctional (meth)acrylate monomer.

8. The photocurable resin composition according to claim 5, characterized in that: The (meth)acrylate diluent monomer comprises at least one of isobornyl acrylate, isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, tricyclohexane dimethanol diacrylate and tricyclohexane dimethanol dimethacrylate; The photoinitiator includes at least one of ethyl 2,4,6-trimethylbenzoylphosphonate, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether and methyl o-benzoylbenzoate.

9. The photocurable resin composition according to any one of claims 5 to 8, characterized in that: In terms of weight, the ingredients include 15 to 20 parts of trifunctional (meth)acrylate monomer, 10 to 15 parts of triallyl cyanurate monomer, 8 to 10 parts of (meth)acrylate diluent monomer, 55 to 65 parts of organic-inorganic hybrid monomer and 0.5 to 2 parts of photoinitiator.

10. Use of the photocurable resin composition according to any one of claims 5 to 9 in 3D printing.

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